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VOLUME 52 NUMBER 3 JULY 2008

Platinum
Metals
Review

www.platinummetalsreview.com
E-ISSN 1471–0676
 E-ISSN 1471–0676

PLATINUM METALS REVIEW

A Quarterly Survey of Research on the Platinum Metals and
of Developments in their Application in Industry
www.platinummetalsreview.com

VOL. 52 JULY 2008 NO. 3

Contents
Platinum Metals Review and Sustainability 132
An editorial by N. A. P. Carson and Barry W. Copping

A New Palladium-Based Catalyst for Methanol Steam 134

Reforming in a Miniature Fuel Cell Power Source
By Oleg Ilinich, Ye Liu, Christopher Castellano, Gerald Koermer,
Ahmad Moini and Robert Farrauto

Noble Metal Catalysts for Mercury Oxidation 144

in Utility Flue Gas
By Albert A. Presto and Evan J. Granite

“Highly Efficient OLEDs with Phosphorescent Materials” 155

A book review by R. J. Potter

Practical New Strategies for Immobilising 157

Ruthenium Alkylidene Complexes: Part II
By Ileana Dragutan and Valerian Dragutan

Novel Lipophilic Platinum(II) Compounds 163

of Salicylate Derivatives
By Wei-Ping Liu, Qing-Song Ye, Yao Yu, Xi-Zhu Chen, Shu-Qian Hou,
Li-Guang Lou, Yong-Ping Yang, Yi-Ming Wang and Qiang Su

CRC International Symposium: 172

Cross Coupling and Organometallics
A conference review by Thomas Colacot

Electrochemical Water Disinfection: A Short Review 177

By Alexander Kraft

Processing of Iridium and Iridium Alloys 186

By E. K. Ohriner

“Platinum 2008” 198

Abstracts 200
New Patents 203
Final Analysis: Accurate and Precise Determination 205
of Platinum in Solution by ICPES
By Peter Ash

Communications should be addressed to: The Editor, Barry W. Copping, Platinum Metals Review, jmpmr@matthey.com;
Johnson Matthey Public Limited Company, Orchard Road, Royston, Hertfordshire SG8 5HE, U.K.
DOI: 10.1595/147106708X325169
Platinum Metals Review
and Sustainability
A Johnson Matthey Initiative
Johnson Matthey has announced a major ini-
tiative on sustainability, with commitment to the
principles of sustainable development and a
quest for outstanding resource efficiency and
carbon neutrality. The company will also
encourage its suppliers and customers to
embrace similar values and will work with them
to exploit the opportunities presented by the
development of more sustainable products. The
initiative is being implemented against a back-
ground of increasing global concern about the
environment and the need to make the most
efficient use of natural resources, including
hydrocarbons. In addition, health issues remain
high on the sustainability agenda and we contin-
ue to see the progressive tightening of
worldwide emissions control legislation.
Platinum Metals Review (PMR) is well placed to
contribute to this initiative. Johnson Matthey
began publication of the Journal in 1957, to dis-
seminate, free of charge, knowledge of the
science and technology of the platinum group
metals (pgms) to a worldwide readership, to
Coverage of Sustainability in P l a t i n u m
Metals Review
One of PMR’s earliest published papers, in
1957, was a conference review dealing with the
importance of pgms for catalysing industrial
reactions (1). Since then, many ‘classic’ articles
have become landmark papers in their fields,
including autocatalysts for reducing harmful
vehicle emissions (2, 3), fuel cells as an alterna-
tive energy technology (4) and the use of
catalysis for improving the efficiency of industri-
al processes (5).
Further themes have included hydrogen as an
alternative fuel (6), solar energy (7), the recovery
of pgms from spent catalysts (8) and the use of
Platinum Metals Rev., 2008, 52, (3), 132–133
support the platinum industry and to encourage
research and development. PMR has followed
the growth of pgm technologies as they have
moved from laboratory to industrial scale,
and has always covered advances in sustainable
technology.
The carbon footprint of PMR’s publishing
operation was significantly reduced in July 2004,
when the electronic-only format superseded
printed copy distribution.
I am delighted that the PMR editorial team
will be actively taking Johnson Matthey’s sus-
tainability initiative forward in commissioning
articles, as well as conference and book reviews.
It is clear that PMR’s contributors and readers
have a fundamental interest in achieving a more
sustainable world, and this will have increasing-
ly important implications for the future
development of pgm science. N. A. P. CARSON
Neil Carson became the Chief Executive of Johnson Matthey
PLC in July 2004. He joined Johnson Matthey in 1980,
becoming Managing Director, Catalysts & Chemicals in 1999. In
2002 he assumed board level responsibility for the Precious
Metals Division. He is Chairman of the U.K. Government
Business Taskforce on Sustainable Consumption and
Production.
pgms in environmental remediation (9). Recent
coverage takes many of these themes forward.
Further improvements to industrial process
catalysis (10, 11), chemical reactions (12) and
‘green’ chemistry (13) have all featured in the last
two years. There is continuing interest in alter-
native fuels (14), and autocatalysts contribute
crucially in the drive to reduce vehicle emissions
(15).
In the current issue of PMR, we present arti-
cles on fuel cells (16), chemical catalysis (17) and
emissions abatement for industrial processes
(18). This proves that research and development
on the use of pgms for sustainable technologies
are alive and well in the 21st century.
132
 With the Journal hosted on the dedicated
website www.platinummetalsreview.com, fea-
tures have been added in the PGM Science
Mine to actively engage the pgm science and
technology community in addressing key issues
such as sustainability. Within the PGM Science
Mine, a range of organisations involved in sus-
tainability issues are now listed in the PMR
Organisation Directory, including:
– Environment, Sustainability & Energy, Royal
Society of Chemistry, U.K.
– Good Practice, Sustainable Development in
the Mining and Metals Sector
References
1 ‘The Platinum Metals in Catalysis’, Platinum Metals
Rev., 1957, 1, (1), 24
2 ‘Automobile Emission Control Systems’, G. J. K.
Acres and B. J. Cooper, Platinum Metals Rev., 1972,
16, (3), 74
3 ‘Twenty-Five Years of Autocatalysts’, M. V.
Twigg, Platinum Metals Rev., 1999, 43, (4), 168
4 ‘Fuel Cell Energy Generators’, D. S. Cameron,
Platinum Metals Rev., 1978, 22, (2), 38
5 ‘The CativaTM Process for the Manufacture of
Acetic Acid’, J. H. Jones, Platinum Metals Rev.,
2000, 44, (3), 94
6 ‘Progress in Hydrogen Energy Systems’, P. A.
Sermon, Platinum Metals Rev., 1978, 22, (4), 130
7 ‘Highly Efficient Nanocrystalline Photovoltaic
Devices’, M. Grätzel, Platinum Metals Rev., 1994,
38, (4), 151
8 ‘Precious Metal Recovery from Spent Catalysts’,
P. Grumett, Platinum Metals Rev., 2003, 47, (4), 163
9 ‘The Dechlorination of Hydrocarbons’, N. Korte,
L. Liang, R. Muftikian, C. Grittini and Q.
Fernando, Platinum Metals Rev., 1997, 41, (1), 2
10 ‘Enhancement of Industrial Hydroformylation
Processes by the Adoption of Rhodium-Based
Catalyst: Part I’, R. Tudor and M. Ashley, Platinum
Metals Rev., 2007, 51, (3), 116
Platinum Metals Rev., 2008, 52, (3)
– Roundtable on Sustainable Platinum Group
Metals
– SusChem, Belgium
– Sustainable Development Commission (SDC),
U.K.
– U.K. Government Sustainable Development
We hope that our readers and authors will
continue to make use of the PMR journal and its
website as valuable resources to further their
work on sustainable pgm science and technol-
ogy into the future.
BARRY W. COPPING, Editor
11 ‘Enhancement of Industrial Hydroformylation
Processes by the Adoption of Rhodium-Based
Catalyst: Part II’, R. Tudor and M. Ashley,
Platinum Metals Rev., 2007, 51, (4), 164
12 ‘Practical New Strategies for Immobilising
Ruthenium Alkylidene Complexes: Part I’, I.
Dragutan and V. Dragutan, Platinum Metals Rev.,
2008, 52, (2), 71
13 ‘Green Chemistry and Catalysis’, D. Macquarrie,
Platinum Metals Rev., 2008, 52, (2), 83
14 ‘Alcoholic Fuels’, G. Acres, Platinum Metals Rev.,
2007, 51, (1), 34
15 ‘Diesel Engine Emissions and Their Control’,
T. Johnson, Platinum Metals Rev., 2008, 52, (1), 23
16 ‘A New Palladium-Based Catalyst for Methanol
Steam Reforming in a Miniature Fuel Cell Power
Source’, O. Ilinich, Y. Liu, C. Castellano,
G. Koermer, A. Moini and R. Farrauto, Platinum
Metals Rev., 2008, 52, (3), 134
17 ‘Practical New Strategies for Immobilising
Ruthenium Alkylidene Complexes: Part II’,
I. Dragutan and V. Dragutan, Platinum Metals Rev.,
2008, 52, (3), 157
18 ‘Noble Metal Catalysts for Mercury Oxidation in
Utility Flue Gas’, A. A. Presto and E. J. Granite,
Platinum Metals Rev., 2008, 52, (3), 144
133
DOI: 10.1595/147106708X324403

A New Palladium-Based Catalyst for

Methanol Steam Reforming in a
Miniature Fuel Cell Power Source
By Oleg Ilinich*, Ye Liu, Christopher Castellano, Gerald Koermer, Ahmad Moini and Robert Farrauto
BASF Catalysts LLC, 25 Middlesex-Essex Turnpike, Iselin, NJ 08830-0770, U.S.A.; *E-mail: oleg.ilinich@basf.com

A novel palladium-based catalyst has been developed for use in a miniature fuel cell power
source for portable applications, incorporating a polymer electrolyte membrane (PEM) fuel
cell. Hydrogen, which is the fuel for the cell, is produced in a ceramic microreactor via the
catalytic reaction of methanol steam reforming: CH3OH + H2O → 3H2 + CO2. The need for
a new catalyst in this application is driven by the limitations of traditional particulate catalysts
based on copper oxide, zinc oxide and alumina (Cu-Zn-Al catalysts), which have low thermal
stability and high sensitivity towards air and condensing steam. These features result in a
declining activity and mechanical integrity of Cu-Zn-Al catalysts under the frequent start-stop
conditions typical of the operational mode of the miniature power source. The new Pd-
based catalyst has activity and selectivity similar to those of Cu-Zn-Al catalysts, but is more
durable and stable under the duty cycle conditions of a portable power source. In the
microreformer, the catalyst is washcoated directly on the walls of the steam reforming section,
providing favourable conditions for efficient heat transfer between the heat-generating catalytic
combustion section of the microreformer and its heat-consuming steam reforming section.

1. Introduction it practically attractive for this application.

Current trends in energy demand for portable
electronics show that the power consumption in
devices such as cell phones, personal digital assis-
tants (PDAs), notebook computers and digital
cameras continues to rise. Consumers demand
small size, light weight, but long battery life. The
batteries most commonly used in these devices are
of the rechargeable (secondary) type. However, in
certain applications such as those used by
exploratory expeditions, first responders and the
military, recharging a battery in the field is often dif-
ficult, if possible at all. Therefore a heavy load of
disposable (primary) batteries must be transported
to remote locations. One solution to this problem
is to use a small portable battery charger powered
by a fuel cell.
Due to the low energy density of compressed
hydrogen, using it as a fuel for a portable fuel cell
charger is not a viable option. Liquid fuel, in partic-
ular methanol, has a much higher energy density
and is easier to transport and handle, which makes
Methanol is used as a fuel in two different types
of fuel cells. In the direct methanol fuel cell
(DMFC) (Figure 1), methanol is fed directly to the
anode where it reacts with water, generating elec-
trons which travel through the external circuit as
electric current, Reaction (i):
CH3OH + H2O → CO2 + 6H+ + 6e– (i)
Protons travel through the proton-conducting
polymer electrolyte membrane (for example,
Nafion®) to the cathode where they react with oxy-
gen from the atmosphere, to produce water.
The subject catalyst of this article was developed
for use in a reformed methanol fuel cell, shown in
Figure 2. In essence this is a classic type of fuel cell,
invented in 1839 by William Grove. Here the fuel is
hydrogen which is fed to the anode, where it splits
electrocatalytically into protons and electrons,
Reaction (ii):
H2 → 2H+ + 2e– (ii)

Platinum Metals Rev., 2008, 52, (3), 134–143 134

 Fig. 1 Schematic
CH3OH of a direct
Anode reaction: methanol fuel cell
2CH3OH + 2H2O → 2CO2 + 12H+ + 12e–

NAFION®
H+ membrane Overall reaction:
70ºC 2CH3OH + 3O2 → 2CO2 + 4H2O

e– Cathode reaction:
12H+ + 12e– + 3O2 → 6H2O

Air
–
e

Fig. 2 Schematic of a
Hydrogen production via methanol steam reforming: reformed methanol fuel cell
CH3OH + H2O → 3H2 + CO2

Anode reaction:
2H2 → 4H+ + 4e–

PBI/H3PO4
Overall reaction:
H+ (Polybenzimidazole)
2H2 + O2 → 2H2O
180ºC

e–
Cathode reaction:
+ –
4H + O2 + 4e → 2H2O

e–
Air

In contrast to Grove’s cell, however, in our appli-
cation the hydrogen is produced by the catalytic
steam reforming of methanol, Reaction (iii):
CH3OH + H2O → 3H2 + CO2 (iii)
This reaction has received much attention in the
last decades as an attractive route to hydrogen sup-
ply. An excellent review on methanol steam
reforming (MSR) for hydrogen production has
recently been published by Palo et al. (1).

Platinum Metals Rev., 2008, 52, (3) 135

 The MSR reaction can be efficiently catalysed of the miniature power source. The catalyst con-
by copper-based catalysts (2–7), including the Cu- sists of Pd and Zn on an oxide support with
Zn-Al particulates otherwise used in methanol proprietary additives. In the present paper this cat-
synthesis (8) and the water-gas shift reaction (9). alyst is designated as ‘Pd-Zn/oxide support’. It is
These catalysts are commercially produced, and fabricated in a powder form, then slurried and used
have been used successfully in industry for many as a washcoat on the channels of the micro-
years. By their nature they are quite sensitive to the reformer (Figure 3) to be incorporated into a
process conditions. In particular, they are prone to miniature fuel cell power source.
sintering at temperatures above about 280 to The catalytic performance of a MSR catalyst is
300ºC, which results in a significant decline in determined by two characteristics: activity and
activity, and also deteriorate both mechanically and selectivity. A good MSR catalyst should provide
in performance if steam condenses on them. high rates of conversion of methanol and water
Besides, a Cu-Zn-Al catalyst can develop danger- into hydrogen and carbon dioxide, while side reac-
ously strong exotherms if in its oxidised state it is tions should be minimised. In the MSR process, in
exposed to a reducing environment, or, in its addition to the target steam reforming Reaction
reduced (active) state, to an oxidising environment, (iii), several undesired side reactions can occur. In
such as ambient air (10). Therefore in industrial particular, carbon monoxide can be formed via
settings Cu-Zn-Al catalysts are operated under methanol decomposition, Reaction (iv):
carefully controlled conditions. The operating CH3OH → CO + 2H2 (iv)
cycle includes a lengthy start-up with slow reduc-
and/or reverse water-gas shift, Reaction (v):
tion in syngas (H2/CO) or hydrogen heavily
diluted with nitrogen to minimise the reduction CO2 + H2 → CO + H2O (v)
exotherm. The reduced and activated catalysts nor-
mally operate under steady-state conditions. (a)
By contrast, the duty cycle anticipated for the
MSR catalyst in the miniature fuel cell power
source is much more demanding. The miniature
power source will be operated with frequent
starts and stops, during which liquid (reformate)
will condense and may even freeze on the cata-
lyst. Besides, slow reduction in dry gas with low
concentrations of a reductant will clearly be
unavailable, and the catalyst will have to be acti-
vated (reduced) upon direct contact with the (b)
methanol/water feed mixture. The properties of
Cu-Zn-Al catalysts are incompatible with these
requirements, and therefore a new application-
specific catalyst had to be developed. This catalyst
is a further improvement over the family of
palladium-zinc-based catalysts which have been
developed for fuel cell applications in recent
years (11–16). Pd-Zn/oxide support

2. Experimental Fig. 3 (a) The prototype microreformer (with U.S.

The novel MSR catalyst has been developed quarter dollar coin for scale); (b) cross section of the
microreformer with Pd-Zn/oxide support washcoated in
using a combination of rapid catalytic screening and the microchannels (Reproduced with permission from
detailed parametric studies simulating the duty cycle Motorola Energy Technologies Lab)

Platinum Metals Rev., 2008, 52, (3) 136

 Carbon monoxide, a known catalytic poison,
can only be tolerated by the fuel cell catalysts if its
concentration in the reformate is low. Even for the
fuel cells based on polybenzimidazole (PBI) mem-
branes, which operate at elevated temperatures
(~ 180ºC) and are more CO-tolerant than the fuel
cells with Nafion® membranes which operate at
~ 80ºC, the CO level in the reformate must not
exceed 1–2%.
Another possible side product is methane,
which could be generated via methanation,
Reactions (vi) and (vii), that consumes considerable
amounts of hydrogen, while generating large
amounts of heat:
CO2 + 4H2 → CH4 + 2H2O
CO + 3H2 → CH4 + H2O
In the context of this article, the selectivity is
understood as the ratio of the concentration of a
given product at certain conversion of methanol to
the sum of concentrations of all carbon-containing
gas-phase products (in our catalytic tests no coke
formation was observed), for example Equation
(viii):
SCO2 =
100 × [CO2]/([CO2] + [CO] + [CH4]) (viii)
where SCO2 (%) is the selectivity towards CO2, and
[CO2], [CO] and [CH4] are the concentrations of
the corresponding species.
3. Results
3.1 Performance Testing of the Cu-Zn-Al
and ‘Pd-Zn/Oxide Support’ Catalysts in
the Simulated Start-Stop Mode
The anticipated duty cycle of the miniature
power source will include frequent starts and stops,
with variable periods of steady-state operation. The
catalysts to be used in the microreformer must be
thoroughly tested under conditions simulating such
operation, and a special laboratory test procedure
has been developed for this purpose. The test con-
(vi)
sisted of the following elements as illustrated in
(vii) Figure 4: (a) initial heat-up of the reactor to the
reaction temperature, followed by starting the flow
of the methanol/water feed mixture and (b) steady-
state operation for approximately sixty hours; (c)
multiple start-stop cycles consisting of (d) cooling
down to 40ºC with the feed flow stopped (simulat-
ed shutdown of the power source); (e) heating up
to the reaction temperature; (f) restarting the flow
of the methanol/water feed mixture with steady-
state operation for approximately two hours.

300
300
(c) Start-stop cycles

250
250
Reactor temperature, ºC

200
200
(a)
Initial (b) Steady-state
heat-up
Temp

150
150

100
100

(d) Stop feed flow

50
50 and cool down

(e) Ramp up to operating temperature (f) Restart CH3OH + H2O feed

0
0
02/07/05 02/07/05 1
02/08/05 02/08/05 2
02/09/05 02/09/05 3
02/10/05 02/10/05 4
02/11/05 02/11/05 5
02/12/05
Time,
Time days

Fig. 4 Experimental temperature profile in methanol steam reforming reactor during the catalyst performance test

Platinum Metals Rev., 2008, 52, (3) 137

 In the catalytic performance test using the
above protocol, the commercial Cu-Zn-Al catalyst,
initially run under steady-state conditions, showed
stable activity for a period of about two weeks.
However, soon after the onset of the start-stop
temperature cycling the activity began decreasing,
which continued for another two weeks of opera-
tion, showing no signs of stabilisation. However
the CO2 selectivity remained very high (in excess
of 99%) throughout the test.
For the catalyst ‘Pd-Zn/oxide support’, tested
using the same protocol, the activity under the
steady-state conditions was also stable and close to
that of Cu-Zn-Al catalyst. At the beginning of the
temperature cycling, a slight drop in the methanol
conversion was registered but the activity remained
stable thereafter. The CO2 selectivity was also sta-
ble throughout the test at 98 ± 0.6%.
The temperature dependence of the initial CO2
selectivity (i.e. SCO2 at low conversions of
methanol) was further investigated in the range
230 to 320ºC, and was found to decrease with the
temperature from 98.2 to 94.2% (Figure 5). It was
also observed that for the given reaction condi-
tions CO2 selectivity is fairly constant over a
broad range of methanol conversions; however
it decreases at high conversions (above
~ 95 to 97%).
3.2 Mechanical Strength of the Cu-Zn-Al
and ‘Pd-Zn/Oxide Support’ Catalysts
It is known that exposure to a liquid can cause
mechanical deterioration of particulate Cu-Zn-Al
catalysts (9). This practically important aspect has
not been sufficiently addressed in the open litera-
ture. Therefore in addition to catalytic per-
formance we also analysed the Cu-Zn-Al catalyst
for its mechanical strength before and after sixty
temperature cycles, and found that the catalyst pel-
lets lose about 80% of their initial strength as a
result of the temperature cycling. The number of
starts and stops of the future miniature power
sources will certainly be much greater, and there-
fore a more significant negative impact on the
mechanical strength and finally on the integrity of
the catalyst should be anticipated. This is yet anoth-
er reason why particulate Cu-Zn-Al catalysts
cannot be used in the miniature fuel reformer,
and why a new and more robust catalyst had to
be developed.
The ‘Pd-Zn/oxide support’ catalyst was
deposited on the walls of the prototype microchan-
nel reformer, with the hydraulic diameter of a
channel measuring a few hundred microns (Figure
3). The catalyst was successfully tested in the
microreformer, producing hydrogen-rich reformate
via MSR. The same catalyst on different support

100
100
95
% (%

90
90
2 selectivity

85
2 selectivity,

80
80
75
70
COCO

70
65
60
60
55
50
50
220 230 240 250 260 270 280 290 300 310 320 330
oo
TeTemperature,
m pe ra ture (C C)
Fig. 5 Initial CO2 selectivity versus the methanol steam reforming reaction temperature for the catalyst ‘Pd-Zn/oxide
support’. Test conditions: molar ratio of feed CH3OH:H2O = 0.88; gas hourly space velocity (GHSV) = 230,000 h–1
(powder catalyst); CH3OH conversions within 11%

Platinum Metals Rev., 2008, 52, (3) 138

structures is now used commercially in other
applications.
3.3 ‘Pd-ZnO/Oxide Support’ Compared
to ‘Pd-ZnO/Al2O3’, Pd/Al2O3 and
Cu/CeO2 Catalysts
High MSR activity with high CO2 selectivity is
well documented for Pd-Zn catalysts, which were
first discovered by Iwasa et al. (17), and are now
being extensively investigated for hydrogen gener-
ation in portable fuel cell power systems. The
literature information pertaining to the MSR per-
formance of the Pd-Zn catalytic system, and
available to the authors, deals with catalysts com-
posed of Pd supported on zinc oxide and also
Pd-ZnO compositions supported on alumina
(12–17).
Driven by a continuing interest in inexpensive
non-precious metal catalysts for MSR applications,
new copper-based catalytic compositions are also
being developed (18, 19). To better understand the
strengths and possible limitations of our Pd-based
catalyst it is important to compare performance of
this catalyst with that of other Pd- and Cu-based
catalysts. To that end, following a procedure simi-
lar to those described in References (14) and (16),
we prepared two Pd-ZnO catalysts on different
supports: alumina and an oxide support material
used in preparation of the new Pd-based catalyst,
both catalysts having equivalent contents of Pd and
ZnO. These catalysts are hereinafter referred to as
‘Pd-ZnO/Al2O3’ and ‘Pd-ZnO/oxide support’,
respectively. For comparison, alumina-supported
palladium catalyst (Pd/Al2O3) with the same
amount of palladium as in Pd-ZnO samples was
also prepared via the same procedure. In addition,
a copper/ceria catalyst with 20 wt.% CuO
(Cu/CeO2), similar to that used in (18), was pre-
pared by incipient wetness impregnation of ceria
with aqueous copper nitrate solution followed by
drying and calcining. All catalysts were compared
in terms of their activities and selectivities, now at
elevated temperatures typical for certain advanced
applications. The samples (3 g of each) were tested
in a laboratory flow reactor as granules 250 to 710
μm in size. This particle size ensures test condi-
tions free of pore diffusion. The feed mixture
Platinum Metals Rev., 2008, 52, (3)
consisted of a reagent grade methanol (Aldrich)
and deionised water in volume ratio MeOH:H2O =
1:1 (molar ratio 0.88:1). The feed flow rates (from
0.3 cm3 min–1 to 2.0 cm3 min–1) and the catalyst
temperatures (375ºC to 475ºC) were programmed
and controlled throughout the test as shown in
Figures 6 to 9. The automated gas chromatograph-
ic analysis was conducted at twenty minute
intervals by sampling the gas mixtures exiting the
reactor. Performance of all of the catalysts
described above is analysed below.
Methanol conversion and CO2 selectivity for
the catalyst ‘Pd-ZnO/oxide support’ are plotted in
Figure 6 for temperatures 375ºC, 425ºC and 475ºC
and a range of flow rates. It can be seen that the
catalyst has stable activity (100% methanol conver-
sion in the first and the last segments of the run,
these segments having identical experimental con-
ditions) with CO2 selectivity ranging from around
70% at full conversion of methanol to around 82%
at lower conversions.
Under the same experimental conditions the
sample ‘Pd-ZnO/Al2O3’ is less active, and has
much lower CO2 selectivity (Figure 7). This catalyst
ages, partially losing activity in the course of the
run. This is illustrated by lower methanol conver-
sion in the last segment of the run as compared
with the first. The main product with this sample is
CO; under the experimental conditions of the test,
methane is also produced with selectivity ranging
from 1 to 6%. This implies significantly less effi-
cient production of hydrogen with
‘Pd-ZnO/Al2O3’, and also different reaction path-
ways for the two similar catalysts – ‘Pd-ZnO/oxide
support’ and ‘Pd-ZnO/Al2O3’.
The Pd/Al2O3 sample is even less active than
‘Pd-ZnO/Al2O3’, is more prone to ageing and has
very poor CO2 selectivity (Figure 8). CO and
methane are the dominant carbon-containing
products with the Pd/Al2O3 catalyst under the
experimental conditions employed, rendering this
catalyst composition unsuitable for hydrogen
generation.
The Pd-free sample with Cu impregnated on
ceria has high initial activity and relatively high CO2
selectivity (up to about 75%); however it ages
rapidly with a significant loss in activity (Figure 9).
139
 CH 3OH
MeOH conversion
con versio n
100
100
selectivities (%) %
CO selectivities,

90
90
–1 1.2
1.2ml min–1,
0.30 .3mlml/m
min –1 0.8 ml min , 2.0 ml min–1, m l/min,
0.3 ml min–1,
in, ,
0 .8 ml/m in,
2.0 m l/min,
425ºC 425ºC
42 5C 0 .3 m l/m in,
375ºC 47 5C475ºC 375ºC
4 25 C
3 75 C 3 75 C
80
80
2.0 ml min–1,
2.0 m l/min,
2.0 ml min–1,
2.0 ml/min,
425ºC
42 5C 42 5C
425ºC
70
70
CO

CO selectivity
C O22 se lectivity
CO2 and 2 and

60
60
MeOH conversion/CO

50
50
CH3OH conversion,

40
40
CO
CO selectivity
se lectivi ty

30
30

20
20

10
10

0
0
2 /8 /08 5 :45 PM 4
2/8/08 10:33
4 PM 8
2/9/08 83:21 AM 2/9/08 12
8:09 AM
12 16
2/9/0 8 12:57
16 PM 20
2/9 /0 820
5 :4 5 PM

Time
Tim eon stream,
on stream (hourhours
s)

Fig. 6 Methanol steam reforming performance test of the catalyst ‘Pd-ZnO/oxide support’

110 77
CH 3OHconversion
MeOH conversion
100
100
CH3OH conversion, CO2 and CO selectivities, %

66
MeOH conversion/CO2 and CO selectivities (%)

90
90
0 .3 ml/m in,–1
0.3 ml min , 0.8 ml min , –1
0.8 m l/min, 2.0 ml/min, –1
2.0 ml min ,
375ºC
3 75 C 425ºC
42 5C 475ºC
47 5C

80
80
in,–1, 55
1.2 ml min–1,
1 .2 ml/min, 0.3
0 .3ml min
ml/m
3 75 C
425ºC
4 25 C 375ºC
70
70
2.0
2.0 ml min
m l/m
–1
in, ,
CH4 selectivity, %
CH4 selectivity (%)

CO selectivity
CO selectivity 425ºC
42 5C 44
60
60
0.6
0 .6 mml in, –1,
l/mmin
375ºC
3 75 C

50
50
CH44 selectivity
CH selectivity 33
40 40

30
30 22
CO
CO2 2selectivity
selectivity

20
20

11
10
10

039519.62
0 00
39519.72
44 39519. 82
8 8
39519.92 39520.02
1239520.12
12 39520. 22
16
16 39520.32
20
20
39520.42

TimeTime
ononstream, hours
str eam (hour s)

Fig. 7 Methanol steam reforming performance test of ‘Pd-ZnO/Al2O3’ catalyst

The ageing in this case is probably due to the ther- methane, but methanation stops as the catalyst ages.
mal sintering of Cu (20). The fresh catalyst at high The results of our comparative study show that
temperatures also produces small amounts of the catalyst ‘Pd-Zn/oxide support’ has an

Platinum Metals Rev., 2008, 52, (3) 140

 110

CH3OH conversion
MeOH conversion
CH3OH conversion, CO2, CO and CH4 selectivities, %
100
100

90
90
MeOH conversion/Selectivities (%)

80
80
CO
COselectivity
selectivity

70
70

60
60
in, –1,
0.30.3ml min–1,
m l/min, 0.80.8ml min
m l/m
–1
in, , 2.02.0ml min
m l/m
–1
in, , 1.21.2ml min–1,
m l/min, 2.0 2ml min–1,
.0 ml/min, 0.4
0.4 ml
m l/mmin
37 375ºC
5C 425425ºC
C 475475ºC
C 42425ºC
5C 4425ºC
25 C 375ºC
37 5C

50
50 0 2 l/m in N2

40
40

30
30

CH
CH44 selectivity
selectivity
20
20

10
10
CO2 selectivity
CO2 selectivity

00
39498. 7 39498. 8 4 4 39498. 9 39499 88 39499. 1 1239499. 2
12 39499. 3 16
16 39499. 4

Time on stream (hours)

Time on stream, hours

Fig. 8 Methanol steam reforming performance test of Pd/Al2O3 catalyst

110 1.1
1.1
CH3OHconversion
MeOH conversion
100
100 1.0
1.0
%
selectivities (%)

90
90 0.9
0.9
COselectivities,

0.3 0.3 min–1,

mlml/min, 2.02.0 min–1,
mlml/min, 1.2 ml min–1,
1.2 ml/min, 2.0 ml min–1,
2.0 ml/min, 2.0
2.0 ml min–1,
ml/min, 0.3
0.3 ml min–1,
ml/min,
0.8 ml min–1,
0.8 ml/min,
375ºC 475ºC 425C425ºC 425C425ºC 425C425ºC 375ºC
375C
375C 425ºC
425C 475C
80
80 0.8
0.8

70 0.7
CH4 selectivity, %
70 0.7

CH4 selectivity (%)

CO

selectivity
CO22 selectivity
2 and

60
60 0.6
0.6
CO2 and
MeOH conversion/CO

50
50 0.5
0.5
CH3OH conversion,

40
40 0.4
0.4

CO selectivity
selectivity
30
30 0.3
0.3

20
20 0.2
0.2

CH44 selectivity
selectivity
10
10 0.1
0.1

00 00.0
39490.58 66
39490.83 12 12
39491.08 18
18
39491.33 24
24
39491.58

Time
Timeon
on stream, hours
stream (hours)

Fig. 9 Methanol steam reforming performance test of Cu/CeO2 catalyst

optimum composition for the MSR reaction. It process conditions. The catalyst ‘Pd-Zn/oxide sup-
possesses high and stable activity, as well as the port’ is hence the most efficient among the cat-
highest CO2 selectivity over a broad range of MSR alysts tested in this study for hydrogen generation.

Platinum Metals Rev., 2008, 52, (3) 141

4. Conclusions
A new active Pd-based MSR catalyst has been
developed for use as a washcoat in a microchannel
reformer integrated to a miniature fuel cell power
source. The catalyst ‘Pd-Zn/oxide support’ with
proprietary additives shows stable performance
under the frequent start-stop operating conditions
typical of a portable fuel cell power source. The
new catalyst is also thermally stable, which enables
its extended operation over a broad range of tem-
peratures and simplifies fabrication of the
miniature power source.
References
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The Authors
Dr Oleg Ilinich is a Senior Chemist at
BASF Catalysts LLC in Iselin, New
Jersey, U.S.A. He received his M.S. in
Chemical Engineering from the St.
Petersburg Institute of Technology in
Russia, which was later followed by
Ph.D. and D.Sci. degrees in Catalysis
from the Boreskov Institute of Catalysis
(Novosibirsk, Russia). His recent work
includes catalyst development as well as
kinetic and mechanistic studies for the
water-gas shift reaction, methanol steam
reforming and direct methanol fuel cells.
Prior to joining BASF Catalysts, Dr Ilinich
was involved in fundamental and applied
research in selective heterogeneous
catalysis, and catalytic and gas
separation membranes.
Platinum Metals Rev., 2008, 52, (3)
Acknowledgements
This article contains information produced in
partnership with the Motorola Energy Tech-
nologies Lab within the National Institute of
Standards and Technology (NIST) Advanced
Technology Program: “Hydrogen Generator for
a Miniature Fuel-Cell Power Source”. Part of this
information was presented at the 31st Annual
Conference of the International Precious Metals
Institute (IPMI) (21). The authors gratefully
acknowledge the kind permission of the IPMI to
publish this article.
12 P. Pfeifer, A. Kölbl and K. Schubert, Catal. Today,
2005, 110, (1–2), 76
13 C. Fukuhara, Y. Kamata and A. Igarashi, Appl. Catal.
A: Gen., 2007, 330, 108
14 C. Cao, G. Xia, J. Holladay, E. Jones and Y. Wang,
Appl. Catal. A: Gen., 2004, 262, (1), 19
15 N. Iwasa and N. Takezawa, Top. Catal., 2003, 22,
(3–4), 215
16 A. Karim, T. Conant and A. Datye, J. Catal., 2006,
243, (2), 420
17 N. Iwasa, S. Kudo, H. Takahashi, S. Masuda and
N. Takezawa, Catal. Lett., 1993, 19, (2–3), 211
18 Y. Men, H. Gnaser, R. Zapf, V. Hessel, C. Ziegler
and G. Kolb, Appl. Catal. A: Gen., 2004, 277,
(1–2), 83
19 P. Clancy, J. P. Breen and J. R. H. Ross, Catal. Today,
2007, 127, (1–4), 291
20 M. V. Twigg and M. S. Spencer, Top. Catal., 2003, 22,
(3–4), 191
21 IPMI, 31st Annual Conference of Precious Metals,
9th–12th June, 2007, Miami, Florida, U.S.A.:
http://www.ipmi.org/seminars/conf_detail.cfm?id
=17
Dr Ye Liu is a Senior Research Engineer
at BASF Catalysts LLC. He received his
B.S. and M.S. in Chemical Engineering
from the Dalian University of
Technology, China, and his Ph.D. in
Material Science and Engineering from
the Pennsylvania State University, U.S.A.
His current work involves catalyst
development for three-way catalysis,
partial oxidation, steam reforming and
the autothermal reforming of
hydrocarbons. His past research
involvement has included catalytic
gasification, combustion, sulfur removal
in flue gases, and product and process
development for carbonaceous
materials – activated carbons and
carbon blacks.
142
 Christopher Castellano is a Chemist at
BASF Catalysts LLC. He received his
B.S. in Ceramic Engineering from
Rutgers University, U.S.A.; and is
currently working on a M.S. in Material
Science and Engineering from
Columbia University, U.S.A. His current
work involves combinatorial catalyst
development for environmental
applications, as well as flexible fuel
catalysts. His previous research
involvement has included methanol
steam reforming catalysis, NH3-
selective catalytic reduction
technology, light-duty diesel catalysts,
ozone conversion and high-throughput
zeolite synthesis. He is also currently
serving as the President of the Rutgers
Engineering Society.
Dr Ahmad Moini is a Senior Research
Associate at BASF Catalysts LLC. He
obtained his Ph.D. in Chemistry from
Texas A&M University, U.S.A., followed
by a postdoctoral appointment at
Michigan State University, U.S.A. Dr
Moini started his career at Mobil
Research & Development Corporation,
where he conducted research in
microporous materials. He joined
Engelhard Corporation (now BASF) in
1996. His research focus is on the
synthesis and development of novel
catalysts and materials.
Platinum Metals Rev., 2008, 52, (3)
Dr Gerald Koermer received a Ph.D.
from the University of Wisconsin,
U.S.A. in Physical Organic Chemistry
and a B.A. in Chemistry from Rutgers
College. He has over twenty-four years
of experience in catalysis and currently
leads the Materials Science and
Enabling Technology group at BASF
Catalysts LLC’s Research and
Development.
Dr Robert J. Farrauto is a Research
Fellow at BASF Catalysts LLC. He
obtained a B.S. in Chemistry from
Manhattan College, New York City and
a Ph.D. in Electrochemistry from
Rensselaer Polytechnic Institute, Troy,
New York, U.S.A. His major
responsibilities have included the
development of advanced automobile
emission control catalysts and process
catalysts for the chemical industry. He
managed an Engelhard research team
that developed and commercialised
diesel oxidation catalysts for the
European, North American and Asian
markets for passenger cars and heavy-
duty trucks. Currently he manages a
research team developing new catalyst
technology for the hydrogen economy,
including hydrogen refueling stations
and fuel cells for stationary, portable
power and vehicular applications. He is
also Adjunct Professor in the Earth and
Environmental Engineering Department
of Columbia University, in the City of
New York, where he teaches a course
in catalysis.
143
DOI: 10.1595/147106708X319256

Noble Metal Catalysts for Mercury

Oxidation in Utility Flue Gas
GOLD, PALLADIUM AND PLATINUM FORMULATIONS

By Albert A. Presto and Evan J. Granite*

National Energy Technology Laboratory, United States Department of Energy, PO Box 10940, MS 58-106, Pittsburgh,
PA 15236-0940, U.S.A.; *E-mail: evan.granite@netl.doe.gov

The use of noble metals as catalysts for mercury oxidation in flue gas remains an area of active
study. To date, field studies have focused on gold and palladium catalysts installed at pilot
scale. In this article, we introduce bench-scale experimental results for gold, palladium and
platinum catalysts tested in realistic simulated flue gas. Our initial results reveal some intriguing
characteristics of catalytic mercury oxidation and provide insight for future research into this
potentially important process.

1. Introduction to capture. It is insoluble in water and is therefore

Coal-fired utility boilers are the largest anthro-
pogenic emitters of mercury in the United States,
accounting for approximately one third of the 150
tons of mercury emitted annually (1, 2). In 2005,
the U.S. Environmental Protection Agency (EPA)
announced the Clean Air Mercury Rule, to limit
mercury emissions from coal-fired utility boilers to
15 tons annually, approximately 30% of 1999
levels, by 2018 (3). At the time of publication (July
2008) this measure is under legal dispute. Of alter-
native legislative proposals to regulate mercury
along with other pollutants, most would require a
90% mercury reduction, with deadlines for control
varying from 2011 to 2015. Mercury exists in three
forms in coal-derived flue gas: elemental (Hg0), oxi-
dised (Hg2+) and particle-bound (Hg(p)) (4). During
combustion, mercury is liberated from coal as Hg0.
As the flue gas cools, some of the Hg0 is oxidised,
presumably to mercury(II) chloride (HgCl2)
because of the large excess of chlorine present in
coal. Both Hg0 and Hg2+ can enter the particulate
phase by adsorption onto fly ash particles (5).
Hg2+ and Hg(p) are relatively easy to remove
from flue gas using typical air pollution control
devices. Hg(p) is captured, along with fly ash parti-
cles, in the particulate control device. Hg2+ is
soluble in water, and is therefore removed with
high efficiency by wet flue gas desulfurisation
equipment (6). Hg0, on the other hand, is difficult
not removed during flue gas desulfurisation.
Activated carbon injection will remove both Hg0
and Hg2+, and currently this is the best method for
removing Hg0 from flue gas (6).
In addition to the Clean Air Mercury Rule, the
U.S. EPA also enacted the Clean Air Interstate
Rule, which requires reductions in NOx and SO2
emissions in twenty-eight states (7). An expected
consequence of this law is increased use of wet flue
gas desulfurisation for SO2 removal (8). Among
the technologies being considered for mercury
abatement in coal-fired boilers is therefore the
combination of a catalyst and a wet scrubber; the
catalyst oxidises Hg0 to Hg2+, and the oxidised
mercury is subsequently absorbed by the scrubber
solution. Catalysts capable of significant conver-
sion (> 80%) of Hg0 to Hg2+ could have tre-
mendous value because the oxidised mercury can
be removed concurrently with acid gases during
flue gas desulfurisation.
Mercury oxidation catalysts can be employed in
either of two configurations. In the ‘co-benefit’
application, selective catalytic reduction (SCR) cat-
alysts with sufficient activity for mercury oxidation
are installed upstream of a flue gas desulfurisation
scrubber. The primary function of the SCR catalyst
is to reduce NOx concentration in flue gas, and
some power plants will need to install SCR to
achieve compliance with the Clean Air Interstate

Platinum Metals Rev., 2008, 52, (3), 144–154 144

Rule (9). During operation, NO is reduced by NH3,
which is injected upstream of the SCR, at tempera-
tures above 300ºC. When the NH3 is consumed
(catalysts are typically oversized to prevent NH3
slip), the catalyst is available for mercury oxidation.
Mercury oxidation catalysts can also be
installed specifically for mercury control. In this
case the catalyst is located downstream of the par-
ticulate control device, where the flue gas
temperature is approximately 150ºC. The lower
temperature favours Hg0 adsorption, and may
therefore lead to more efficient mercury oxidation.
Catalysts tested in this configuration include gold,
palladium and vanadium-tungsten (10).
The catalytic oxidation of mercury to
mercury(II) chloride typically assumes an overall
reaction between Hg0 and HCl, for example,
Reaction (i):
Hg + 2HCl → → HgCl2 (i)
Cl2 may also play a role in the formation of
HgCl2, but the equilibrium concentration of Cl2 is
only ~ 1% of the HCl concentration. Several key
questions exist regarding this reaction. Specifically,
the reaction mechanism is uncertain. The bimole-
cular reaction between two species adsorbed to a
surface can be described by a Langmuir-
Hinshelwood mechanism (11), Reactions (ii)–(v):
A(g) ' A(ads) (ii)
B(g) ' B(ads) (iii)
A(ads) + B(ads) → AB(ads) (iv)
AB(ads) → AB(g) (v)
For this mechanism, the rate of reaction is
dependent on the concentrations of reactants A
and B, the adsorption equilibrium constant (Ki),
and the rate constant for the surface reaction
(ksurf). Mercury could also react via an Eley-Rideal
mechanism, which is the reaction between a sur-
face-bound species and a gas-phase (or weakly
adsorbed) species, Reactions (vi)–(vii):
A(g) ' A(ads) (vi)
A(ads) + B(g) → AB(g) (vii)
Eley-Rideal and Langmuir-Hinshelwood mech-
anisms can be inferred by surface analysis of used
Platinum Metals Rev., 2008, 52, (3)
catalysts to confirm adsorption of specific reactants
such as mercury and HCl. Additionally, pre-expo-
sure of the catalyst to an oxidant, followed by
mercury oxidation in the absence of the oxidant,
would suggest either a Langmuir-Hinshelwood
reaction or an Eley-Rideal reaction with the oxidant
as the adsorbed species. A Langmuir-Hinshelwood
mechanism can also be identified via chemical
kinetics, though the relative adsorption behaviour
of the reacting species may complicate analysis. In
some cases, a Langmuir-Hinshelwood mechanism
is characterised by a reaction that is first-order in
each of the reactants (for example, Hg0 and HCl).
However, if one species saturates the surface, the
reaction order with respect to the saturating species
can be –1 (11).
Granite et al. (12) proposed that mercury oxida-
tion could occur via a Mars-Maessen (13)
mechanism. In this mechanism, adsorbed Hg0
would react with a lattice oxidant (either O or Cl)
that is replenished from the gas phase. Reactions
(viii)–(xii) show the Mars-Maessen mechanism for
the reaction of an adsorbed species (for example,
Hg0) with lattice oxygen:
A(g) ' A(ads) (viii)
A(ads) + MxOy → AO(ads) + MxOy–1 (ix)
MxOy–1 + ½O2 → MxOy (x)
AO(ads) → AO(g) (xi)
AO(ads) + MxOy → AMxOy+1 (xii)
The Mars-Maessen mechanism can be confirmed
by the observation of mercury oxidation in the
absence of gas-phase oxygen or chlorine, respec-
tively (through variations of Reaction (ix)).
Medhekar et al. postulated that catalytically
active mercury(II) chloride forms on the surfaces
of many materials (14). They observed the reaction
between elemental Hg and Cl2 catalysed by
Inconel® (an austenitic nickel-based alloy), quartz,
stainless steel and Teflon®-coated stainless steel.
Medhekar et al. found that many surfaces can catal-
yse the reaction between Hg and Cl2 and that the
surfaces are difficult to passivate with oxygen or
fluorine. This suggests that the adsorbed HgCl2
product is the actual catalyst. Ariya et al. observed
145
that the Hg + Cl2 reaction proceeded faster when
the reactor surface was covered with the reaction
products of Hg + Br2 than with a clean surface,
suggesting a similar effect (15).
To date, none of the above mechanisms has
been verified as the dominant mechanism for cat-
alytic mercury oxidation. Mercury appears to react
from an adsorbed state (10), but the phase of the
HCl is uncertain. Furthermore, it is unknown
whether Hg and HCl react directly, or if another
species, such as mercury(II) oxide (HgO), is
formed first (16, 17). The role of other flue gas
species, specifically NO and SO2, is unclear, and
the behaviour of these species in mercury oxida-
tion may depend strongly upon the nature of the
catalyst. The deactivation mechanisms for the var-
ious mercury catalysts are also unknown.
In a previous article (10), we asserted that fur-
ther research into the fundamental aspects of
catalytic mercury oxidation is required to answer
these significant questions. The information pre-
sented in this article is part of an ongoing effort
toward that goal. We present initial results for
mercury oxidation over three noble metal cata-
lysts, Au, Pd and Pt. We envision that these
materials could be used downstream of particulate
control devices as mercury-specific catalysts. The
results reveal several important aspects of the cat-
alysts, and highlight some of the differences
between Au and the platinum group metals (pgms)
in mercury oxidation.
2. Experimental
Noble metal catalyst samples were exposed to
mercury in a bench-scale packed bed reactor that
has been described previously (18) and is shown
schematically in Figure 1. The bench-scale assem-
bly consisted of a quartz tube reactor, 22 mm
internal diameter and 61 cm long, contained in a
clamshell tube furnace. A catalyst bed containing
approximately 0.5 g of catalyst was placed in the
reactor and was supported by a quartz frit.
Alumina beads were placed above the catalyst bed
to ensure plug flow. A mass spectrometer was
located downstream of the packed bed to monitor
potential side reactions such as the formation of
flue gas halides.
Platinum Metals Rev., 2008, 52, (3)
Gas inlet
Adjustable
thermocouple
Heated quartz
reactor
Alumina beads
Catalyst
Quartz frit
Gas out to
mercury monitor
Fig. 1 Schematic diagram of the packed bed reactor
The catalysts used in this study were 1 wt.% Au,
Pd and Pt, respectively, supported on 2 mm alumi-
na beads (Johnson Matthey PLC). The BET
surface area of the alumina beads was approxi-
mately 200 m2 g–1. The catalysts were air calcined at
elevated temperatures, thereby decomposing the
precursor salts. It is very unlikely that the Au par-
ticles are of nanometre size because they sinter at
the calcination temperatures. Therefore, the Au
catalyst should have typical properties of bulk Au.
The mercury concentration and speciation exit-
ing the packed bed were measured using a P S
Analytical model 10.525 ‘Sir Galahad’ continuous
mercury monitor. A wet conditioning system with
two channels for determining elemental and total
mercury was placed upstream of the mercury mon-
itor. The elemental mercury channel used an
impinger filled with KCl solution to remove Hg2+
from the sample, and the total mercury channel
used a SnCl2/HCl solution to reduce Hg2+ to Hg0.
Both the KCl and SnCl2/HCl impingers were fol-
lowed by impingers containing NaHCO3 solution
that captured the acid gases SO2 and HCl.
The mass of catalyst was selected to provide a
small (10 to 50%) conversion of Hg0 to Hg2+. Very
high or very low fractional conversions
are unfavourable because they complicate the
146
interpretation of the experimental results. The pre- Table I
cision of the mercury monitor used in this study is
Typical Simulated Flue Gas Conditions for the
approximately 10 to 20% (1σ); therefore gas mix-
Experiments Conducted in This Study
tures containing less than 10%, or more than 90%,
oxidised mercury are statistically indisinguishable Parameter Units Baseline value Range
from gas mixtures that contain 0% or 100% oxi- [O2] % 5.25 0–5.25
dised mercury, respectively. The instrument [SO2] ppm 500 0–1000
precision is summed in quadrature for kinetics [NO] ppm 0 500
[CO2] % 12.5 –
measurements, which require both elemental and
[HCl] ppm 50 0–100
oxidised mercury concentrations. The total uncer- [CO] ppm 0 0–35
tainty for the kinetics measurements is therefore [Hg] μg Nm–3 10 6–18
15 to 30% (Figure 2), and small fractional mercury Temperature ºC 149 138–160
Flow rate slpm 8 8–10
conversions are nearly indistinguishable from the
noise.
Difficulty in obtaining consistent mercury mea- conditions are roughly consistent with previous
surements in real or simulated flue gas at levels of work from this laboratory, with the exception that
parts per billion by volume is a common problem. NO was excluded from all but one experiment in
For example, results from field studies indicate sig- this study because its presence interferes with mer-
nificant variability in mercury capture efficiency cury detection by the mercury monitor. The
during activated carbon injection. Specifically, dur- baseline conditions serve two purposes: first, they
ing long-term injection tests, individual provide the basis for a like-for-like comparison for
measurements of mercury capture efficiency each of the catalysts tested. We will refer to the
(timescale of minutes to hours) can differ signifi- mercury oxidation rate measured in the presence
cantly from the long-term results (timescale of of the baseline simulated flue gas as the ‘baseline
months) (19). When all of the potential sources of reaction rate’. The effects of excursions from the
experimental uncertainty are considered, it is our baseline gas composition are measured as devia-
opinion that the precision presented here is appro- tions from the baseline reaction rate. Second,
priate for our experimental system, and is consistent because the baseline conditions are used at the
with previous work from this laboratory (20). start of each experiment, they provide a way to
The catalysts were exposed to simulated flue measure catalyst deactivation over time.
gas containing O2, CO2, HCl, SO2, Hg0 and N2. Excursions from baseline conditions were
Each catalyst sample was tested using the ‘baseline’ undertaken in order to gain a more complete
simulated flue gas detailed in Table I. The baseline understanding of the reaction order with respect to

Fig. 2 Fractional mercury oxidation

20 conversion across a gold catalyst as a
Baseline [HCl] = [HCl] = [HCl] =
75 ppm 0 ppm 50 ppm function of time, from a typical
Hg oxidation conversion, %

[O2] = 0% experiment. The open symbols, ‘,

15 indicate the average conversion for the
baseline and [HCl] = 75 ppm time
periods. Mercury conversion is
expected to be nominally constant
10 during these phases of the experiment.
The error bars, I, show the 1σ level of
precision
5

0
9:00 11:00 13:00 15:00
Time

Platinum Metals Rev., 2008, 52, (3) 147

mercury and/or HCl, potential side or interfering
reactions, and apparent activation energy. The effects
of other flue gas species, such as SO2 and CO, were
also considered. These species can possibly bind to
and deactivate the catalyst, or can participate in parallel
reactions, such as flue gas halide formation, that may
inhibit mercury oxidation.
The catalyst samples were tested for approximate-
ly six hours per day for several days. This procedure
contrasts with packed bed experiments conducted by
this group using mercury sorbents. In those experi-
ments (18) the sorbent was exposed for six hours and
removed from the packed bed reactor. The procedur-
al difference between catalyst and sorbent
experiments is intended to partially mimic the appli-
cation of the two technologies in power plants:
sorbents are typically injected and subsequently dis-
posed of, whereas catalysts need to stay in place for
months or years in order to be an economically viable
option for mercury control (21). Exposing the cata-
lysts for multiple six-hour experiments also allows for
an initial investigation into the flue gas species and/or
processes that can deactivate the catalyst.
3. Results
The data presented in this article were analysed
according to the chemical kinetics framework previ-
ously outlined by this group (22). The catalysts are
compared by considering the overall reaction rate for
Hg2+ formation, measured in (mol Hg2+) (g catalyst)–1
s–1. The results presented in this section focus specif-
ically on the roles of HCl and oxygen in mercury
oxidation.
12
[Hg] at reactor bed exit, μg Nm–3
10
8 (0 ppm) and O2-free conditions in successive
Baseline [HCl] =
75 ppm
6 [O2] = 0%
4 rate was measured during the steady state
2 [Hg0]
0
9:00 11:00
Time
Platinum Metals Rev., 2008, 52, (3)
A time series from a typical experiment is
shown in Figure 3. In this experiment, the HCl and
O2 concentrations were changed in successive
steps, and the mercury oxidation rate was mea-
sured following each change in simulated flue gas
composition. Please note that the total concen-
tration of mercury exiting the reactor bed, [HgT], is
equal to the concentration entering the reactor.
This steady state, with no net adsorption of mer-
cury, is typically referred to as ‘complete
breakthrough’. As with other studies of mercury
oxidation catalysts, oxidation rate measurements
were only made under conditions of complete
breakthrough (22, 23).
At the start of the test series for each catalyst, the
samples adsorbed mercury for two to six hours before
reaching complete breakthrough. During most of
the subsequent experiments, the catalyst sample
adsorbed mercury for a short period, typically one
hour, prior to reaching complete breakthrough. The
mercury adsorbed during this start-up period likely
replaced mercury that was desorbed during the
cooldown period of the previous experiment.
During the first experiment for each catalyst,
Hg/CO2/N2 and Hg/CO2/O2/N2 gas mixtures
were passed prior to the baseline simulated flue
gas. All subsequent experiments were initiated with
the baseline simulated flue gas (Table I). Complete
mercury breakthrough occured quickly in the
Hg/CO2/N2 atmosphere, and no mercury oxida-
tion was evident in either of the mixtures. The
onset of mercury oxidation coincided with the use
of the baseline simulated flue gas.
Fig. 3 Mercury monitor data showing
mercury oxidation across a gold catalyst
from a typical experiment. The simulated flue
gas composition was changed from baseline
conditions to high HCl (75 ppm), low HCl
[HCl] = [HCl] = steps. The system was allowed to reach an
0 ppm 50 ppm (apparent) steady state after each change to
the simulated flue gas composition before
another change was imposed. The oxidation
portion of each time interval. [HgT] = total
mercury concentration
[HgT]
13:00 15:00
148
3.1 Gold Catalyst
The Au catalyst exhibited a consistent baseline
rate of Hg2+ formation, as shown in Figure 4. The
baseline reaction rate remained constant over a
period of seven experiments, suggesting that there
was no apparent catalyst deactivation. The mean
baseline reaction rate was (2.2 ± 0.3) × 10–10
(mol Hg2+) (g catalyst)–1 s–1. The baseline reaction
rate remained constant when the flow rate was
raised from 8 standard litres per minute (slpm) to
10 slpm with no change in simulated flue gas com-
position. This result suggests that the mercury
oxidation reaction is not limited by mass transfer
under the conditions tested here.
The HCl concentration was varied from the
baseline level of 50 parts per million (ppm) to
75 and 0 ppm. Raising the HCl concentration to
75 ppm had no effect on the reaction rate (Figure
2). Even though the reaction rate, and therefore
the fractional conversion to oxidised mercury,
were nominally constant during the baseline and
elevated HCl portions of the experiment, the data
in Figure 2 exhibit considerable scatter. As noted
above, the precision for the kinetics measurements
is approximately 15 to 30%. Due to the scatter in
the data and the difficulty in making precise kinet-
ic measurements with our current system, reaction
rates reported here often represent time averages
over periods of relative consistency (for example,
the diamond symbols in Figure 2).
When the HCl concentration was set to 0 ppm,
mercury oxidation continued, but the reaction rate
slowed. The reaction rate fell to ~ 85% of the
3.0
1010 × Baseline reaction rate,
(mol Hg2+) (g catalyst)–1 s–1
2.5
2.0
1.5
1.0
0.5
0
1 2 3 4
Experiment number
Platinum Metals Rev., 2008, 52, (3)
baseline rate after 1.5 hours and ~ 45% of the
baseline rate after 2.5 hours. Time limitations pre-
vented further testing, though we assume that
mercury oxidation would have eventually stopped
in the absence of an HCl source.
The mercury oxidation rate was also dependent
on the presence of O2. Removing O2 from the
simulated flue gas produced a similar effect to
removing HCl: mercury oxidation continued at a
reduced rate. Upon stopping O2 flow, the Hg2+
formation rate fell to < 50% of the baseline rate.
Mercury oxidation in the O2-free simulated flue
gas was only monitored for approximately 45 min-
utes, and as shown in Figure 2, the fractional
mercury conversion was trending downward at the
conclusion of the experiment. However, we are
uncertain whether the reaction rate would have
continued to decline as in the case of 0 ppm HCl.
In a separate experiment the temperature was
varied from 138 to 160ºC. An apparent activation
energy of 40 kJ mol–1 for the global reaction (i):
Hg + 2HCl → → HgCl2 (i)
was calculated for this temperature range. This is
consistent with the apparent activation energy of
~ 30 kJ mol–1 measured by Zhao et al. (24) for the
reaction of mercury with Cl2 across a Au catalyst.
3.2 Palladium Catalyst
The baseline reaction rate across the Pd catalyst
(Figure 4) declined over the course of the test peri-
od, falling from 1.6 × 10–10 to 3.3 × 10–11 (mol
Hg2+) (g catalyst)–1 s–1. Because of the rapid decline
Fig. 4 Baseline reaction rate across the gold
(squares) and palladium (circles) catalysts for
the experiments presented here. Experiments
were conducted on consecutive days
(excluding weekends), with one experiment
per day. — = the mean baseline reaction rate
for the gold catalyst; – – – = one standard
deviation
„ Au
§ Pd
5 6 7
149
in the baseline oxidation rate, all comparisons with
the baseline rate are limited to a particular experi-
ment. The baseline reaction rate was measured at the
start of each experiment, and we assume that the
baseline rate is roughly constant during a given
experiment. The decrease in the baseline reaction
rate with time suggests that the Pd catalyst is de-
activated or fouled more readily than the Au catalyst.
The Pd catalyst exhibited similar responses to
changes in HCl concentration to those of the Au
catalyst. Raising the HCl concentration from 50
ppm to 100 ppm had no impact on the reaction
rate. Lowering the HCl concentration to 0 ppm
slowed, but did not halt, mercury oxidation. The
oxidation rate fell to ~ 45% of the baseline rate
after 80 minutes, and ~ 42% of the baseline rate
after 150 minutes.
NO (500 ppm) was added for one experiment
near the end of the test period. The baseline rate
for this experiment was 3.3 × 10–11 (mol Hg2+)
(g catalyst)–1 s–1, and the mercury was approxi-
mately 10 to 20% oxidised downstream of the
catalyst bed. Adding NO to the simulated flue gas
reduced the sensitivity of the mercury monitor,
and the observed total mercury concentration fell
from 10 μg Nm–3 to 4 μg Nm–3. With NO present,
the mercury downstream of the catalyst bed was
90% oxidised. The reaction rate is not reported
here because the measurement for the total Hg
concentration is biased low. Regardless of the
actual reaction rate, adding NO to the simulated
flue gas resulted in significantly greater fractional
mercury oxidation downstream of the catalyst bed.
3.3 Platinum Catalyst
As with the Pd catalyst, the baseline reaction rate
observed with the Pt catalyst decreased over the
course of the test period. The baseline rate fell from
an initial maximum of 4.1 × 10–10 to 1.5 × 10–11
(mol Hg2+) (g catalyst)–1 s–1. As with the Au and Pd
catalysts, increasing the HCl concentration to 75 ppm
and 100 ppm had no impact on the mercury oxidation
rate. Reducing the HCl concentration to 0 ppm
yielded an immediate halt to mercury oxidation. This
behaviour is in contrast to that of the Au and Pd
catalysts, both of which continued oxidising mercury
at reduced rates when HCl flow stopped.
Platinum Metals Rev., 2008, 52, (3)
Prior to one experiment the Pt catalyst was
reduced at 165ºC with 60 ppm CO in N2. The cat-
alyst was then exposed to a mixture of
Hg/CO2/HCl/SO2/N2 at 150ºC. No oxidised
mercury formation was observed. When O2 was
added to the gas mixture to form the baseline sim-
ulated flue gas, mercury oxidation was evident. The
HCl flow was then stopped, with the expectation
that mercury oxidation would again stop. Instead,
oxidation continued at a reduced rate, consistent
with the behaviour observed for the Au and Pd
catalysts.
The apparent activation energy for mercury oxi-
dation across the Pt catalyst was measured for the
temperature range 140 to 157ºC. The measured
activation energy was ~ 120 kJ mol–1, significantly
higher than that measured for the Au catalyst.
4. Discussion
As stated in the Introduction, previous investi-
gations of mercury oxidation over a variety of
catalysts indicate that mercury reacts from a bound
state, for example, Hg(ads). It is well established that
mercury adsorbs to Au, Pt and Pd surfaces. Gold
(25, 26), palladium (27) and iridium (28) have all
been used as modifiers for improving mercury cap-
ture in graphite tube atomic absorption
spectrometry. The mercury monitor used in this
study removes mercury vapour from the sample
gas using Au/sand traps. The captured mercury is
thermally desorbed during the analysis step of the
instrument cycle. Mercury is also known to adsorb
to Pt and form a solid solution with it (29).
Therefore, we are confident in assuming that mer-
cury adsorbs to the catalyst surface prior to
reacting.
The dependence of the mercury oxidation rate
on the presence of HCl in the simulated flue gas
suggests that the oxidised mercury species
observed by the mercury monitor is indeed HgCl2.
Mercury oxidation was not observed when the cat-
alyst was exposed to the Hg/CO2/O2/N2 gas
mixture used prior to the simulated flue gas, indi-
cating that the observed oxidised mercury species
is unlikely to be HgO. Mercury(I) chloride (Hg2Cl2)
is also a possibility, as it can form via the Boliden-
Norzink reaction (30), Reaction (xiii):
150
 Hg(g) + HgCl2 → Hg2Cl2 (xiii)
However, themodynamic calculations indicate that
Hg2Cl2 is not stable under typical flue gas condi-
tions (31).
For all three noble metal catalysts tested here,
increasing the HCl concentration above 50 ppm
had no impact on the reaction rate. In a previous
study, we made an initial assumption that the mer-
cury oxidation rate can be described by
r = k[Hg][HCl] (22). This assumption is obviously
false for HCl concentrations > 50 ppm.
The assumption above required Hg + HCl as
participants in the rate-limiting step. At this point,
the rate-limiting step is unclear. When HCl was
removed from the simulated flue gas during the
tests with the Au and Pd catalysts, the reaction rate
immediately fell, suggesting that the lack of a chlo-
rine source to replenish the surface reduced the
reaction rate. Mulla et al. suggested that the adsorp-
tion of O2 to an empty surface site was the
rate-limiting step for NO oxidation over a
Pt/Al2O3 catalyst (32). Perhaps this step is also
rate-limiting for the formation of the presumed
HgO intermediate product detailed below.
The data for the Au and Pd catalysts suggest
that mercury reacts with HCl that is bound to the
catalyst surface. This explains why mercury oxida-
tion continues in the absence of gas-phase HCl,
but with a declining reaction rate. Cl2 can
chemisorb to Au surfaces and form AuCl3 (33).
HCl dissociatively adsorbs to Pt surfaces (34), and
similar behaviour might be expected for Pd. Thus,
surface-bound Cl should be available for reaction
on the Au and Pd surfaces.
The Pt catalyst exhibited different behaviour in
the absence of HCl, and mercury oxidation
stopped. This might be evidence of an Eley-Rideal
mechanism for mercury oxidation across the Pt
catalyst, with adsorbed Hg (or an intermediate such
as HgO, described below) reacting with gas-phase
HCl. Eley-Rideal kinetics would not suggest the
zero-order dependence on [HCl] for concentra-
tions greater than 50 ppm, but the overall reaction
could exhibit a zero-order dependence on [HCl] if
the Hg(ads) + HCl(g) step is not rate-limiting.
In a chlorine- and sulfur-free flame, Schofield
(16, 17) observed HgO deposition on Pt and stain-
Platinum Metals Rev., 2008, 52, (3)
less steel surfaces. When HCl was added to the
flame, the HgO desorbed as HgCl2. The implica-
tion of this observation is that Hg and HCl do not
react directly to form HgCl2, but rather form via a
HgO intermediate. Pt is an effective adsorber of
oxygen (32, 35–37), hence surface-bound oxygen
should be present in excess for the conversion of
Hg0(g) to HgO(ads). In the absence of HCl(g), the
HgO remains bound to the surface because of its
low vapour pressure. When HCl is present, the
HgO is converted to HgCl2, which desorbs from
the surface and allows more Hg to react. The
vapour pressure of HgCl2 is sufficiently high
(1 Torr at 136ºC), and the concentration is suffi-
ciently low, that the simulated flue gas stream can
hold HgCl2 as a vapour even at temperatures well
below the sublimation point.
We tested the Schofield hypothesis in the
experiment that used the reduced Pt catalyst. This
test yielded two important results: (a) O2 and HCl
(or possibly Cl2) are required for mercury oxida-
tion across a Pt catalyst, possibly because HgCl2
formation is preceded by HgO; (b) the Pt catalyst
can display a significant history effect.
In the initial series of experiments, the catalyst
was exposed to an O2-containing gas mixture prior
to the introduction of HCl. In the experiment with
the reduced Pt, the catalyst was exposed to HCl
prior to O2. We hypothesise that in the initial tests,
O(ads) greatly outnumbers Cl(ads) to the point of
exclusion. Thus, HgO is easily formed on the sur-
face, and HCl reacts with the adsorbed HgO from
the gas phase. Without HCl, there is no chlorine
source for HgCl2 formation. In the experiment
using the reduced Pt, the initial exposure to HCl
allows for an ample concentration of adsorbed
chlorine that is joined by adsorbed oxygen when
O2 is introduced. When HCl is removed from the
simulated flue gas, there is sufficient surface-
bound chlorine to sustain HgCl2 formation at a
reduced rate. The reaction mechanism remains
unclear. The initial experiments suggest the possi-
bility of an Eley-Rideal mechanism, and the
experiments with the reduced Pt catalyst might
suggest a Langmuir-Hinshelwood mechanism.
The data suggest that mercury oxidation across
the Au catalyst is dependent on the presence of O2.
151
This behaviour, while puzzling, may indicate the
formation of the HgO intermediate. HgO binds to
Au surfaces, and density functional theory calcula-
tions indicate that the binding energy for mercury
species on Au(001) decreases in the series: HgO >
Hg0 > HgCl2 (38). The predicted energy of binding
of HgCl2 to the Au(001) surface is only 17.2
kJ mol–1, suggesting that this species could easily
desorb from the catalyst surface at the tempera-
tures tested here.
The mechanism governing the oxygen depen-
dence of mercury oxidation across the Au catalyst
is unknown at this time. Unlike with Pt, oxygen is
not expected to efficiently adsorb to the Au surface
(39), suggesting that adsorbed oxygen for HgO for-
mation is not readily available at the surface. One
could postulate an Eley-Rideal reaction between
bound Hg and O2(g) to form HgO, but this reaction
requires accounting for the second oxygen atom,
suggesting either a ternary reaction (xiv):
2Hg + O2 → 2HgO (xiv)
which is unlikely, or the migration of an oxygen
atom to the Au surface, which is also unlikely.
Further research is required to elucidate this
behaviour.
The nature of the bonding of mercury, chlorine
and oxygen species to the catalyst surface is
unknown at this time. One possibility is that each
species adsorbs to the surface individually – Hg(ads),
Cl(ads), HgO(ads), etc. Mercury is known to interact
with other metals to form a variety of oxides and
halides (40) that could participate in the surface
reactions which lead to the formation of HgCl2.
Surface analysis of fresh and used catalyst samples
will be conducted in the future in order to gain
more insight.
The most significant difference between the
performance of the Au and the pgm catalysts, was
the loss of catalytic activity for the Pd and Pt over
the course of the test period. The presence of
adsorbed oxygen on the catalyst surface may offer
an explanation for the observed drop in catalyst
activity. While testing Pt/Al2O3 catalysts for the
oxidation of NO to NO2, Mulla et al. observed that
the catalyst deactivated during cooldown and other
changes to process conditions (32). The
Platinum Metals Rev., 2008, 52, (3)
researchers proposed that deactivation may have
been the result of the oxidation of the Pt surface.
Olsson et al. also observed deactivation of
Pt/Al2O3 and Pt/BaO/Al2O3 catalysts during the
same reaction and attributed the loss of catalytic
activity to the formation of unreactive PtO (41).
The formation of Pt and Pd oxides, especially
while exposed to O2 during cooldown, may also
explain the deactivation observed here. The poor
reactivity of PtO might also suggest that the possi-
ble HgO intermediate product is not formed via a
Mars-Maessen reaction. Au, on the other hand, is
typically a poor adsorber of oxygen and is likely
not subject to this deactivation mechanism (39).
Mulla et al. found that their Pt/Al2O3 catalyst
could be regenerated with CO or H2 (32). This
observation agrees well with the data presented
here; Hg oxidation proceeded at nearly the initial-
ly observed baseline reaction rate after the Pt
catalyst was exposed to CO. The enhanced extent
of Hg oxidation observed across the Pd catalyst in
the presence of NO also suggests that surface
oxygen inhibits Hg oxidation. When NO was
added to the simulated flue gas used here, it is
possible that surface oxygen was removed, allow-
ing for increased conversion of mercury (32,
35–37, 41).
It is unclear at this time whether the Pt and Pd
catalysts were deactivated by the formation of oxides
(for example, PtO and PdO), surface-bound oxygen,
or both. While NO may have removed adsorbed
oxygen from the Pd surface, the presence of PtO
has been observed to inhibit NO oxidation across
Pt catalysts (41). Thermal regeneration of Pt catalysts
requires temperatures of 600 to 650ºC, significantly
higher than the temperatures used here. Surface
analysis will be required to confirm the nature of the
catalyst surface following exposure to the simulated
flue gas.
Of concern with all potential mercury oxidation
catalysts are the unwanted side reactions (xv) and
(xvi):
NO + ½O2 → NO2 (xv)
and
SO2 + ½O2 → SO3 (xvi)
152
Stack NO2 concentrations as low as 15 ppm (42)
can lead to the formation of a brown plume and
enhanced local ozone production. SO3 is captured
poorly in most wet flue gas desulfurisation sys-
tems, and can lead to sulfuric acid mist in the
downstream plume. In each case, a small concen-
tration can produce a significant impact – 15 ppm
NO2 corresponds to only 3% NO conversion for
flue gas containing 500 ppm NO. To date, both
Au and Pd catalysts have been tested at pilot scale,
and neither SO3 nor NO2 formation was observed
(23). However, formation of these unwanted by-
products remains a concern.
The results introduced here may have several
implications for the use of noble metal catalysts in
mercury abatement schemes. Perhaps most impor-
tant is the observation that Au exhibits superior
resistance to deactivation than Pd and Pt. Contrary
to our short-term, bench-scale results, pilot-scale
testing of Au and Pd showed similar performance
and deactivation over time (23). A likely explana-
tion is the presence of NO in the real flue gas; as
shown here, NO appears to regulate the surface
oxygen concentration on the Pd catalyst, leading
to improved Hg oxidation versus a NO-free simu-
lated flue gas. The oxygen resistance of Au may
come into play during periods of down time, when
the catalyst beds come into contact with air at
ambient temperature. This condition favours oxy-
gen adsorption onto Pt and Pd. However, a
preference for Au remains to be seen, and future,
longer-term testing may be warranted.
5. Conclusions
The results presented here provide an initial
investigation into the mechanisms behind mercury
oxidation across noble metal catalysts, and more
work is needed. Investigations are needed into the
role of other potential flue gas catalyst poisons
such as arsenic, selenium and SO3. Selenium is sus-
pected to deactivate Au catalysts tested at pilot
scale (23), and initial experiments conducted in our
laboratory suggest that high concentrations of SO3
can deactivate Au catalysts. Future work should
also focus on the possible beneficial role of differ-
ent promoters, alloys and supports. At the size and
timescale presented here, both Au and pgms show
Platinum Metals Rev., 2008, 52, (3)
promise for use as mercury oxidation catalysts. As
we begin to understand mercury oxidation across
these catalysts – specifically the roles of O2 and
HCl and the apparent deactivation mechanisms –
improvements can be made that will help mercury
oxidation catalysts become economically competi-
tive as part of a mercury abatement strategy.
Acknowledgements
The authors thank Johnson Matthey PLC for
providing the catalyst samples. Hugh Hamilton of
the Johnson Matthey Technology Centre, U.K.,
provided excellent insight into the catalyst prepa-
ration and properties. The comments of the
reviewers are greatly appreciated. Albert Presto
acknowledges the support of a postdoctoral
fellowship at the U.S. Department of Energy
(DOE) administered by the Oak Ridge Institute
for Science and Education (ORISE). Funding sup-
port from the DOE Innovations for Existing
Power Plants (IEP) Program is greatly appreciated.
We thank Gregson Vaux, Power/Energy Engineer
for the Science Applications International
Corporation (SAIC), for his kind help in under-
standing the regulatory status for mercury
emissions as of April 2008.
Disclaimer
References in this paper to any specific com-
mercial product, process, or service are to facilitate
understanding, and do not necessarily imply its
endorsement by the U.S. DOE.
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The Authors
Dr Albert A. Presto is currently a Research Scientist
and Laboratory Manager for the Air Quality
Laboratory in the Center for Atmospheric Particle
Studies at Carnegie Mellon University. Prior to his
current position he was an ORISE postdoctoral
fellow at the U.S. Department of Energy’s National
Energy Technology Laboratory (NETL) in Pittsburgh.
His research interests include mercury removal
from coal-derived flue and fuel gas, atmospheric
secondary organic aerosol formation, the
atmospheric processing of organic aerosol, and
atmospheric radical chemistry.
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Schnyder and A. Wokaun, Appl. Catal. B: Environ.,
2004, 50, (2), 73
36 R. Marques, P. Darcy, P. Da Costa, H. Mellottée, J.-
M. Trichard and G. Djéga-Mariadassou, J. Mol. Catal.
A: Chem., 2004, 221, (1–2), 127
37 M. F. Irfan, J. H. Goo, S. D. Kim and S. C. Hong,
Chemosphere, 2007, 66, (1), 54
38 E. Sasmaz and J. Wilcox, ‘The Binding of Flue Gas
Components on CaO, TiO2, Pd, Au and PdAu Alloy’,
Paper No. 409, in “Proceedings of the Air & Waste
Management Association’s 100th Annual Conference
and Exhibition”, Pittsburgh, PA, June, 2007,
A&WMA, Pittsburgh, PA, 2007
39 X. Deng, B. K. Min, A. Guloy and C. M. Friend,
J. Am. Chem. Soc., 2005, 127, (25), 9267
40 J. W. Mellor, “A Comprehensive Treatise on Inorganic
and Theoretical Chemistry”, Longmans, Green and
Company, London, New York, 1952, Vol. IV
41 L. Olsson and E. Fridell, J. Catal., 2002, 210, (2), 340
42 A. S. Feitelberg and S. M. Correa, J. Eng. Gas Turbines
Power, 2000, 122, (2), 287
Dr Evan J. Granite is a Research Group Leader at
the NETL. His research has focused on mercury
and carbon dioxide removal from flue and fuel
gases. Dr Granite is the principal investigator for
three projects on the capture of mercury, arsenic
and selenium from coal-derived flue and fuel
gases, and carbon dioxide separation from flue
gas. His research interests are in catalysis and
surface chemistry, pollution clean-up,
electrochemistry and photochemistry.
154
DOI: 10.1595/147106708X332215
“Highly Efficient OLEDs with
Phosphorescent Materials”
EDITED BY HARTMUT YERSIN (University of Regensburg, Germany), Wiley-VCH, Weinheim, Germany, 2007, 458 pages,
ISBN 978-3-527-40594-7, £100.00, €135.00, U.S.$190.00
Reviewed by R. J. Potter
Johnson Matthey Technology Centre, Blounts Court, Sonning Common, Reading RG4 9NH, U.K.; E-mail: potterj@matthey.com
In January 2008 Sony announced the release of
the first organic light-emitting diode (OLED)-based
television (Figure 1) into the U.S. consumer market
(1). This was a milestone in the development of
materials that for over twenty years have been
heralded as the successor to liquid crystal displays.
Fig. 1 Side view of Sony
XEL-1 television (Courtesy
of OLED Display.net)
This new monograph on OLEDs joins a small
but growing number of books on the subject,
including a 2006 publication from Wiley-VCH
entitled “Organic Light Emitting Devices:
Synthesis, Properties and Applications” (2), which
was reviewed in this Journal (3). The new book
reviewed here concentrates on recent advances in
the materials characterisation and development
aspects of OLEDs. There is a strong emphasis on
the special role played by the platinum group metal
(pgm) complexes as dopants to improve critical
light-emitting characteristics; see Figure 2 for exam-
ples. It is revealing that of the thirty-three
contributors, over a quarter are from China, with
the rest spread evenly between Japan, the U.S.A.,
Germany, The Netherlands and Switzerland; there
are no U.K. contributors.
Platinum Metals Rev., 2008, 52, (3), 155–156
(a) (b)
Fig. 2 Examples of structures of iridium
electrophosphorescent dopant complexes:
(a) fac-tris(phenylpyridine) iridium, Ir(ppy)3;
(b) bis(2-(2'-benzothienyl)-pyridinato-N,C)-
iridium(acetylacetonate), Ir(btp)2(acac)
The reader of the book is required to be familiar
with basic concepts in photophysics and coordina-
tion chemistry. Although much of the work is
clearly very specialised, it should prove accessible
to those seeking an introduction to the field.
Complexes of the pgms (platinum, palladium, iridi-
um, rhodium, osmium and ruthenium are all
represented) dominate eleven out of twelve chap-
ters, with in-depth reviews of the design, synthesis,
modelling and behaviour of a fascinatingly diverse
range of molecules. For the important Ir complex-
es, ligands include (as their anions):
acetylacetonate (acac), 2-benzo[b]thiophen-2-yl-
pyridine (btp), 1-phenylisoquinoline (1-piq) and
2-phenylpyridine (ppy). (See Figure 2(a) for ppy and
Figure 2(b) for acac and btp.)
There is much less emphasis on OLED device
architectures and the practical side of converting the
science into working technology, such as material
processing and durability.
The monograph is very well packaged, with a
remarkably high standard of English and very few
editing errors. It contains prolific, clear figures of
molecular structures and performance data. Most of
the chapters include a useful summary and
conclusions at the end of the section, followed by
155
references. The indexing and overall layout are
exemplary, as you would expect for the price! The
occasional repetition of the basics in some of the
introductions will probably be useful to newcomers,
like myself, who read this in the hope of quickly
learning about the field. Conversely, those already
knowledgeable should find plenty of detail to
engage with. Gripes are minor; one or two of the
photographs would have benefited from colour, a
list of acronyms would have helped, and perhaps a
summary of the pros and cons of small-molecule
versus polymer materials in OLED devices would
have been useful.
To conclude, this is an excellent book for physi-
cists and chemists alike interested in the role of pgm
complexes in OLEDs, and the challenge of building
nanometre-thick multilayers of functional materials.
Platinum Metals Rev., 2008, 52, (3)
References
1 ‘Sony bringing super-thin high-quality organic LED
television to US this month’, International Herald
Tribune, 7th January, 2008:
http://www.iht.com/articles/ap/2008/01/07/busi-
ness/NA-TEC-US-Sony-OLED-TV.php
2 “Organic Light Emitting Devices: Synthesis,
Properties and Applications”, eds. Klaus Müllen and
Ullrich Scherf, Wiley-VCH, Weinheim, Germany,
2006
3 J. A. G. Williams, Platinum Metals Rev., 2007, 51, (2), 85
The Reviewer
Rob Potter has worked in electrochemistry and
photoelectrochemistry for over thirty years. Having
joined Johnson Matthey, U.K., in 1986, he has
spent much of his time since in research and
development on fuel cells, electrochemical
synthesis and, more recently, photovoltaics.
156
DOI: 10.1595/147106708X322720

Practical New Strategies for Immobilising

Ruthenium Alkylidene Complexes: Part II
IMMOBILISATION VIA SCHIFF BASES, ARENES, AND ANIONIC AND TAGGED LIGANDS

By Ileana Dragutan* and Valerian Dragutan**

Institute of Organic Chemistry “Costin D. Nenitescu”, Romanian Academy, 202B Spl. Independentei, PO Box 35-108,
060023 Bucharest, Romania; E-mail: *idragutan@yahoo.com; **vdragutan@yahoo.com

Following Part I, previously published in this Journal (1), the present paper discusses new
routes for immobilisation of ruthenium alkylidene complexes through their ligands. Systematically
addressed as suitable participants for immobilisation are Schiff bases, arenes, anionic ligands
and specifically tagged (ionic liquid tag, fluoro tag) substituents.

1. Immobilisation via the Schiff 32–34) in which the homogeneous Ru complex

Base Ligand was anchored to the carrier by a non-labile tether,
Detailed studies by Verpoort et al. (2–5) have bound to the Schiff base ligand yet imposing little
been directed towards the design, synthesis and or no steric hindrance at the reactive site (18–20)
progressive development of homogeneous and (Scheme I). (Structures 1–31 are given in Part I (1).)
immobilised N,O-bidentate ruthenium complexes From all potential inorganic supports, the
bearing Schiff base ancillary ligands, as an attrac- mesoporous silica gel MCM-41 (mobile crystalline
tive alternative to N-heterocyclic carbenes (NHCs) material) was selected as most appropriate because
(6–15) for applications in ring-closing metathesis of its advantages (21–24): (i) retention of a con-
(RCM), Kharasch addition, ring-opening metathe- stant exposed surface area, in contrast to
sis polymerisation (ROMP), atom transfer radical conventional polymer beads that typically swell
polymerisation (ATRP) and vinylation reactions and shrink variably in different media, resulting in
(16, 17). Structurally robust and effective support- unpredictable effects on the catalyst activity; (ii)
ed catalysts have been devised (for example, the greater robustness of MCM-41 than organic
Scheme I
Immobilised
O
O Schiff base
H H
H ruthenium
O Si
Si O complexes 32–34
N Si
Si O N
N O
CCll Cl
Cl
Ru
Ru
O
CHPh Ru
O CHPh O
O CHPh
C HPh
PCy33
PCy PCy
PCy33
32 33

O
Si
Si O
O
O
N Cl
Cl
Ru
Ru
O

34

Platinum Metals Rev., 2008, 52, (3), 157–162 157

polymers and inorganic solids and, particularly for
types with a structured surface, a considerably
larger area; (iii) anchoring the active catalytic
species on a larger surface area would help to over-
come the activity loss (due to an inefficient
interfacial mass transfer between the liquid phase
and the solid), currently encountered in passing
from homogeneous to heterogeneous catalysis; (iv)
the MCM-41 solid support consists of an ordered
array of hexagonal channels with the pore diameter
in the mesoporous region, allowing lower resistance
to diffusion of the reactant molecules accessing the
metal active sites that are located within the chan-
nels (vs. nanoporous zeolite supports).
The methodology followed in preparing the
MCM-41 supported catalyst systems 32–34 implies
the prior synthesis of the immobilised Ru precur-
sors 35–37 endowed with an anchorable
tris(alkoxy)silyl functionality, followed by tethering
onto the mesoporous silica surface (Schemes
II–IV). Chemical tethering, as employed for 32–34,
is one of the best strategies for anchoring a homo-
geneous catalyst to a solid support, in view of its
minimising leaching behaviour. Structural measure-
ments on the above immobilised complexes carried
out by X-ray diffraction (XRD), N2-adsorption
analysis, Raman spectroscopy, X-ray fluorescence
(XRF) spectroscopy and solid-state nuclear mag-
netic resonance (NMR) spectroscopy evidenced
that in all cases, the homogeneous catalyst is
anchored to MCM-41 via a spacer having two or
three covalent bonds.

H
H O
OEt
MCM-41 N Si O
N Si OEt
Ru CHPh O
OEt THF, 40 oC,2424h h
THF, 40ºC, O
Ru CHPh
O Cl
Cl PCy3
PCy3 35 32

Scheme II Synthesis of immobilised ruthenium complex 32

OEt O
H H
Si OEt Si O
N N O
OEt
MCM-41
Ru CHPh Ru CHPh
O THF,
THF,40ºC, 2424h h
40 o C, O
Cl Cl
PCy3 36 PCy 3 33

Scheme III Synthesis of immobilised ruthenium complex 33

OEt O
Si OEt3
Si(OEt) Si O
OEt O
N MCM-41 N
Cl Cl
Ru MCM-41 Ru
Ru
O THF, 24 h, RT O
THF, RT, 24 h

37 34

Scheme IV Synthesis of immobilised ruthenium complex 34

Platinum Metals Rev., 2008, 52, (3) 158

2. Immobilisation via the Arene support. Using this method, they replaced the chlo-
Ligand ride ligand from the first-generation Grubbs
Arene ligands coordinated to Ru have also been catalyst Cl2(PCy3)2Ru(=CHPh), 2, with a carboxy-
employed to immobilise homogeneous complexes late group attached to a polystyrene (PS) resin via a
onto solid supports. This approach has been used strongly electron-withdrawing tether, finally gain-
by Akiyama and Kobayashi (25) to prepare the ing access to the immobilised Ru complex 39
polystyrene-bound Ru-allenylidene complex 38 (Scheme VI).
(Scheme V). Surprisingly, catalyst 38 showed wide-
ranging activity, for example in RCM, PR
PR33
Cl
Cl Ph
Ph
hydrogenation and cyclisation reactions of olefins. Ru
Cl
Cl H
H
PR33
PR
3. Immobilisation via Anionic R = Cy 2
Ligands
A totally different protocol for immobilisation Complex 39 was very active and versatile in self-
of Ru complexes has been devised by Mol et al. metathesis of internal olefins (trans-decene and
(26). Taking advantage of the capacity of anionic methyl oleate) and RCM of α,ω-dienes (diethyl
ligands to create strong bonds with Ru which diallylmalonate); it could easily be separated from
remain intact throughout the entire catalytic cycle, the reaction products, resulting in virtual freedom
the authors used such ligands to generate a perma- from Ru contamination. Additionally, catalyst 39
nent covalent link between the Ru centre and the could be recycled for at least six reaction cycles and

CO2 Et
OH
Cl Ru nn
Ph Ph
Cl PPh3 nn
nn Ph
Ph
Ph PCy 3
PCy3 , NaPF6
Cl Ru | PF |
Cl 6
Ru C
Cl
PPh3 C
C Ph
38 Ph

Scheme V Synthesis of immobilised ruthenium arene complex 38

O O O
(a)a.THF
THF O (CF2) 3 OH
OH + F F
1.5
1.5 hh
F F O O
F F
PS Resin
(b) b.(Me
(Me3Si) 2NNa,
3Si)
THF,
2 NNa, THF
2 2h h c.AgNO
(c) 3,THF/EtOH,
AgNO 12 h12 h
3, THF/EtOH,

(d) Catalyst 2 PCy3

d. 2(0.5
(0.5equiv.)
equiv.) O (CF2)3 O
O (CF2)3 OAg Ru CHPh
THF/Hexane,
THF/Hex
15 O O Cl PCy3
O O 15 h
h
39

Scheme VI Synthesis of immobilised ruthenium benzylidene complex 39 ((Me3Si)2NNa = sodium

bis(trimethylsilyl)amide)

Platinum Metals Rev., 2008, 52, (3) 159

be stored for more than six months, under nitro-
gen, retaining its initial activity intact.
Functionalised, partially fluorinated Hoveyda and
Grubbs-Hoveyda catalysts supported on silica gel
(SG 60), were obtained by Blechert et al. (27) from
their homogeneous counterparts; these catalysts
performed conventional RCM with activity com-
parable to that of similar heterogeneous systems
(28–31).
4. Tagged Ruthenium Alkylidene
Complexes
A fairly recent technique for non-covalent
immobilisation of homogeneous Ru metathesis
catalysts onto liquid supports focuses on the
advantages provided by room temperature ionic
liquids (RTILs). Applied first in reactions involv-
ing RTILs merely as reaction media, in particular
in earlier work by Dixneuf et al. using allenylidene-
Ru precatalysts (32–34), the technique was further
extended to ionic liquid-tagged catalyst precursors.
Thus, several NHC-Ru complexes, in particular
the IL-tagged counterparts of the Hoveyda or
Hoveyda-Grubbs catalysts, such as 40 (35), 41 (36,
37) and 42 (38) or 43 (39), have been used with
improved results in various metathesis reactions
conducted in ILs or IL/organic solvent mixtures
(biphasic catalysis) (Scheme VII). Complexes
40–43 demonstrated convenient recyclability,
combined with high reactivity and extremely low
residual Ru levels in the products.
Two new Hoveyda-type catalysts, containing an
IL-tag linked either to the ortho-oxygen substituent
(44) or to the meta-position (45) of the styrenyl-
idene ligand have recently been reported (40). In
catalyst 44, the IL-tag is innovatively attached
through the Ru-chelated oxygen atom. The
catalysts were evaluated for RCM of N,N-diallyl-
tosylamide and dimethyldiallylmalonate,
conducted in an IL medium, showing moderate
recyclability, yet good activity for the first cycle
(Scheme VIII).
As an alternative for tagging Ru complexes, the
‘light fluorous’ versions, 46 and 47, of the first-
and second-generation Grubbs-Hoveyda metathe-
sis catalysts have also been proposed (41) (Scheme
IX). Catalysts 46 and 47 exhibit the expected reac-
tivity profile, are readily recovered from reaction
mixtures by fluorous solid-phase extraction, and
can routinely be recycled five or more times. They
can be used in a stand-alone fashion, or supported
on fluorous silica gel.

PCy
PCy33 |
PF6 N Me N N
ClCl Mes |
Ru |N ClCl Mes PF 6 N Me
Cl Ru |N
H
O Cl H
O

40 41

PCy
PCy33 N N
Mes Cl Mes
Cl
Cl Cl
Ru Ru
Cl | Cl
|
PF6 PF6
O O | O O |
N N Me N N Me

42 43

Scheme VII Representative ionic liquid-tagged PCy3- and NHC-ruthenium complexes 40–43

Platinum Metals Rev., 2008, 52, (3) 160

 Scheme VIII
PCy
PCy33 PCy
PCy33 Representative
Cl Cl
Cl ionic liquid-tagged
Ru Ru PCy3-ruthenium
Cl Cl complexes 44
O and 45
O

O
O
N
N

N | Me
N Me N
N
Me
Me PF6 | N | Me
Me
PF6 N
44 Me PF6 |
Me 45
PF6

Scheme IX Fluoro-tagged
first- and second-
PCy
PCy33 N N generation Grubbs-
Cl Mes Cl Mes Hoveyda catalysts
Cl Cl
Ru Ru 46 and 47
Cl Cl
O (CH2 )n C8F17 O (CH2) 2C8 F17

46 47

5. Conclusion provide important advantages, among which the

As described here and in Part I (1), immobil-
isation of well defined homogeneous Ru alkyli-
dene complexes by means of their anionic and
coordinative ligands is now a readily accessible,
efficient technique, providing active catalysts for
metathesis reactions. Immobilisation is achieved
on a broad range of solid supports ranging from
organic polymers (polystyrene, vinyl polystyrene)
to inorganic matrices (silica, mesoporous silica
gel, zeolites) and the fashionable ionic liquids. So
far immobilisation through NHCs appears to be
the most popular approach. Synthetic applications
of immobilised catalysts in the metathesis field
References
1 I. Dragutan and V. Dragutan, Platinum Metals Rev.,
2008, 52, (2), 71
2 R. Drozdzak, B. Allaert, N. Ledoux, I. Dragutan, V.
Dragutan and F. Verpoort, Coord. Chem. Rev., 2005,
249, (24), 3055
3 B. Allaert, N. Dieltiens, C. Stevens, R. Drozdzak, I.
Dragutan, V. Dragutan and F. Verpoort, in
“Metathesis Chemistry: From Nanostructure Design
to Synthesis of Advanced Materials”, eds. Y.
Imamoglu and V. Dragutan, NATO Science Series
II: Mathematics, Physics and Chemistry, Vol. 243,
Springer Verlag, Berlin, Heidelberg, 2007, pp. 39–78
4 R. Drozdzak, N. Ledoux, B. Allaert, I. Dragutan, V.
most valued are a high catalytic activity and stere-
oselectivity, simpler, clean and recyclable
processes, and low impurity content in the reac-
tion products. Future scale-up to industrial
exploitation of the immobilised Ru catalysts is to
be envisaged, allowing promotion of sustainable
technologies within the framework of ‘green’
chemistry protocols. An attractive aspect of
immobilisation is that it holds great promise for
elaborate syntheses of fine chemicals, pharmaceu-
ticals, nutraceuticals and speciality polymers,
where a very low residual metal content from the
catalyst is a requirement.
Dragutan and F. Verpoort, Cent. Eur. J. Chem., 2005,
3, (3), 404
5 R. Drozdzak, B. Allaert, N. Ledoux, I. Dragutan, V.
Dragutan and F. Verpoort, Adv. Synth. Catal., 2005,
347, (14), 1721
6 W. A. Herrmann, Angew. Chem. Int. Ed., 2002, 41, (8),
1290
7 “Handbook of Metathesis”, ed. R. H. Grubbs, in 3
vols., Wiley-VCH, Weinheim, Germany, 2003, Vol. I
8 V. Dragutan, I. Dragutan and A. Demonceau,
Platinum Metals Rev., 2005, 49, (3), 123
9 I. Dragutan, V. Dragutan, L. Delaude and A.
Demonceau, ARKIVOC, 2005, (x), 206

Platinum Metals Rev., 2008, 52, (3) 161

10 “N-Heterocyclic Carbenes in Synthesis”, ed. S. P.
Nolan, Wiley-VCH, Weinheim, 2006
11 “N-Heterocyclic Carbenes in Transition Metal
Catalysis”, ed. F. Glorius, Topics in Organometallic
Chemistry, Vol. 21, Springer-Verlag, Berlin, 2007
12 S. Díez-González and S. P. Nolan, Coord. Chem. Rev.,
2007, 251, (5–6), 874
13 “Metathesis Chemistry: From Nanostructure Design
to Synthesis of Advanced Materials”, eds. Y.
Imamoglu and V. Dragutan, NATO Science Series
II: Mathematics, Physics and Chemistry, Vol. 243,
Springer Verlag, Berlin, Heidelberg, 2007
14 V. Dragutan, I. Dragutan, L. Delaude and A.
Demonceau, Coord. Chem. Rev., 2007, 251, (5–6), 765
15 I. Dragutan, V. Dragutan, L. Delaude, A.
Demonceau and A. F. Noels, Rev. Roumaine Chim.,
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16 V. Dragutan and I. Dragutan, J. Organomet. Chem.,
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17 V. Dragutan and F. Verpoort, Rev. Roumaine Chim.,
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18 K. Melis, D. De Vos, P. Jacobs and F. Verpoort,
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19 H. I. Beerens, W. Wang, L. Verdonck and F.
Verpoort, J. Mol. Catal. A: Chem., 2002, 190, (1–2), 1
20 B. De Clercq, T. Opstal, K. Melis and F. Verpoort, in
“Ring Opening Metathesis Polymerisation and
Related Chemistry: State of the Art and Visions for
the New Century”, eds. E. Khosravi and
T. Szymanska-Buzar, NATO Science Series II:
Mathematics, Physics and Chemistry, Vol. 56,
Kluwer Academic Publishers, Dordrecht, The
Netherlands, 2002, p. 451
21 “Heterogeneous Catalysis and Fine Chemicals IV”,
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Surface Science and Catalysis, Vol. 108, Elsevier,
Amsterdam, 1997
22 S. Ernst, R. Gläser and M. Selle, in “Progress in
Zeolite and Microporous Materials, Proceedings of
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H. Chon, S. Kilhm and Y. S. Uh, Studies in Surface
Science and Catalysis, Vol. 105, Part 2, Elsevier,
Amsterdam, 1997, pp. 1021–1028
The Authors
Ileana Dragutan is a Senior Researcher at the
Institute of Organic Chemistry “Costin D.
Nenitescu” of the Romanian Academy. Her
interests lie in the synthesis of stable organic
radicals, EPR spin probe applications in
organised systems and biological
environments, late transition metal complexes
with radical ligands, ruthenium catalysis in
organic and polymer chemistry, iminocyclitols
and prostaglandin-related prodrugs.
Platinum Metals Rev., 2008, 52, (3)
23 B. De Clercq, F. Lefebvre and F. Verpoort, New J.
Chem., 2002, 26, (9), 1201
24 B. De Clercq, F. Lefebvre and F. Verpoort, Appl.
Catal. A: Gen., 2003, 247, (2), 345
25 R. Akiyama and S. Kobayashi, Angew. Chem. Int. Ed.,
2002, 41, (14), 2602
26 P. Nieczypor, W. Buchowicz, W. J. N. Meester,
F. P. J. T. Rutjes and J. C. Mol, Tetrahedron Lett., 2001,
42, (40), 7103
27 K. Vehlow, S. Maechling, K. Köhler and S. Blechert,
J. Organomet. Chem., 2006, 691, (24–25), 5267
28 D. Fischer and S. Blechert, Adv. Synth. Catal., 2005,
347, (10), 1329
29 L. Li and J.-l. Shi, Adv. Synth. Catal., 2005, 347, (14),
1745
30 X. Elias, R. Pleixats, M. Wong Chi Man and J. J. E.
Moreau, Adv. Synth. Catal., 2006, 348, (6), 751
31 M. R. Buchmeiser, New J. Chem., 2004, 28, (5), 549
32 D. Sémeril, H. Olivier-Bourbigou, C. Bruneau and
P. H. Dixneuf, Chem. Commun., 2002, (2), 146
33 S. Csihony, C. Fischmeister, C. Bruneau,
I. T. Horváth and P. H. Dixneuf, New J. Chem., 2002,
26, (11), 1667
34 R. Castarlenas, C. Fischmeister, C. Bruneau and P. H.
Dixneuf, J. Mol. Catal. A: Chem., 2004, 213, (1), 31
35 N. Audic, H. Clavier, M. Mauduit and J.-C.
Guillemin, J. Am. Chem. Soc., 2003, 125, (31), 9248
36 H. Clavier, N. Audic, M. Mauduit and J.-C.
Guillemin, Chem. Commun., 2004, (20), 2282
37 H. Clavier, N. Audic, J.-C. Guillemin and
M. Mauduit, J. Organomet. Chem., 2005, 690, (15), 3585
38 Q. Yao and Y. Zhang, Angew. Chem. Int. Ed., 2003, 42,
(29), 3395
39 Q. Yao and M. Sheets, J. Organomet. Chem., 2005, 690,
(15), 3577
40 C. Thurier, C. Fischmeister, C. Bruneau, H. Olivier-
Bourbigou and P. H. Dixneuf, J. Mol. Catal. A: Chem.,
2007, 268, (1–2), 127
41 M. Matsugi and D. P. Curran, J. Org. Chem., 2005, 70,
(5), 1636
Valerian Dragutan is a Senior Researcher at the
Institute of Organic Chemistry “Costin D.
Nenitescu” of the Romanian Academy. His
research interests are homogeneous catalysis
by transition metals and Lewis acids; olefin
metathesis and ROMP of cycloolefins;
bioactive organometallic compounds; and
mechanisms and stereochemistry of reactions
in organic and polymer chemistry. He is a
member of several national and international
chemical societies, and has contributed
significant books, book chapters, patents and
papers to the scientific literature.
162
DOI: 10.1595/147106708X324845

Novel Lipophilic Platinum(II)

Compounds of Salicylate Derivatives
RESEARCH, DEVELOPMENT AND LIPOSOMAL FORMULATION

By Wei-Ping Liu*, Qing-Song Ye, Yao Yu, Xi-Zhu Chen and Shu-Qian Hou
Platinum-Based Drug Lab, Kunming Institute of Precious Metals, Kunming, Yunnan 650021, P.R. China;
*E-mail: liuweiping0917@126.com

Li-Guang Lou and Yong-Ping Yang

Shanghai Institute of Materia Medica, Chinese Academy of Sciences, Shanghai 201203, P.R. China

and Yi-Ming Wang and Qiang Su

Tsinghua University, Department of Chemistry, Beijing 100084, P.R. China

A series of novel lipophilic platinum(II) compounds containing salicylate derivatives as the

leaving group have been designed, synthesised and characterised. Most of the platinum
compounds exhibit high solubility and have a partition coefficient suited to liposomal
encapsulation. Some of the compounds are more pharmacologically active and/or less toxic
than carboplatin and oxaliplatin. The liposomal formulation of the most promising compound
has been successfully prepared with long stability and high encapsulation rate, showing great
potential to be developed as a new tumour-target drug.

In developed countries, such as the U.S.A.,
Canada, Australia and European countries, about
25% of deaths are related to malignant diseases.
Chemotherapy is a central component in the fight
against cancer. It is based on various classes of
compounds, among which platinum-based drugs
are a unique class. cis-Diamminedichloro-
platinum(II) (cisplatin), first approved for clinical
use in 1978 in the U.S.A., is one of the most effec-
tive anticancer drugs currently available for the
treatment of testicular, lung and bladder carcino-
mas. Driven by the impressive impact of cisplatin
on cancer therapy, numerous analogues have been
prepared and evaluated in a search for alternative
active agents, leading to the discovery of another
important Pt drug, carboplatin, cis-diammine(1,1-
cyclobutanedicarboxylato)platinum(II) in 1986.
Today, carboplatin has become one of the most
successful anticancer drugs after cisplatin and has
received worldwide approval for treating ovarian
and small lung cancers (1, 2). Carboplatin shows a
spectrum of activity identical with that of cisplatin,
but is much less nephrotoxic and emetic.
However carboplatin is not effective in treating
cancer cells resistant to cisplatin, possibly due to
the same diammine carrier, suggesting that cross-
resistance exists between the two Pt drugs (3, 4).
Therefore, the search for new potent Pt complex-
es possessing high antitumour activity and lack of
cross-resistance continues. The so-called ‘third
generation’ Pt drug, oxaliplatin, (trans-1R,2R-
cyclohexane-1,2-diamine)oxalatoplatinum(II), was
approved in 1999 as the first line therapy for
metastatic colorectal cancer in combination with
5-fluoroural. Oxaliplatin has also shown potency
in many cancer cell lines, including some cells
resistant to cisplatin and carboplatin (5). Further
Pt-based drugs, nedaplatin, lobaplatin and epta-
platin, have gained regionally limited approval,
respectively, in Japan, China and South Korea, for
the treatment of certain kinds of cancers (6). Pt-
based drugs currently in clinical use are shown in
Figure 1.
In the meantime, the rational design of Pt anti-
cancer compounds with specific characteristics
has led to the invention of the orally available
drugs satraplatin (JM216) and picoplatin
(AMD473, a sterically hindered complex), see

Platinum Metals Rev., 2008, 52, (3), 163–171 163

 O
O O
H3N Cl H3N O C NH22
C
Pt Pt Pt
H3N Cl H3N O C NH
NH22 C
O O
O
Cisplatin
Cisplatin Carboplatin
Carboplatin Oxaliplatin
Oxaliplatin

O
O
O O
O
O
O NH
NH22 O
O O NH22 O C
HH33N
N
Pt
Pt Pt
Pt Pt CH
CH22
HH33N
N O
O NH22
NH O O
O CH
CH33 NH22 O C
O
Nedaplatin
Nedaplatin Lobaplatin
Lobaplatin Eptaplatin
Eptaplatin

Fig. 1 Platinum-based drugs currently in clinical use

Figure 2. Satraplatin and picoplatin are able to cir-
cumvent some drug resistance. They have recently
shown promising clinical activity, respectively, in
hormone-refractory prostate cancer and in small-
cell lung cancer, and are strongly anticipated to
receive clinical approval (7, 8).
The clinical use of Pt-based drugs is frequently
limited by severe toxic side effects such as nephro-
toxicity, neurotoxicity and meylosuppression, as
well as drug resistance. One of the most intriguing
strategies to overcome these drawbacks is to
encapsulate the agent in a liposome (9). Some anti-
cancer drugs such as doxorubicin have been
approved in their liposomal formulations (doxil in
the case of doxorubicin) for the treatment of
AIDS-related Kaposi’s sarcoma (AIDS-KS) and
relapsed ovarian cancer in the U.S.A. and Europe
(10). Several different liposomal formulations of
cisplatin have also been prepared and biologically
evaluated. Among them, SPI-77 and lipoplatin are
currently in Phase I and II clinical trials (11–14).
To date, none of the liposomal formulations of cis-
platin have been approved for clinical use. The key
reasons for this are the poor water solubility and
low lipophilicity of cisplatin (other Pt anticancer
drugs show similarly poor lipophilicity), which
makes it difficult to efficiently encapsulate the drug
in a liposome. An alternative approach is to syn-
thesise lipophilic Pt complexes. NDDP
(cis-bis-neodecanoato-trans-R,R-1,2-diaminocyclo-
hexane platinum(II)) is an example of such a
complex, and its liposomal formulation L-NDDP
(aroplatin) has entered Phase II clinical trials (15,
16). Unfortunately, NDDP is intraliposomally

Fig. 2 Chemical structures of

satraplatin (JM216) and picoplatin
H3C C O (AMD473)
O H3N Cl
H3 N Cl
Pt Pt

NH 2 N Cl
O Cl
CH3
O C CH3

Satraplatin
JM216 Picoplatin
(JM216) (AMD473)

Platinum Metals Rev., 2008, 52, (3) 164

unstable due to the presence of two monodentate
carboxylate leaving groups (17, 18). Furthermore,
in order to improve the liposolubility of NDDP,
highly branched aliphatic carboxylate groups were
used, greatly increasing the molecular weight and
making passive diffusion through the cell mem-
brane difficult. It is therefore important to identify
lipophilic Pt complexes using chelating bidentate
ligands of small molecular weight.
Design and Synthesis
On the basis of the above findings, we designed
a series of novel lipophilic platinum(II) compounds
of salicylate derivatives (19) including 3,5-diiodo-
salicylate (DISA), 3-isopropyl-6-methylsalicylate
(o-thymotate) and 3,5-diisopropylsalicylate
(DIPSA) as the leaving groups. DISA is a food
additive used as an iodine source and o-thymotate
is derived from plants of the genus Thymus.
Salicylate and its derivatives are important non-
steroidal anti-inflammatory agents. Their capacity
to block metastasis of cancer cells by inhibiting
synthesis of prostaglandin is well known, as well as
their reduction of the ototoxic and nephrotoxic
side effects caused by cisplatin (20). This is a fur-
ther reason for selecting salicylate derivatives as
leaving groups in the target Pt complexes.
As for non-leaving groups, the diammines of
cisplatin, oxaliplatin and eptaplatin were used. The
design strategy in our research is to develop Pt
complexes providing higher liposolubility and
chemical stability, along with higher antitumour
activities and lower systemic toxicity. The com-
pounds we designed are illustrated in Figure 3.
O
O H H
H H22
22
HH33N O
O R
R N
N O
O R
Pt
Pt Pt
Pt
11
HH33N
N O R
R N
N O
O R
H2
H H
2 H
R
R R
Compounds 1–3: R = R1 = I, R2 = H
Compounds 4–6: R = CH3, R1 = H, R2 = CH(CH3)2
Compounds 7–9: R = R1 = CH(CH3)2, R2 = H
Fig. 3 Structures of platinum(II) complexes of salicylate derivatives
Platinum Metals Rev., 2008, 52, (3)
All the compounds can be synthesised as pre-
cipitates from aqueous solution by the general
method shown in Scheme I, owing to their low
water solubility. Potassium tetrachloroplatinate
(K2PtCl4) was first converted to potassium
tetraiodoplatinate (K2PtI4) in situ by reaction with
potassium iodide (KI). K2PtI4 was then treated
with ammine/diamine (‘A2’) to form diam(m)ine-
diiodoplatinum(II) complexes, which were reacted
with silver nitrate (AgNO3), giving rise to
[PtA2(H2O)2](NO3)2. The addition of sodium sali-
cylate derivatives (‘Na2X2’) to the solution of
[PtA2(H2O)2](NO3)2 precipitated the target com-
pounds. Purification was carried out by
re-precipitation from an ethanol or acetone solu-
tion of the compound after adding water.
Characterisation and Lipophilicity
The compounds were characterised by elemen-
tal analysis, Fourier transform infrared (FTIR)
spectroscopy, 1H nuclear magnetic resonance
(NMR) spectroscopy and positive ion fast atom
bombardment mass spectrometry (FAB+-MS).
The elemental analysis data for each compound
were in good agreement with the empirical for-
mula proposed. All the compounds developed
[M + H]+ peaks in the FAB+-MS spectra, corre-
sponding to their molecular weights. The binding
of the salicylic acid derivatives to Pt(II) atoms as
a bidentate ligand was confirmed by the shift of
the C=O absorption frequency, νC=O, to lower
values and the absence of νO–H absorption in the
IR spectra in the resulting compounds. 1H NMR
spectral peaks were compatible with the chemical
O
O 2 H
H H
H22 O
O
R 2
2
O
O N
N O
O R
R
2
Pt
Pt
R 11 1
O
O
N
N O R
R
1
H2
H H 2
R R
R
165
 KI A2 AgNO3 Na2X2
K2PtCl4 K2PtI4 cis-[Pt(II)A2I2] cis-[Pt(II)A2(H2O)2]2+ cis-[Pt(II)A2X2]

H H
H
NH
N H22 O
O NH
NH 22
A22==2NH
A 2NH33 , ,
, O
O
NH
N H2
, NH
NH 22
H HH
O
O
–- 2
O
O R
R2
X22==
X
–- 1
O
O R
R1

R
R

Scheme I General procedure for the synthesis of the platinum(II) compounds of salicylate derivatives

structures given in Figure 1. In order to further
explore the chemical structures, we attempted to
prepare single crystals suitable for X-ray crystal-
lography, but failed. So we resorted to the
“Gaussian 03” computer software (21, 22) and
constructed the chemical structures of two repre-
sentative Pt compounds 6 and 8, as shown in
Figure 4.
The Pt(II) compound had the expected square
planar geometry exhibiting the usual structural
parameters. Pt-N1, Pt-N2, Pt1-O1, and Pt1-O2
distances were in the normal range, and bond
angles of O2-Pt1-O1, N1-Pt1-N2 were also within
the normal values for other diaminedicarboxylato-
platinum(II) complexes (23–25).
The solubilities of the compounds 1–9 in both
water and organic solvents such as ethanol, ace-
tone and ether were determined. All the
compounds except for compounds 1 and 4 had
low solubility in water but high solubility in the
organic solvents (> 20 mg cm–3). Partition coeffi-
cients in an octanol/water system were measured
for the lipophilic Pt compounds 2, 3, 5, 6, 7, 8 and
9. The partition coefficients and solubility in water
are listed in Table I. The lipophilic complexes were
stable in the organic solvents for five days at room
temperature, as indicated by monitoring their ultra-
violet (UV) spectra. Presumably this stability
results from the chelation effect of the leaving
groups.
From Table I it appears that both the carrier
and leaving group influenced the lipophilicity of
the compounds. For the same leaving group the
order of lipophilicity was: DACH > BAMID >
NH3, and DIPSA > thymotate > DISA when the
carrier is the same. (DACH = trans-1R,2R-

N1-N2-O1-O2: 0.44º N1-N2-O1-O2: 0.56º

Fig. 4 The steric structures of platinum compounds 6 and 8

Platinum Metals Rev., 2008, 52, (3) 166

 Table I
Partition Coefficients and Solubility of the Platinum Compounds

Compound 1 2 3 4 5 6 7 8 9 Cisplatin Carboplatin

Solubility
in water, 300 12 25 250 12 7.3 5.9 5.7 3.5 1000 17,500
–
μg cm 3
Partition
coefficient, – 3.3 3.1 – 3.4 4.3 4.1 4.4 4.3 – –
log P

diaminocyclohexane; BAMID = (4R,5R)-
4,5-bis-(aminomethyl)-2-ispropyl-1,3-dioxolane.)
Biological Evaluation
The target Pt compounds 1–9 were assayed in
vitro against several human cancer cell lines, including
A549 (human lung carcinoma) and SGC-7901
(human gastric carcinoma). Cellular survival was
evaluated by the MTT (3-(4,5-dimethylthiazol-2-yl)-
2,5-diphenyltetrazolium bromide) method (26). The
median inhibitory concentration (IC50) values were
calculated from plots of cell survival (%) versus
compound concentration (in μM).
Surprisingly, all the compounds were more
active against A549 and SGC-7901 cell lines with
lower IC50 values than the parent drugs carbo-
platin, oxaliplatin and SKI-2053R
(cis-malonato(4,5-bis(aminomethyl)-2-isopropyl-
1,3-dioxolane)platinum(II)) (Table II). Among the
lipophilic compounds 2, 3 and 5–9, compounds 6
and 8 were the most active. No clear structure-
activity relationship could be established from in
vitro activity.

Table II
In Vitro Cytotoxicity of the Platinum Compounds Against Selected Human Tumour Cell Lines

Compounds Carriers Leaving groups IC50, μM

(non-leaving groups)
A549 SGC-7901

1 2NH3 DISA 1.54 ± 0.08 2.65 ± 0.16

2 DACH DISA 1.05 ± 0.05 2.93 ± 0.13
3 BAMID DISA 2.16 ± 0.11 2.93 ± 0.15
4 2NH3 thymotate 0.89 ± 0.03 1.83 ± 0.09
5 DACH thymotate 1.49 ± 0.04 6.95 ± 0.62
6 BAMID thymotate 1.27 ± 0.07 2.64 ± 0.06
7 2NH3 DIPSA 0.33 ± 0.03 7.63 ± 0.82
8 DACH DIPSA 0.28 ± 0.03 1.09 ± 0.06
9 BAMID DIPSA 1.80 ± 0.07 2.54 ± 0.34
Carboplatin 2NH3 CBDCA* 9.26 ± 0.25 16.34 ± 0.69
Oxaliplatin DACH oxalate 3.54 ± 0.18 7.77 ± 0.56
SKI-2053R BAMID malonate 3.56 ± 0.20 2.36 ± 0.07
*CBCDA = cyclobutane-1,1-dicarboxylate

Platinum Metals Rev., 2008, 52, (3) 167

 Compounds 6 and 8 were therefore evaluated
for their in vivo antitumour activity using conven-
tional methods (27). Sarcoma S180 tumour-
bearing mice and NCI-H460 (human lung cancer)
xenograft mice were established and used as the in
vivo models, as described in previous studies (28,
29). The potency of the antitumour effects was
measured in terms of the ratio of tumour weights
for treated (T) and control (C) animal groups
(T:C), expressed as a percentage. Tables III and IV
show the antitumour activity of compound 6 in
solid S180 tumour-bearing mice, and of compound
8 in mouse NCI-H460 xenograft following
intraperitoneal (i.p.) administration. The results
indicate that compound 6 exhibited in vivo activity
comparable to carboplatin in treating animals with
S180. However compound 6 was much more
active in vitro than carboplatin, probably due to its
different pharmacokinetic behaviour. Nevertheless
compound 8 was more effective on mouse NCI-
H460 xenograft than carboplatin and oxaliplatin.
We also tested the preliminary toxicity of com-
pound 8. A range of doses (mg kg–1) of the test
compound were administered i.p. to healthy
Institute of Cancer Research mice in volumes of
0.1 cm3 per 10 g body weight (n = 10, 12–22 g, in
standard environmental conditions).
After fourteen days, the median lethal dose
(LD50) was calculated by the Bliss method (30).
The data in Table V show the LD50 value to be
230 mg kg–1 (95% confidence limit 207 to 258
mg kg–1) by i.p. administration to ICR mice, much
larger than that of carboplatin (150 mg kg–1) and
oxaliplatin (19.8 mg kg–1), indicating that
compound 8 was less toxic. Antitumour activity
of the two compounds on other animal models
is being assayed at the Shanghai Institute of
Materia Medica.

Table III
Antitumour Activity of Platinum Compound 6 in Mice with S180

Group Dose, Treatment Number Tumour T:C, %

mg kg–1 scheme of mice weight, g,
x ± SD
Control – – 12 1.42 ± 0.25 –
Compound 6 30 i.p., d 1, 4 6 1.26 ± 0.34 83.4
60 6 0.74 ± 0.51 53.1*
90 i.p., d 1 6 0.96 ± 0.29 67.6*
Carboplatin 60 i.p., d 1, 4 8 0.62 ± 0.29 43.7*

Note: The compound was dissolved in arachis oil before administration; SD = standard deviation; d = day(s);*P < 0.01 vs. control

Table IV
Antitumour Activity of Platinum Compound 8 in Mouse NCI-H460 Xenograft

Group Dose, mg kg–1 Scheme Number of mice RTV, x ± SD T:C, %

Control – – 12 18.5 ± 5.4 –
Compound 8 15 i.p., d 0, 4, 8 6 11.5 ± 3.8 62.2
30 6 5.7 ± 2.0 38.8*
60 i.p., d 0 6 7.1 ± 1.9 30.4*
Carboplatin 60 i.p., d 0, 4, 8 8 8.5 ± 4.1 45.9*
Oxaliplatin 9 i.p., d 0, 4, 8 6 11.2 ± 7.3 60.5*
Note: The compound was dissolved in arachis oil before administration; *P < 0.01 vs. control; RTV = relative tumour volume

Platinum Metals Rev., 2008, 52, (3) 168

 Table V
Acute Toxicity of Platinum Compound 8 Following Intraperitoneal Administration in Mice
Group Dose, mg kg–1 Number of mice
1 197.0
2 226.0
3 260.0
4 299.0
5 344.0
Liposomal Platinum Compound
A liposomal formulation of compound 8 has
been successfully prepared in our laboratory by an
evaporation-lypophilisation method. The com-
pound, lipoid Emblica officinalis (Indian gooseberry)
polyphenol fraction (EOP) and cholesterol were
mixed and dissolved in chloroform. After removal
of chloroform at 37ºC in a rotary evaporator, tert-
butanol was added to form a clear solution. The
solution was freeze-dried, yielding lyophilised pre-
liposomal powder from which the final liposomal
Pt compound can be obtained by reconstitution in
aqueous solution.
The liposomal entrapment efficiency (EE) was
greatly influenced by pH, as shown in Table VI.
EE exceeded 95% when pH was below 4.0, indi-
cating good compatibility between compound 8
and the lipids used. The optimal pH was 3.4 to 4,
since the compound would undergo dissociation
under more acid conditions. The average size of
the liposome reconstituted in saline varied from
100 to 300 nm with a distribution index of 0.1 to
0.2 (Figure 5). As observed by transmission elec-
tron microscopy (TEM), the particles were of
elliptical or ellipsoidal form, containing about 5%
of Pt compound (Figure 6). The liposomal formu-
lation of compound 8 so prepared was determined
by high-performance liquid chromatography
Table VI
Effect of pH on Liposomal Entrapment Efficiency (EE)
pH 2.6–3.0 3.5
EE, % 99 95–97
Platinum Metals Rev., 2008, 52, (3)
Death number LD50, mg kg–1
10 2
10 6
10 7 230.9
10 7
10 10
(HPLC) to be stable for ninety days when kept at
4ºC in a sealed, nitrogen-filled container.
Conclusion
The three principal Pt drugs, cisplatin, carbo-
platin and oxaliplatin, along with other Pt drugs
including nedaplatin, lobaplatin and eptaplatin,
continue to have a major role in contemporary
medical oncology. Should other Pt drugs such as
satraplatin and picoplatin receive approval for clin-
ical use, they would further broaden the
applicability of Pt compounds to prostate cancer
and small-cell lung cancer. However, reducing tox-
icity and increasing activity are still the most
important goals for Pt drug development. These
will be achieved only by targeting tumours or
tumour cells either via liposomal formulations or
with new tumour-specific Pt compounds.
Therefore an effective liposomal formulation
affording antitumour activity must be developed,
while preserving the chemical stability of Pt com-
pounds within the liposomes up to the point of
administration to cancer patients. Lipophilic Pt
complexes with chelating bidentate ligands as the
leaving group are required for such a liposomal
formulation.
Our studies show that the Pt(II) compounds
with salicylate derivatives as the leaving group are
4.0 4.5 5.0 6.0–7.0
93–95 90 85 80
169

Proportion of sample of given diameter, %
40
20
5 10
Diameter, nm
100 nm
Fig. 6 Transmission electron microscope image of the
liposome
lipophilic with partition coefficients of 3 to 4, and
are stable as a result of the chelation effect of the
leaving groups. Among them, Pt compound 8
shows greater antitumour activity and less toxicity
than carboplatin and oxaliplatin. Its liposomal for-
mulation has the advantages of high liposomal
entrapment efficiency, high drug content and long
stability, showing great potential for further devel-
opment as a novel liposomal Pt drug which will
directly target tumours. Further biological evalua-
tion for compound 8 and its liposomal formulation
including antitumour activity, toxicities and drug
Platinum Metals Rev., 2008, 52, (3)
Fig. 5 The size distribution of the
liposomal formulation of platinum
compound 8
50 100 500 1000
distribution are being carried out in our labora-
tories. Of course, there are many hurdles to be
overcome and much research to be done before
clinical testing can begin.
Acknowledgements
We are grateful to the Yunnan Provincial
Government for financial support for this research
and development (No. 2004KFZX-17,
2006C0070M).
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The Principal Author

Professor Wei-Ping Liu was born in 1963 in the People’s Republic of
China and received his Bachelor’s degree in Chemistry in 1983 from
Wuhan University. He obtained his Master’s degree in the chemistry
of the precious metals in 1986 at the Kunming Institute of Precious
Metals, where he is currently a research professor and the Head of
the Chemistry and Pharmacy Department. He specialises in research
and development on platinum-based antitumour compounds.

Platinum Metals Rev., 2008, 52, (3) 171

DOI: 10.1595/147106708X333818
CRC International Symposium:
Cross Coupling and Organometallics
Reviewed by Thomas Colacot
Johnson Matthey, Catalysis and Chiral Technologies, West Deptford, New Jersey 08066, U.S.A.; E-mail: colactj@jmusa.com
The third CRC International Symposium on
Cross Coupling and Organometallics (1) was con-
ducted on 25th September 2007 at the Université
de Lyon, ESCPE Lyon, France; the institution
where Victor Grignard was a Chemistry
Professor. Although it was a one-day gathering,
about 250 participants attended from all over the
world. Out of the nine speakers, I was the only
one from industry. In addition to the talks there
were a poster session and vendor booths. The
details of the meeting are summarised in this
report.
The opening address was given by Professor
Tamotsu Takahashi who emphasised that CRC
stands for Catalysis Research Center of Hokkaido
University, Japan, which is the main sponsor of
the Symposium. Professor Takahashi strongly
believes that the area of cross-coupling will be
recognised by the award of a Nobel Prize in the
near future, as no other field of chemistry has
grown like this one over the past two decades. He
thanked agencies such as the Japan Interaction in
Science and Technology Forum (JIST) and various
fine chemicals companies for their sponsorship.
The purpose of this review is to provide a back-
ground about the speakers and their original
contributions to the area of coupling.
In 1966 Professor E. Negishi joined H. C.
Brown’s group to work on C–C bond forming
reactions using organoboron compounds. From
1976 to 1978 he published about ten papers
describing palladium- and nickel-catalysed cross-
coupling reactions using magnesium, zinc, boron,
aluminium and tin, while he was working at
Syracuse University as an Associate Professor.
Currently he occupies the chair of the H. C.
Brown Distinguished Professor of Chemistry at
Purdue University, U.S.A. Negishi is known for
his work on coupling using organozinc reagents;
Platinum Metals Rev., 2008, 52, (3), 172–176
these allow cross-coupling under milder condi-
tions than is the case using organomagnesium
reagents.
During his talk Negishi praised Grignard for
initiating a new era in organometallic chemistry
relevant to organic synthesis. However,
“Grignard left a big hole”, he said, which Negishi
and others are trying to fill currently. The devel-
opments in this area are summarised in a recent
review (2). Negishi has been very successful in
using [1,1'-bis(diphenylphosphino)ferrocene]-
dichloropalladium (dppfPdCl2), bis(2-diphenyl-
phosphinophenyl)ether dichloropalladium
(DPEphosPdCl2) and bis(tri-tert-butylphosphine)-
palladium (Pd(tBu3P)2) catalysts for various
organozinc-based transformations to make natur-
al products such as xerulin, carotenes,
scyphostatin, γ -bisabolenes, 6,7-dehydrostipi-
amide, O-methylmyxalamide D, amphotericin B,
mycolactone A/B and epolactaene, by simple and
efficient ways. He has also successfully complet-
ed asymmetric syntheses of various molecules.
One of the recent examples from his group is the
stereoselective synthesis of (+)-epolactaene, 1, a
microbial metabolite isolated from fungal strain,
Penicillium.
Professor A. Suzuki spent his entire academic
life at Hokkaido University, starting from 1954 as
a B.S. student, except for his postdoctoral studies
at Purdue with Professor H. C. Brown from 1963
to 1965. He is currently a Professor Emeritus at
Hokkaido University. Of the various coupling
reactions, Suzuki coupling has received the most
attention both in industry and academia, with the
greatest number of publications/patents since
1990. Part of the reason for this growth is due to
the non-toxicity of readily available boron
reagents such as boronic acid, pinacolboronate
and potassium salts of trifluoroboronate for
172
 O
O
HO
N O
H 1(+)-epolactaene
(+)-Epolactaene
coupling reactions with both alkenyl- and aryl-
based electrophiles. These reactions can be carried
out under both homogeneous and heterogeneous
conditions in the presence or absence of water.
The conditions are typically milder. Because of the
wider applications of his work in industry, Suzuki
should be the first name to be considered for a
Nobel Prize in the area of cross-coupling.
In his talk, Suzuki highlighted the develop-
ments in this area from 1979 onwards. Some of
the important generations of catalysts which were
mentioned in his talks were tetrakis-
(triphenylphosphine)palladium (Pd(Ph3P)4),
dppfPdCl2, Pd(tBu3P)2 and Buchwald ligands in
conjunction with Pd. The electron-rich and bulky
ligand-based catalysts were responsible for cou-
pling aryl chlorides (3) and hindered substrates (4).
Suzuki also touched upon recent progress on alkyl
halide coupling, a very challenging area due to the
propensity of alkyl substrates to undergo β-hydro-
gen elimination. Interestingly, Professor Suzuki
2 Palytoxin, C129H223N3O54
(Molecular weight = 2678.6)
Platinum Metals Rev., 2008, 52, (3)
COOMe
had published a paper in 1992 (5) on the coupling
of n-hexyl iodide with n-octyl 9-borabicy-
clo[3.3.1]nonane (n-octyl-9-BBN) to produce
tetradecane in 64% yield using the catalyst
Pd(Ph3P)4. Fu’s reinvestigation of the reaction
using n-dodecyl bromide yielded 93% product
when the catalyst system was changed
to palladium acetate/tricyclohexylphosphine
(Pd(OAc)2/Cy3P) (6). Suzuki’s talk also pointed
towards the Suzuki coupling step in Kishi’s syn-
thesis of palytoxin, 2, an incredibly complex
marine natural product containing 71 stereo-
chemical elements (7). This is still considered by
many to be the greatest synthetic accomplish-
ment ever, due to its structural complexity.
Professor K. Tamao has been the Director of
RIKEN’s Advanced Science Institute since 2005.
Earlier, he spent most of his career at Kyoto
University. His lecture was dedicated to M.
Kumada who died on 28th June 2007.
Tamao started his lecture by stating that
173
Ni-catalysed cross-coupling was reported inde-
pendently by Corriu (8) from France and Kumada
(9) from Japan in 1972. Applications of Ni chem-
istry were different from those of Pd chemistry
even in the 1970s, in the sense that some Ni cat-
alysts were useful for aryl chloride and aryl
fluoride coupling. Although his lecture gave a
brief account of what has happened in the area of
Ni- and Pd-catalysed Kumada type coupling since
1972, Tamao’s major focus was on communicat-
ing some characteristic features of Ni-catalysed
coupling, in addition to providing insights into
the mechanistic understanding of Ni-catalysed
coupling vs. Pd-catalysed coupling. Tamao also
emphasised the common role of Lewis acids in
activating aryl–fluoride and aryl–nitrogen bonds
in cross-coupling reactions (10).
Professor G. Fu is currently a full professor at
the Massachusetts Institute of Technology (MIT),
U.S.A. He worked with Professor Evans (Harvard
University, U.S.A.) and Professor Grubbs
(California Institute of Technology (Caltech),
U.S.A.) for his Ph.D. and postdoctoral studies,
respectively. Fu’s contributions are very significant
in revitalising the area of coupling by establishing
the importance of bulky electron ligands (such as
t
Bu3P) in aryl chloride coupling, although Koei
from Japan has also earlier worked on the
bulky tBu3P.
In his lecture Fu described his latest work in one
of the yet challenging areas in coupling namely,
coupling reactions between two sp3-hybridised car-
bon centres (Csp3–Csp3 coupling). His recent
contributions in developing Ni- and Pd-based
methodologies for coupling unactivated primary
and secondary alkyl electrophiles that bear
β-hydrogen were discussed in detail. In his lecture
he also suggested that Kochi’s radical mechanism
might be more suited to explaining the Ni-catalysed
coupling in comparison to the oxidative addition,
transmetallation and reductive elimination steps in
the Pd-catalysed coupling. His work on asymmetric
Negishi coupling was also discussed in some detail.
Professor T. Hiyama has been a full professor at
Kyoto University since 1997. Prior to this he held
various academic and industrial positions
in Japan.
Platinum Metals Rev., 2008, 52, (3)
The Hiyama coupling involves the coupling
of aryl, alkenyl or alkyl halides or pseudohalides
with organosilanes. To drive silicon-based
cross-coupling, formation of a pentacoordinat-
ed silicate intermediate is required in the
catalytic cycle. Therefore this reaction requires
an activating agent such as a base or fluoride
ions, for example tris(dimethylamino)sulfonium
difluorotrimethylsilicate (TASF) or tetra-n-
butylammonium fluoride (TBAF). The reaction
rate is typically increased by using silanes con-
taining R groups such as fluoro or alkoxy
instead of alkyl. In his talk Hiyama discussed
stable and easy-to-handle tetraorganosilicon
reagents with 2-hydroxymethylphenyl groups
on Si as reagents to deliver organic groups to
palladium, copper and rhodium during catalysis,
Scheme I.
In general, organosilanes are stable and easi-
ly prepared compounds, with lower toxicity
than their Sn analogs. Hiyama’s talk also
focused on some of his recent published results;
see References (11–13).
Professor P. Dixneuf is a Professor of
Chemistry at the Université de Rennes, France.
He has published over 350 papers in inter-
national journals including several reviews; also
book chapters and patents.
Unlike conventional cross-coupling process-
es, Dixneuf ’s focused on making C–C bonds
using ruthenium-based organometallics. The
use of Ru(II) complexes such as cyclopenta-
dienyl 1,5-cyclooctadienyl ruthenium chloride
(Cp*Ru(COD)Cl) in regio- and stereoselective
oxidation was highlighted with several exam-
ples. His approach is to develop novel greener
pathways to organic molecules in an atom eco-
nomic way. The details of the work are already
published; see References (14–16).
Professor G. Balme has been a Research
Director first class (DR1) at the Centre National
de la Recherche Scientifique (CNRS), Université
Claude Bernard Lyon 1, France, since 2005. Her
talk was centred on ‘cyclo-functionalising’ un-
activated C–C multiple bonds using Pd
catalysts. Her work has practical applications
such as one-pot synthesis of substituted furans,
174
 Scheme I
O
R-R'
RMgX/H2O
Me2Si
PdCl2
CuI catal. K2CO3 {
Ligand DMSO
O
HO Me {
R'-I Si K
Me
R R
Si
Me2

lactone lignans and cyclopropanes. Professor
Balme has published several articles in this area.
Professor O. Baudoin has been an Associate
Professor of Chemistry at the Université Claude
Bernard Lyon 1 and ESCPE Lyon, France, since
2006. In his talk Professor Baudoin discussed the
Pd-catalysed C–H activation, also called direct
arylation. This area has received much attention
recently as it is one step ahead of the convention-
al C–C cross coupling chemistry such as that of
Suzuki, Hiyama and Negishi. The other signifi-
cant players in this area are Fagnou, Samford,
Sames and Lautens. Some of the important pub-
lications in this area are References (17–19).
Thomas J. Colacot has been working as a
Research and Development Manager in
Homogeneous Catalysis at Johnson Matthey
Catalysis and Chiral Technologies (CCT) with
global responsibilities since 2004, in addition to a
part-time assignment as a visiting graduate pro-
fessor at Rutgers, the State University of New
Jersey, U.S.A.
The work is mainly aimed at developing and
commercialising Pd-based catalysts, as well as
providing practical catalytic solutions to challeng-
ing coupling reactions in the fine chemicals and
pharmaceuticals arena. In addition to developing
new catalysts, research involves understanding
the roles of the catalyst, substrate and reaction
conditions. One of the air-stable, highly active
and versatile catalysts that has been developed
recently is [1,1'-bis(di-tert-butylphosphino)-
ferrocene]dichloropalladium (dtbpfPdCl2), 3. An
example of a supported Pd catalyst is structure 4.
A few typical publications in this are given in
References (20–23).

Cl
P Pd
Pd P
Fe
Fe Cl
Ph
Ph Ph

Ph Ph

3 dtbpfPdCl2 4 Q-Phos based FibreCat

Platinum Metals Rev., 2008, 52, (3) 175

Conclusion
Although work on coupling dates back to the
1970s, the last two decades have seen major
breakthroughs in the area. These have been dri-
ven by applications in the fine chemical and
pharmaceutical industries for the construction of
complex organic molecules. This area will grow
continuously. Remaining challenges include
Csp3–Csp3 coupling, asymmetric coupling and
metal residues in the product.

References
1 CRC International Symposium: Cross Coupling
and Organometallics, 25th September, 2007, Lyon,
France: http://www.cpe.fr/crcsymposium/;
Catalysis Research Centre, Hokkaido University:
http://www.cat.hokudai.ac.jp/
2 E. Negishi, Bull. Chem. Soc. Jpn., 2007, 80, (2), 233
3 A. F. Littke, C. Dai and G. C. Fu, J. Am. Chem. Soc.,
2000, 122, (17), 4020
4 T. E. Barder, S. D. Walker, J. R. Martinelli and S. L.
Buchwald, J. Am. Chem. Soc., 2005, 127, (13), 4685
5 T. Ishiyama, S. Abe, N. Miyaura and A. Suzuki,
Chem. Lett., 1992, 21, (4), 691
6 M. R. Netherton, C. Dai, K. Neuschütz and G. C.
Fu, J. Am. Chem. Soc., 2001, 123, (41), 10099
7 R. W. Armstrong, J.-M. Beau, S. H. Cheon, W. J.
Christ, H. Fujioka, W.-H. Ham, L. D. Hawkins, H.
Jin, S. H. Kang, Y. Kishi, M. J. Martinelli, W. W.
McWhorter, Jr., M. Mizuno, M. Nakata, A. E.
Stutz, F. X. Talamas, M. Taniguchi, J. A. Tino, K.
Ueda, J. Uenishi, J. B. White and M. Yonaga, J. Am.
Chem. Soc., 1989, 111, (19), 7525
8 R. J. P. Corriu and J. P. Masse, J. Chem. Soc., Chem.
Commun., 1972, (3), 144a
9 K. Tamao, K. Sumitani and M. Kumada, J. Am.
Chem. Soc., 1972, 94, (12), 4374
10 N. Yoshikai, H. Mashima and E. Nakamura, J. Am.
Chem. Soc., 2005, 127, (51), 17978
11 Y. Nakao, Y. Hirata and T. Hiyama, J. Am. Chem.
Soc., 2006, 128, (23), 7420
12 Y. Nakao, T. Yukawa, Y. Hirata, S. Oda, J. Satoh
and T. Hiyama, J. Am. Chem. Soc., 2006, 128, (22),
7116
13 Y. Nakao, A. Yada, S. Ebata and T. Hiyama, J. Am.
Chem. Soc., 2007, 129, (9), 2428
14 “Ruthenium Catalysts and Fine Chemistry”, eds. C.
Bruneau and P. H. Dixneuf, Topics in
Organometallic Chemistry, Vol. 11, Springer,
Berlin, Heidelberg, 2004
15 C. Bruneau, S. Dérien and P. H. Dixneuf, in “Metal
Catalyzed Cascade Reactions”, ed. T. J. J. Müller,
Topics in Organometallic Chemistry, Vol. 19,
Springer, Berlin, Heidelberg, 2006, pp. 295–326
16 C. Bruneau and P. H. Dixneuf, Angew. Chem. Int.
Ed., 2006, 45, (14), 2176
17 K. Goldula and D. Sames, Science, 2006, 312, (5770),
67
18 D. Alberico, M. E. Scott and M. Lautens, Chem.
Rev., 2007, 107, (1), 174
19 L.-C. Campeau and K. Fagnou, Chem. Commun.,
2006, (12), 1253
20 G. A. Grasa and T. J. Colacot, Org. Lett., 2007, 9,
(26), 5489
21 G. A. Grasa and T. J. Colacot, Org. Proc. Res. Devel.,
2008, 12, (3), 522
22 T. J. Colacot and H. A. Shea, Org. Lett., 2004, 6,
(21), 3731
23 Y. Wang and D. R. Sauer, Org. Lett., 2004, 6, (16),
2793

The Reviewer
Thomas Colacot is a Research and Development Manager in the Catalysis and Chiral Technologies Division at
Johnson Matthey, West Deptford, U.S.A. with global reports and responsibilities. He holds a Ph.D. in Chemistry
and an MBA in Strategic Management. He is involved in the development of new organometallic compounds for
catalysis, process development, supported homogeneous catalysts and high throughput screening of catalysts for
organic reactions, such as C–C couplings and C–heteroatom couplings. He is also a visiting faculty member of
Rutgers University in the Graduate School of Chemistry, where he teaches an applied organometallic chemistry
course relevant to the fine chemicals and pharmaceutical industries. He has published over fifty papers, in addition
to giving numerous lectures all over the world.

Platinum Metals Rev., 2008, 52, (3) 176

DOI: 10.1595/147106708X329273

Electrochemical Water Disinfection:

A Short Review
ELECTRODES USING PLATINUM GROUP METAL OXIDES

By Alexander Kraft
Gesimat GmbH, Köpenicker Str. 325, D-12555 Berlin, Germany; E-mail: alexander.kraft@gesimat.de

Electrochemical water disinfection is a rarely used but convenient and highly efficient way to
produce germ-free water. The technique works without the addition of chemical compounds
to the water to be treated, but is nevertheless based on the biocidal action of various chemical
substances. Electrodes with platinum group metals (pgms) or their oxides as active coatings
are generally the best suited to electrochemical water disinfection. In special cases, novel
doped diamond electrodes can be applied. A short historical and technical overview of the
process is given, augmented by some application examples.

1. Background disinfection’, ‘anodic oxidation’, ‘functional

Electrochemical water disinfection can be
defined as the eradication of microorganisms by
using an electric current passed through the water
under treatment by means of suitable electrodes.
At the phase boundary between the electrodes
and the water, the electric current leads to the
electrochemical production of disinfecting
species from the water itself (for example,
ozone), or from species dissolved in the water
(for example, chloride is oxidised to free
chlorine).
Attempts to clean or disinfect water by direct
electrolysis had been reported as early as the
nineteenth century (see, for example, Reference
(1)). It has even been speculated that the electri-
cal elements (the so-called ‘Baghdad battery’),
which were discovered in 1936 in the ruins of a
Parthian city (inhabited from about 300 BC to
300 AD) near Baghdad in Iraq, were in use for
the electrochemical preparation of germ-free
water (2). Since the end of the nineteenth centu-
ry there have been frequent attempts to use
electrochemical disinfection (for example,
References (3–6)). Until recently none have been
successful, at least not for long-term practical use.
Different terms are or have been in use to
describe this type of water treatment process or
the water produced by this process, such as
‘electrolytic disinfection’, ‘electrochemical
water’ and ‘electrochemically activated water’
among others.
There are three reasons why electrochemical
water disinfection has arrived at technical matur-
ity only recently, rather than earlier in the
(possibly) 2000 years since its discovery:
(a) Sufficiently stable and efficient electrode
materials for electrochemical water disinfec-
tion have been developed and optimised only
in the last forty years. These are titanium elec-
trodes with mixed oxide coatings based on
iridium and/or ruthenium oxide (7–9), and
doped diamond electrodes (10).
(b)The functional interrelationships between
chloride concentration in the water, current,
current density, electrode material, water qual-
ity, electrochemical production of free
chlorine and disinfecting action have been
investigated in detail only recently (11–15).
(c) Development work on electrochemical water
disinfection has often been undertaken by
amateurs in both electrochemistry and water
chemistry, and this remains somewhat true
today. Only a few electrochemists have been
interested in this topic, mostly only for a short
period in their career. This has resulted in mis-
takes in device dimensioning and in
unscientific explanations of the mechanism of
the process.

Platinum Metals Rev., 2008, 52, (3), 177–185 177

2. General Processes for Water
Disinfection
Conventional disinfection methods may be
divided between chemical and physical processes.
In chemical processes, disinfecting substances
such as ozone, chlorine, sodium hypochlorite or
chlorine dioxide are added to the water to be treat-
ed. These processes are reliable, and have proven
their efficiency over many decades. They not only
kill microorganisms, but also provide a disinfection
reservoir which protects the water against recon-
tamination for a certain time. A frequent drawback
of the chemical processes is unwanted side reac-
tions of the disinfectants with substances present
in the water. These reactions lead to disinfection
byproducts, some of which are considered danger-
ous. There are also hazards in producing,
transporting and handling large amounts of such
substances as chlorine and ozone.
In physical disinfection processes the micro-
organisms are removed or killed by means of
irradiation with ultraviolet or ionising radiation,
heating to elevated temperatures, ultrasound, or
separation through membrane filtration. The main
drawback of the physical disinfection methods is
the lack of a reservoir effect. These processes are
only effective in the immediate surroundings of
their operating devices.
As compared with other chemical disinfection
methods, the advantages of electrochemical water
disinfection are obvious: no transport, storage and
dosage of disinfectants are required. The disinfect-
ing effect can be adjusted according to the on-site
demand. Electrochemical water disinfection shows
a reservoir effect and is often more cost-effective
and requires less maintenance than other disinfec-
tion methods. Photovoltaic power supply makes it
possible to use electrochemical water disinfection
far from the electrical supply grid. This may be
important for its application to drinking water in
developing countries. Electrochemical water disin-
fection can also be used in conjunction with other
disinfection methods.
In electrochemical water disinfection, elec-
trodes (at least one cathode and one anode) are
inserted either directly into the volume of water to
be disinfected, or into a bypass pipe. A DC voltage
Platinum Metals Rev., 2008, 52, (3)
is applied between the electrodes, leading to the
electrolysis of the water. At the anode the main
product is oxygen (Equation (i)):
2H2O → O2 + 4H+ + 4e– (i)
accompanied by an acidification of the water in the
vicinity of the anode. At the cathode, hydrogen is
formed (Equation (ii)):
2H2O + 2e– → H2 + 2OH– (ii)
and the water near the cathode becomes alkaline.
Since the evolved hydrogen is generally unwanted,
it must be separated from the water stream.
Because only small amounts are formed at normal
currents (about 0.4 litres of hydrogen is produced
per amp-hour), this is possible without problems
in most cases.
In most practical applications, simple undivided
electrochemical reactors employing parallel-plate,
monopolar electrode stacks are inserted into the
reactor pipe. The electrode plates may be config-
ured as unperforated or perforated plates, or as
expanded metal.
Recently, an electrochemical disinfection
process which completely avoids hydrogen pro-
duction has been developed. Atmospheric oxygen
is reduced to hydroxyl ions at a gas diffusion cath-
ode (16) (Equation (iii)):
O2 + 2H2O + 4e– → 4OH– (iii)
Here the cathodic reaction (Equation (iii)) replaces
the hydrogen producing reaction (Equation (ii)).
The gas diffusion electrodes are composed of a
porous graphite-polytetrafluoroethylene (PTFE)
layer, in contact with a metal mesh as current
collector, and backed by an oxygen-permeable
PTFE layer to prevent water leakage. The graphite
carries a manganese oxide catalyst which eliminates
unwanted hydrogen peroxide.
3. Production of Free Chlorine
from the Chloride Content of
the Water
If electrochemical disinfection is applied to
drinking water, industrial water, seawater or other
solute-containing water, its effect is mainly based
on the electrochemical production of hypochlorite
178
and/or hypochlorous acid from the chloride
content of the water. The effectiveness of this
method has always been accepted for water which
contains higher concentrations of chloride ions (17),
such as seawater with about 19 g l–1 chloride (18), or
where large amounts of sodium chloride have been
added, for instance to swimming pool water
(chloride concentrations here are usually about 2–5
g l–1). For the disinfection of drinking water and
other waters with much lower chloride content, the
effectiveness of the method was not clear for a long
time (19). It was eventually demonstrated that even
at very low chloride concentrations (less than
100 mg l–1) sufficient free chlorine can be produced
to efficiently disinfect water (11–15).
The disinfectant hypochlorous acid/hypochlorite
is produced at the anode in a side reaction to oxygen
evolution. The following simplified reaction mecha-
nism is proposed. First, chlorine is produced
electrochemically from chloride ions dissolved in the
water (Equation (iv)):
2Cl– → Cl2 + 2e–
Chlorine hydrolyses in water and hypochlorous acid
(HClO) is formed (Equation (v)):
Cl2 + H2O → HClO + HCl
Hypochlorous acid and the hypochlorite anion form
a pH-dependent equilibrium (Equation (vi)):
HClO ' ClO– + H+
Free chlorine production efficiency, mg Ah–1
125
100
75
50
25
0 20
Platinum Metals Rev., 2008, 52, (3)
In the nomenclature of water disinfection, the
sum of hypochlorous acid and hypochlorite concen-
trations is usually termed ‘free chlorine’ or ‘active
chlorine’. The disinfecting effect of free chlorine is
based on the release of atomic oxygen according to
Equations (vii) and (viii):
HClO → O + Cl– + H+ (vii)
ClO → O + Cl
– –
(viii)
During the disinfection, chloride ions which have
been consumed by electrochemical free chlorine
production are reformed. Thus there is no overall
change in the chemical composition of the water
during electrochemical water disinfection.
Where there is a low chloride concentration in
the water to be treated (as in drinking water) the cur-
rent efficiency of the electrode material for the
production of free chlorine is crucial; it should be as
high as possible. Very great differences have been
found in the efficiency of free chlorine production
between different electrode materials at low chloride
concentrations (11–13, 15). Figure 1 shows the
(iv)
dependence of the free chlorine production efficien-
cy on chloride concentration for two dimensionally
stable anode (DSA®) type electrodes (using active
coatings of IrO2 or IrO2/RuO2), platinum and
(v)
boron-doped diamond electrodes. It can be seen
that DSA® type electrode materials clearly outper-
form diamond and Pt electrodes, which are
therefore not generally applicable as anodes for
(vi) water disinfection based on the electrochemical
Fig. 1 Dependence of the
electrochemical free chlorine
10 production efficiency on the
chloride content of the
electrolysed water under
IrO2 8
standard conditions using four
different anode materials
Current efficiency, %
(iridium oxide, mixed
6 iridium/ruthenium oxides,
IrO2/RuO2 platinum, doped-diamond)
4
Doped-diamond Pt
2
0
40 60 80 100 120 140 160 180
Chloride concentration, mg l–1
179
production of free chlorine. Diamond electrodes
have another disadvantage in this application area.
Because of their high overvoltage for both oxygen
and chlorine evolution, they may further oxidise
hypochlorite to chlorate and perchlorate (20). Only
very low levels of these disinfection byproducts are
permissible in potable water. Chlorate and per-
chlorate are not formed at DSA® type and Pt
electrodes (11, 13). Earlier devices for electro-
chemical water disinfection employed anode
materials such as carbon (1) or Pt (3, 4) with very
low production efficiency for free chlorine.
Another important aspect in choosing the
appropriate electrode material is electrode lifetime.
Although electrode lifetime has been improved
where electrode polarity remains constant, fre-
quent polarity change between anode and cathode
is still problematic in this regard. Because of the
formation of calcareous deposits at the cathode
during electrolysis in water containing calcium and
magnesium ions, polarity reversal is necessary to
clean the cathode surface of these deposits at reg-
ular intervals (12, 13). The alkaline pH in the
vicinity of the cathode (see Equation (ii)) leads to
the precipitation of calcium carbonate (CaCO3)
and magnesium hydroxide (Mg(OH)2). On revers-
ing the polarity, the former cathode acts as an
Electrolysis time, years
0 1
30
25 IrO2 IrO2/RuO2
20
Cell voltage, V
15
10
5 RuO2
0 100 200 300 400 500 600 700 2250
Electrolysis time, days
Platinum Metals Rev., 2008, 52, (3)
anode and the scaling is removed due to the acidic
anodic pH (see Equation (i)). But polarity reversal
reduces electrode lifetime. This is especially true
for IrO2 or mixed IrO2/RuO2 electrodes (12, 13).
Figure 2 shows the results of a long-term experi-
ment (still running) on the lifetime of electrodes of
various materials under periodic reversal of polari-
ty. A steep rise in cell voltage indicates the total
stripping of the active coating at the end of the
electrode lifetime. The shortest lifetime of the elec-
trodes tested was observed for the RuO2-coated Ti
electrodes, followed by IrO2-coated electrodes
with a lifetime of about three months. Mixed
IrO2/RuO2-coated electrodes had a lifetime of
nearly one year under our experimental conditions.
These materials are all clearly outperformed by
platinised Ti electrodes, which are still running
seemingly unaffected after nearly eight years.
Other means for cathode cleaning have been
investigated, such as ultrasonication (21), and con-
tinuously rotating brushes (22) or vanes (23) which
move over the cathode surface. Another method is
the imposition of a current pulse, which increases
the formation of gas bubbles (24). None of these
techniques have been successful in long-term
operation, so that polarity reversal remains the best
automatic cathode cleaning technique to date.
Fig. 2 Cell voltage
versus electrolysis
6 7 8 time in Berlin tap
water (conductivity
about 0.8 mS cm–1)
for titanium
electrodes coated
with different active
electrode materials
(ruthenium oxide,
iridium oxide,
mixed
iridium/ruthenium
oxides, platinum):
polarity reversal
every 30 minutes,
current density 20
mA cm–2, electrode
distance 4 mm
Pt
2500 2750
180
 An example of an application of electrochemi-
cal water disinfection based on free chlorine
production is the ‘AQUADES-EL’ device. This is
optimised for the cyclic operation of hot water
recirculating systems in larger residential and com-
mercial buildings. Potable water, especially in such
systems, is especially prone to microbial contami-
nation. This is due to high water temperatures
which favour the growth of microorganisms such
as Legionella. From time to time the media report
on legionellosis outbreaks due to contaminated
drinking water systems in hotels, hospitals etc.
However, Legionella is only the most notorious
genus of germs. Others are also dangerous, such as
Pseudomonas aeruginosa, Escherichia coli and
Staphylococcus aureus, to name but a few.
The AQUADES-EL system has been pro-
duced and distributed since 1998 by the German
Platinum Metals Rev., 2008, 52, (3)
companies AquaRotter GmbH and G.E.R.U.S
mbH. More than 400 systems have been sold and
installed in hotels, hospitals, barracks, retirement
homes and other buildings. Figure 3 shows the
AQUADES-EL device, which is usually located in
a bypass to the water recirculation system. It
employs Ti electrodes coated with mixed
IrO2/RuO2. An advanced control system mea-
sures the free chlorine concentration in the water
at several locations in the distribution system at
regular time intervals by amperometric detection.
In many industrial areas, large amounts of
water are used for cooling purposes, as evidenced
by the cooling towers dominating the landscape.
Microbial contamination of cooling water,
whether in cooling towers or air conditioning
systems, currently poses a major problem. Large
concentrations of disinfectant are usually added to
Fig. 3 Electrochemical disinfection
device AQUADES-EL (AquaRotter GmbH
and G.E.R.U.S mbH, Germany) equipped
with mixed iridium/ruthenium oxide-
coated titanium electrodes:
right-hand side: reactor pipe with
inserted electrode stack; upper middle:
power supply and control unit; upper left:
amperometric free chlorine sensor
equipment
181
the cooling water. The two commonest biocides
for cooling towers are free chlorine and quartenary
ammonium compounds. New biocides continue to
be developed, but electrochemical water disinfec-
tion is a promising alternative for this application.
Electrochemical disinfection has been success-
fully implemented in the cooling water
recirculation system of a German paper mill
(Figure 4). The ‘Hypocell® B4’ device from
G.E.R.U.S mbH employs four parallel reactor
pipes. The titanium electrodes carry a mixed
IrO2/RuO2 coating. About 130 m3 of water is
treated. The water has a typical pH of 8.3, a con-
ductivity of 1.9 mS cm–1 and a chloride
concentration of about 280 mg l–1. The flow rate in
the treatment bypass is 1000 l h–1.
4. Ozone Production
If water with low or zero chloride concentra-
tion is required, the addition of sodium chloride is
not acceptable and free chlorine cannot be pro-
duced in situ. Disinfection must therefore be based
on other electrogenerated species. By using anodes
with a high oxygen overvoltage, a high current
® equipped with this technology. An improved
Fig. 4 Hypocell B4 electrochemical disinfection device
(G.E.R.U.S. mbH, Germany), with four pipe reactors
equipped with mixed iridium/ruthenium oxide-coated
titanium electrodes in a cooling water system, installed at
a German paper mill
Platinum Metals Rev., 2008, 52, (3)
density and a low water temperature it is possible
to produce ozone directly from the water accord-
ing to Equation (ix):
3H2O → O3 + 6e– + 6H+ (ix)
Electrochemical ozone production has been
known since the nineteenth century (25).
Electrolysis was the first production method for
ozone (25), but for most applications ozone is now
produced by corona discharge. The disadvantages
of electrolytic production include too low a current
efficiency, complicated production systems, un-
stable electrode materials (such as lead oxide
(PbO2) anodes) and/or difficult-to-handle elec-
trolytes. Electrolytic production may become more
attractive using a new simple electrode assembly
(26) of a ‘sandwich’ configuration: diamond
anode/solid polymer electrolyte (SPE)/cathode
sandwich.
By using such a diamond-SPE sandwich or sim-
ilar device in deionised water, ozone can be
produced with a high current efficiency (up to
47%) (27, 28). These devices can easily be inserted
into water pipes or reservoirs to produce the
required quantity of ozone directly from the water
to be treated. The Nafion® ion exchange mem-
brane may be employed as the SPE material. If the
doped diamond anode is replaced by a Pt- or
IrO2-coated anode, a much lower ozone produc-
tion rate is measured. On the other hand, if Pt is
used as the cathode material, the overvoltage for
hydrogen production can be lowered, minimising
the cell voltage.
For the electrochemical disinfection of ultra-
pure water, or other waters with very low
conductivity (such as rain water), electrochemical
ozone production with diamond-SPE sandwich
electrodes is the method of choice. Figure 5 shows
a small stack of two diamond electrode/SPE/dia-
mond electrode sandwiches. With this technology,
water volume rates from 60 l h–1 up to 5 m3 h–1 can
be treated using different sized electrode stacks. In
recent years several pilot projects have been
ozone generating device is in development. This
produces no hydrogen, and the cathode consumes
oxygen.
182

5. Disinfection or Germ Minimis-
ation by Electrochemically
Produced Oxygen
In some applications, electrolytically produced
oxygen, the main anodic reaction product, shows
some germicidal activity. This is especially true if
anaerobic bacteria are the disinfection target.
An example of this type of application is the
wash water cycle of car wash stations. Here, the
formation of anaerobic digestion products often
leads to bad odours. Anaerobic conditions are
eliminated via the fine dispersion of bubbles of
electrolytically produced oxygen in the water. This
is a highly effective mode of dissolution. For this
application, Pt-coated electrodes are the most suit-
able anodes, because the main germicidal effect is
based on electrolytically produced oxygen and not
on free chlorine. Figure 6 shows the Hypocell® B4
device for germ minimisation in car wash stations,
based on this technology. About twenty-five
systems have been successfully installed.
6. Disinfection by Cathodically
Produced Hydrogen Peroxide
While most of the possible disinfectants in
electrochemical water treatment are produced at
the anode, hydrogen peroxide may also be pro-
duced at the cathode. This process has been used
by Dhar et al. (29) and Drogui et al. (30, 31) for
water disinfection (Equation (x)):
O2 + 2H2O + 2e– → H2O2 + 2OH– (x)
Oxygen dissolved in the water may serve as
the reactant in Equation (x). The maximum
Platinum Metals Rev., 2008, 52, (3)
Fig. 5 Electrode stack with two
diamond-SPE-electrode sandwiches for
ozone production in deionised water
(Gerozon device by G.E.R.U.S. mbH,
Germany)
concentration of oxygen in water which is in equi-
librium with air at 25ºC is about 10 mg l–1
(0.3 mmol l–1). The oxygen produced by the anod-
ic half reaction according to Equation (i) can also
be used for the cathodic production of hydrogen
peroxide. In this case, higher concentrations of
dissolved oxygen are possible, because the water is
in contact with pure oxygen, and not merely with
air. It is also possible to use a gas diffusion cath-
ode on which the oxygen from the surrounding air
is reduced to H2O2. In terms of energy efficiency,
the electrode material best suited to H2O2 produc-
tion is graphite. This material (without additional
catalysts) is also the core component in gas
diffusion electrodes for H2O2 production.
Because of its lower oxidation potential, H2O2
is a less effective disinfectant than free chlorine or
ozone. Therefore, higher concentrations and/or
longer disinfection times are necessary, limiting its
applicability. Hydrogen peroxide has the advan-
tage that its disinfectant action produces neither
byproducts nor residues.
7. Conclusion
Electrochemical water disinfection has many
advantages compared with conventional disinfec-
tion technologies. It has proven its reliability in
several practical applications, mainly for the dis-
infection of drinking water, swimming pool water
and industrial cooling water. Electrochemical
water disinfection has also been used or tested
for the reduction of bacterial contamination in
dental water supplies (32), and for the disinfec-
tion of contact lenses (33) and ion exchange
183

®
Fig. 6 Hypocell B4 electrochemical disinfection device
(G.E.R.U.S. mbH, Germany) equipped with platinised
titanium electrodes, mounted in a car wash station
References
1 J. Chisholm, British Patent 1,499; 1858
2 W. König, “Neun Jahre Irak”, Rudolf M. Rohrer
Verlag, Brünn, München, Wien, 1940, p. 167
3 C. F. Burgess, U.S. Patent 1,200,165; 1916
4 P. M. R. Salles, British Patent 271,721; 1927
5 W. Juda and W. A. McRae, Ionics, Inc., U.S. Patent
2,752,306; 1956
6 A. Reis, N. Kirmaier and M. Schöberl, Institut für
Biomedizinische Technik, U.S. Patent 4,188,278;
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7 P. C. S. Hayfield, Platinum Metals Rev., 1998, 42,
(1), 27
8 P. C. S. Hayfield, Platinum Metals Rev., 1998, 42,
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9 P. C. S. Hayfield, Platinum Metals Rev., 1998, 42,
(3), 116
10 A. Kraft, Int. J. Electrochem. Sci., 2007, 2, (5), 355
11 A. Kraft, M. Stadelmann, M. Blaschke, D. Kreysig,
B. Sandt, F. Schröder and J. Rennau, J. Appl.
Electrochem., 1999, 29, (7), 859
12 A. Kraft, M. Blaschke, D. Kreysig, B. Sandt,
F. Schröder and J. Rennau, J. Appl. Electrochem., 1999,
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13 A. Kraft, M. Wünsche, M. Stadelmann and
M. Blaschke, Recent Res. Devel. Electrochem., 2003, 6, 27
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resins (34) etc. However, only a few electrochem-
ical water disinfection products are currently
available on the market. This is due to the relative
unfamiliarity of the technology, and to fierce
market competition with other technologies.
Eventually, the cost and performance advantages
of electrochemical technology should lead to its
wider use.
RuO2 and/or IrO2-coated electrodes are the
best suited to disinfection based on hypochlorite
generation. This is due to their high production
efficiency for hypochlorite from water with a very
low chloride content. Pt is the favoured electrode
material for oxygen production from natural
waters. Pt electrodes are also the most stable.
For the production of ozone and hydrogen per-
oxide, pgm electrodes are not the first choice,
being outperformed by carbon electrodes, i.e.
doped diamond for ozone, and graphite for hydro-
gen peroxide production.
This article is a translated and revised version of
Reference (35).
14 N. Nakajima, T. Nakano, F. Harada, H. Taniguchi,
I. Yokoyama, J. Hirose, E. Daikoku and K. Sano,
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15 M. E. H. Bergmann and A. S. Koparal, J. Appl.
Electrochem., 2005, 35, (12), 1321
16 M. Wünsche, A. Kraft, W. Kirstein, M. Blaschke and
H. Petzer, AquaRotter GmbH, European Patent
1,326,805; 2005
17 A. T. Kuhn and R. B. Lartey, Chem. Ing. Tech., 1975,
47, (4), 129
18 A. F. Adamson, B. G. Lever and W. F. Stones,
J. Appl. Chem., 1963, 13, (11), 483
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1990, 24, (12), 1491
20 S. Palmas, A. M. Polcaro, A. Vacca, M. Mascia and
F. Ferrara, J. Appl. Electrochem., 2007, 37, (11), 1357
21 A. Kraft, M. Blaschke and D. Kreysig, J. Appl.
Electrochem., 2002, 32, (6), 597
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G.E.R.U.S. mbH, German Patent Appl. 19,836,431;
1999
23 M. A. Silveri, BioQuest, U.S. Patent 5,885,426; 1999
24 Y. Gao, T. Gao, B. Han, D. Zhang and J. Li, The
National Engineering Research Center for Urban
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25 M. B. Rubin, Bull. Hist. Chem., 2001, 26, (1), 40
184
26 M. Stadelmann, M. Blaschke, M. Wünsche,
H. Petzer, A. Kraft, T. Matthee and M. Fryda,
CONDIAS GmbH and G.E.R.U.S. mbH, European
Patent Appl. 1,730,080; 2006
27 A. Kraft, M. Stadelmann, M. Wünsche and
M. Blaschke, Electrochem. Commun., 2006, 8, (5), 883
28 K. Arihara, C. Terashima and A. Fujishima,
J. Electrochem. Soc., 2007, 154, (4), E71
29 H. P. Dhar, J. O. Bockris and D. H. Lewis,
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30 P. Drogui, S. Elmaleh, M. Rumeau, C. Bernard and
A. Rambaud, J. Appl. Electrochem., 2001, 31, (8), 877
31 P. Drogui, S. Elmaleh, M. Rumeau, C. Bernard and
A. Rambaud, Water Res., 2001, 35, (13), 3235
32 L. Jatzwauk and B. Reitemeier, Int. J. Hyg. Environ.
Health, 2002, 204, (5–6), 303
33 G. R. Holland and B. E. Cloud, Allergan, Inc., U.S.
Patent 5,129,999; 1992
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Technologies A/S, World Patent Appl. 02/22,506;
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35 A. Kraft, M. Wünsche, M. Stadelmann and
M. Blaschke, Wasserwirtschaft Wassertechnik, 2006, (9), 36

The Author
Alexander Kraft is co-founder and Managing Director of
Gesimat GmbH, Berlin, Germany, a company which develops
‘smart’ switchable electrochromic glazing. Before starting
Gesimat in 1998, he developed electrochemical water
disinfection technologies and devices at G.E.R.U.S. mbH,
Germany, from 1994. He continued to work for G.E.R.U.S. as a
scientific adviser until 2006. Alexander Kraft received a Ph.D. in
Physical Chemistry (semiconductor electrochemistry) from
Humboldt University, Berlin, in 1994.

Platinum Metals Rev., 2008, 52, (3) 185

DOI: 10.1595/147106708X333827

Processing of Iridium and Iridium Alloys

METHODS FROM PURIFICATION TO FABRICATION

By E. K. Ohriner
Oak Ridge National Laboratory, Materials Science and Technology Division, PO Box 2008, Oak Ridge, TN 37831, U.S.A.;
E-mail: ohrinerek@ornl.gov

Iridium and its alloys have been considered to be difficult to fabricate due to their high melting
temperatures, limited ductility, sensitivity to impurity content and particular chemical properties.
The variety of processing methods used for iridium and its alloys are reviewed, including
purification, melting, forming, joining and powder metallurgy techniques. Also included are
coating and forming by the methods of electroplating, chemical and physical vapour deposition
and melt particle deposition.

Introduction extraction process (4). In the conventional meth-

The metal Ir has a unique combination of prop-
erties, including a high melting temperature,
strength at high temperature, oxidation resistance
and corrosion resistance, that are useful in a range
of applications, particularly at elevated tempera-
ture. However Ir is also one of the more difficult
materials to process into finished products, in
many cases due to the same properties that recom-
mend its use. This was highlighted by the review ‘A
History of Iridium’ published twenty years ago in
this Journal with the subtitle ‘Overcoming the
Difficulties of Melting and Fabrication’ (1). The
purpose of the present review is to summarise
advances in the processing of Ir during the past
two decades. In some cases processing methods
have been refined and improved, while in others
entirely new processing methods have been devel-
oped to serve new applications of Ir. The scope of
this review is limited to the processing of pure Ir
and Ir alloy materials in which Ir constitutes the
majority of the composition. The processing meth-
ods that are reviewed include purification, melting,
powder processing, forming, joining and coating.
Purification
The purity of Ir has been shown to have impor-
tant effects on the mechanical properties of both
the nominally pure metal and its alloys (2, 3). Ir is
separated from platinum group metal (pgm)
concentrates and purified either by conventional
chemical refining methods or by a solvent
ods Ir oxide is dissolved in aqua regia (a mixture of
concentrated nitric and hydrochloric acids) and
precipitated with ammonium chloride. After a
series of dissolutions and precipitations the salt is
heated in a hydrogen atmosphere to produce Ir
sponge. In the solvent extraction method, a series
of organic liquids are used to concentrate various
pgms from aqueous solutions. The Ir can then be
precipitated and heated in hydrogen to produce Ir
sponge. Solvent extraction methods may offer cost
and environmental benefits over conventional
chemical precipitation methods.
The purity of the sponge is sensitive to both the
details of the processing and the starting materials.
A method of chemical purification of Ir com-
pounds following dissolution is reported to
achieve removal of platinum, rhodium, ruthenium
and palladium to levels below 5 parts per million
by weight (ppm) (5). A method of scrap purifica-
tion, as well as fabrication, uses electrodeposition
of Ir from molten salt solution (6). Purification is
effective in removing many base metals, but less so
for some others including pgms. A pyrometallurgi-
cal method for purification of Ir scrap employs
induction melting in a crucible of magnesium
oxide with an air atmosphere, to remove both
volatile impurities through vaporisation and oxide-
forming impurities as a vapour or as a slag (7).
This is a relatively low-cost method, although
some impurities, including iron, are not easily
removed by it.

Platinum Metals Rev., 2008, 52, (3), 186–197 186

 Electron beam melting has been used for
purification and is effective for removal of most
impurities with the exception of refractory metal
elements (8, 9). Recent work treated removal of a
large number of impurity elements by electron
beam melting (10). It showed that titanium, vana-
dium and zirconium were not removed by
electron beam melting, due to negative deviations
from ideal solution behaviour (10). In addition,
several other elements were only partially
removed even under optimal conditions of melt
stirring. The impurity ratio, defined as the ratio by
weight of the final impurity content to the initial
impurity content, was measured for electron beam
melting of Ir buttons under conditions producing
Ir vaporisation of 5.6% by weight. Low ratios
were observed for iron, aluminium and chromium
of 0.004, 0.014 and 0.06, respectively.
Intermediate ratios were obtained for the impuri-
ties platinum, silicon and carbon of 0.11, 0.2 and
0.3, respectively. The results were shown to be
consistent with ideal mixing and vaporisation. The
observed purification behaviour for the impurity
elements Fe, Al, Cr and Si was explained by their
low activity coefficients.
Melting
Melting of Ir is performed by induction melt-
ing, electron beam melting and arc melting
methods. Induction melting, frequently used for
initial melting (11), is performed in air with zirco-
nia or magnesia crucibles. Due to excessive
volatilisation of the crucible material at the Ir melt-
ing temperature (5), the crucibles are not suitable
for use in vacuum. Ceramic inclusions are avoided
by the use of electron beam, plasma or arc melting
with water-cooled copper crucibles. Plasma melt-
ing of Ir is performed at a moderate pressure of
about 50 Pa and provides for some purification by
vaporisation of impurities, although to a lesser
extent than with electron beam melting. In some
cases, the final melting operation prior to defor-
mation processing (12) is electron beam melting
(discussed above under purification). Button arc
melting is used for relatively small quantities of Ir
and Ir alloys, particularly those with alloying
additions subject to vaporisation during melting.
Platinum Metals Rev., 2008, 52, (3)
Vacuum arc remelting (VAR) is applicable to larg-
er-size melts, and provides ingots with little or no
internal porosity (13). The VAR ingots have a rel-
atively large grain size with some degree of
directional solidification. Melting of 27 mm dia-
meter electrodes to produce 63 mm diameter
ingots of an Ir alloy is performed with a direct
current (DC) of 3000 A at 31 V in a vacuum of
about 13 mPa with a melt rate of about 3 kg min–1.
Control of porosity is important even in the case
of ingots to be forged or rolled, since porosity in
the melted ingot may never be completely sealed
even with extensive hot deformation, such as by
hot extrusion (14).
Powder Metallurgy
The powder metallurgy methods of pressing
and sintering can be used to prepare billets for
subsequent hot working to produce a fully dense
product (15), but progress in producing a fully
dense near-net shape by these means has been lim-
ited. In a study of powder metallurgy methods for
pgms and their alloys, including pure Ir and Ir-Pt
alloys, neither pure Ir nor Ir-30 wt.% Pt were
amenable to pressing and sintering, nor to hot iso-
static pressing (HIP) (16). The problems with Ir
include its high melting temperature, which pre-
cludes standard gas atomisation methods, and
contamination from can materials during HIP. An
Ir-50 wt.% Pt alloy was processed to powder by a
plasma rotating electrode process and brought to
near theoretical density by HIP (16). Ir powder or
sponge typically consists of agglomerates of Ir
crystals, with crystal sizes of the order of 1 μm and
agglomerates in the size range 10 μm to 150 μm.
Sintering of Ir powder with subsequent hot press-
ing has been used for the fabrication of Ir
crucibles (17). An Ir composite with 15% by
weight of yttrium oxide, selected for the necessary
combination of high melting temperature and
electrical conductivity together with a low electron
work function, was developed as an electrode
material for plasma cutting (18). The material was
prepared by pressing and sintering in hydrogen at
2273 K for 30 minutes to obtain a density of 94%.
Ir-base alloys containing up to 15% alloy additions
of niobium, titanium, zirconium or hafnium have
187
been consolidated on a laboratory scale from pre-
alloyed powders using a pulse electric current
sintering method (19). Homogeneity was
improved over earlier work with elemental pow-
ders, and densities close to 98% were achieved.
The use of elemental powders was also found
unsuitable for preparing quaternary alloys of Ir
because the desired microstructures could not be
obtained in melted alloys (20).
Powder metallurgy methods have been used to
produce porous Ir for use as filters or in other
applications. Conventional pressing and sintering
methods have been used to produce a porous Ir
metal filter which is bonded to Ir alloy compo-
nents (21). The bonding and final sintering at 2173
K were performed in a vacuum furnace under an
applied load of 22 N over an area of 0.5 cm2 using
graphite tooling. A density of 47% of theoretical
was achieved. Compression at room temperature
subsequently increased the density to 67% in order
to obtain the desired flow rates for the filter. Slurry
casting has been investigated as a method for pro-
ducing porous Ir components with controlled
density and pore size (22). After removal of the
wax binder the samples were presintered in argon
for one hour at 1273 K to achieve a density of
33%. Sintering in vacuum for one hour at 1473 K
and 1573 K resulted in densities of 35% and 46%
respectively.
Deformation Processing
Ir and its alloys can be processed using standard
metalworking methods including forging, extru-
sion, rolling and drawing, but only with some
difficulty (23). In general deformation is per-
formed at elevated temperature in order to avoid
crack formation and propagation (15). The defor-
mation behaviour depends on impurity content,
impurity distribution, microstructure and texture.
Annealing at temperatures of 2273 K and higher
was shown to result in homogenisation of some
potentially deleterious impurities and to decrease
the tendency for grain boundary fracture (24). In
contrast, small additions of elements such as thori-
um and cerium have been shown to segregate to
grain boundaries and to improve ductility (2, 25).
The very coarse grain structure of Ir and Ir alloys
Platinum Metals Rev., 2008, 52, (3)
in cast ingot form makes the material particularly
sensitive to cracking at relatively small tensile
strains. Preheat temperatures for the initial defor-
mation of cast Ir by extrusion, forging or rolling
are 1500 K or higher (26). Initial working temper-
atures for Ir ingots can be as high as 2075 K (27).
Hot extrusion minimises tensile stresses during the
initial deformation processing. Canning in molyb-
denum for extrusion minimises cooling of the Ir
during the extrusion process and permits preheat
temperatures in the range of 1600 to 1700 K
with an extrusion ratio of 6.4:1 (28). (The extrusion
ratio is defined as the ratio of the container bore
area to the total cross-sectional area of extrusion.)
Hot rolling of Ir and its alloys following initial
ingot breakdown is generally performed with pre-
heat temperatures in the range 1100 to 1500 K. In
order to minimise chill during rolling, covers of
Mo have been used (29). In-process recrystallisa-
tion is also used to minimise cracking during
rolling. Ir alloy sheet of about 0.5 mm thickness or
less can be rolled to foil at room temperature with
cold work levels of more than 80%. A schematic
flow diagram of the production of the DOP-26
alloy sheet material from Ir powder through multi-
ple melting and deformation processing steps is
shown in Figure 1. (DOP-26 contains (by weight)
3000 ppm tungsten, 60 ppm thorium and 50 ppm
aluminium.)
Ir wire is normally produced from a melted Ir
stock with deformation performed at elevated tem-
perature. An enriched 191Ir isotope was forged
square at about 1775 K and then rod rolled begin-
ning at 1675 K preheat temperature (12). The final
circular cross section of about 0.6 mm was achieved
by swaging. Another method uses repeated hot
extrusion of a melted ingot followed by warm
drawing, and is applicable for initial ingots
as small as 30 g (30). Trials of upset forming
of annealed Ir wire determined that limited cold
deformation of up to 25 to 30% could be
achieved, but forming of complex geometries was
unsuccessful (27).
Forming of sheet or plate of Ir and its alloys is
generally performed at elevated temperature.
Warm drawing, that is deformation below the
recrystallisation temperature, has been successfully
188

DOP-26 Iridium Alloy Processing
Iridium powder Compact Electron beam button
Arc-melted ingot Electrode Drop-cast segment
Extruded bar Sheet
performed on Ir and its alloys. Hemispherical cups
of an Ir alloy were hydroformed using tooling pre-
heated to 775 K (31). Prior to forming, the blanks
were encapsulated in evacuated stainless steel cov-
ers that were preheated to 1175 K. Similar
encapsulation in stainless steel was used for deep
drawing with preheated steel tooling (32). The
encapsulation and subsequent removal of the cap-
sule materials does add processing steps and
potentially decreases dimensional control. Crack-
free cups may be formed from similar Ir DOP-26
alloy without encapsulation, using preheated tool-
ing, isothermal forming temperatures of 825 K to
875 K and a draw ratio of about 2 (33). Cracking
occurred at a draw temperature of 775 K. An ear-
lier work on deep drawing of Ir cups reported
wrinkling of the drawn cups (34), and incorrectly
concluded that drawing below the recrystallisation
temperature was not possible. Increasing the hold-
down pressure minimises wrinkling, and improved
lubrication minimises loads on the cup wall. By
Platinum Metals Rev., 2008, 52, (3)
Fig. 1 Schematic diagram of the processing
of iridium powder to a DOP-26 iridium alloy
forming blank. Note: photographs are not to
the same scale
Blank
way of example, blanks of 51 mm diameter and
0.65 mm thickness, in stress-relieved conditions,
were drawn with a hold-down force of 65 kN
using flexible graphite sheet as a lubricant (33).
The advantages and disadvantages of various deep
drawing methods for DOP-26 Ir alloy have been
evaluated (35). No substantial differences were
found between the inspection yields of formed
cups with and without encapsulation. Additional
processing steps associated with encapsulation and
later removal of the encapsulation material
increase processing costs, but the potential for sur-
face contamination of the Ir alloy is minimised.
Also, as reported elsewhere (36), the tendency for
fracture near the cup radius might possibly be
minimised by maintaining the punch at a lower
temperature to increase the strength of the mater-
ial in that region. Hot drawing of Ir has also been
reported, using a preheat temperature up to
1625 K with tooling heated to about 650 K. The
blanks were of 2 mm thickness and the draw ratio
189
was 1.1 (27). In general, Ir sheet material has been
formed by deep drawing, spinning or pressing at
temperatures in the range 1175 to 1675 K (26).
The minimum working temperature increases
with increased material thickness and increased
applied tensile strain levels.
Joining
Ir is weldable by a number of methods, as are
some Ir alloys. The applications for welding Ir and
its alloys include the fabrication of spark plug elec-
trodes, nuclear fuel containers and crucibles for
crystal growth. Arc welding 0.63 mm thick
Ir metal was performed in a helium atmosphere
with a 3.2 mm diameter thoriated tungsten elec-
trode, an arc gap of 1 mm, a weld velocity of
5 mm s–1 and a current of 41 A DC with straight
polarity (37). The weld metal along the centreline
exhibited an unfavourable microstructure, with
single grains extending through the thickness of
the weld. An increase in weld velocity, with corre-
sponding increases in welding current, reduced
the size of grains along the centreline. Oscillation
of the arc across the weld centreline by magnetic
deflection, equivalent to a square wave at a fre-
quency of 6.25 Hz, produced a microstructure
with smaller and more equiaxed grains along the
weld centreline.
Some modifications to these methods were
required for welding of the DOP-26 Ir alloy con-
taining 60 ppm Th (38). The alloy was found to be
more susceptible to hot cracking during welding, a
phenomenon associated with grain boundary sep-
aration during the solidification process. A weld
current of 83 A was used and hot cracking was
minimised by using long initial and final tapers,
and a short arc length. The use of arc deflection
with a four-pole oscillator tended to further
reduce hot cracking and gave a smaller average
grain size in the weld (39). The grain orientations
and grain sizes in the weld were associated with
changes in the shape of the weld pool from
teardrop to elliptical (40). This improvement in
grain structure with four-pole oscillation resulted
in increased tensile elongation from 4% to 14%, as
measured in tests at 923 K.
The effect of weld width on the DOP-26 alloy
Platinum Metals Rev., 2008, 52, (3)
was studied under similar conditions at a weld
speed of 12.5 mm s–1, with current adjusted to give
weld bead widths of 3.7 mm or 2.5 mm (41). The
narrow welds exhibited a finer grain size, and a
tensile impact elongation more than double that
for the wider bead as measured at 5000 s–1 and
temperatures of 1253 and 1373 K. Scanning elec-
tron microscopy showed equiaxed particles of
Ir-Th intermetallic along grain boundary fracture
surfaces within the narrow weld, whereas the
wider weld gave aligned intermetallic precipitates
similar to a eutectic structure. The cracking at
grain boundaries during solidification was attrib-
uted to segregation of Th and local melting point
depression, resulting in strain concentration at
weld grain boundaries.
Arc welding of the Ir alloys has been auto-
mated. Autogenous, full joint penetration gas
tungsten arc (GTA) girth welds were made to join
two DOP-26 Ir alloy shells over a plutonium
oxide fuel pellet using computer-based control
(38). This process was later updated to use a PC-
based commercial controller that continuously
monitors and controls welding current, rotational
speed, and the composition and flow of the torch
gas (42). The use of precision tooling and controls
for location, rotation and joint loading allowed
tack welding to be eliminated and improved yields
of defect-free welded components (43).
Electron beam welding provides some advan-
tages in the welding of Ir alloys that are difficult to
join by arc welding. An alloy of Ir with 200 ppm
Th was successfully welded without cracking by
electron beam, but was not weldable by arc weld-
ing (44). At low speed, successful electron beam
welds could only be made over a narrow range of
beam focus conditions, whereas at high speeds
welds could be made over a wide range of focus
conditions. This behaviour at high welding speeds
was associated with fusion zone grain structure
and positive segregation of Th at the fusion
boundary under conditions leading to cracking.
High heat input led to more rapid solidification,
finer grain size and lower levels of segregation
(45). The micrograph in Figure 2 shows the align-
ment of grain boundaries in the weld metal along
the centreline of a weld obtained at the relatively
190
(a) Welding direction
300 μm
(b)
200 μm
Fig. 2 Optical micrographs of an electron beam weld in
iridium alloy sheet, showing regular grain alignment
along the weld centreline associated with a relatively low
weld traverse speed (Reproduced with permission from
(45))
low travel speed of 2.5 mm s–1. At higher speeds
the grain boundaries become less uniformly ori-
ented. The shape of the weld pool during electron
beam welding was also found to influence the ori-
entation of grains in the weld pool (46), as
discussed above for arc welding of Ir. Electron
beam welding of Ir alloy components has been
practiced, although control of heat input and tool-
ing is essential to obtaining acceptable welds (47).
Figure 3 shows an example of an electron beam
weld in a DOP-26 Ir alloy cup assembly.
Laser welding has shown benefits in welding an
Ir alloy that is subject to hot cracking (48). An
alloy containing 200 ppm Th was welded with a
continuous-wave high-power carbon dioxide laser
system without hot cracking. This was explained in
a manner similar to that for electron beam weld-
ing, a highly concentrated heat source and a
relatively fine fusion zone microstructure. Laser
welding has been used to join Ir wire segments to
nickel or nickel alloy for use in spark plug applica-
tions (49). Electric resistance welding, a potentially
lower-cost alternative for this joining process, was
also evaluated using a programmable high-fre-
quency power supply. Direct bonding of Ir to the
Platinum Metals Rev., 2008, 52, (3)
5 mm
Fig. 3 DOP-26 iridium alloy cups with electron beam
welded frit vent component. The light coloured area, seen
as four semi-circular regions, is a porous iridium metal
filter or frit (Photograph courtesy of G. B. Ulrich, Oak
Ridge National Laboratory)
Ni was not achieved but metallurgical bonding was
achieved with the use of an intermediate layer. The
intermediate layers were chosen to assist in alloy-
ing between the dissimilar joint materials and to
provide an orderly transition in the thermal expan-
sion coefficient of the material across the joint.
Ir alloys have been characterised with respect
to weldability, defined as the capacity to produce
crack-free welds. Since there are multiple mecha-
nisms by which cracks may initiate and propagate,
there are a variety of methods for measuring weld-
ability of Ir and its alloys.
The simplest method of determining whether
autogenous welds can be made without cracks in
sheet material under specific conditions was
employed to show that Ir containing up to 100
ppm Th produced sound welds by arc welding,
whereas alloys containing 200 ppm or greater did
not produce crack-free welds (44). The more sen-
sitive modified circular patch test employs a disk
of material which is clamped to a test fixture and
arc welded to produce two concentric autogenous
welds in sequence (50). This test introduces ther-
mal stresses from mechanical constraint as well as
increased residual stresses from the multiple
welds. The modified circular patch test was used
191
to characterise various individual lots of the DOP-
26 alloy with respect to hot cracking. Another test
employed the detection of underbead cracks in
arc-welded DOP-26 Ir alloy capsules (51). Here, a
closure weld was made by arc welding the circum-
ference of two mating Ir alloy cups, followed by
additional circumferential welds and shorter arc
welds in the same locations as the previous welds.
The welded cups were examined for cracks by
both non-destructive and destructive methods.
This permitted the selection of improved weld
parameters, in particular current ramp rates, as well
as characterisation of various lots of Ir alloy sheet
materials.
In the Sigmajig weldability test for hot cracking,
an initial tensile stress is applied to the test sample,
and threshold cracking stress is determined; this is
the maximum applied stress at which a crack-free
weld can be made (52). This test has been used
both to characterise the weldability of Ir alloy
materials and to characterise the effects of varying
some welding parameters (53). A study of the
effect of Th concentration in Ir-0.3 wt.% W alloy
showed that the threshold cracking stress
decreased from 170 MPa at 37 ppm Th to 85 MPa
at 94 ppm Th. Neither oxygen impurities up to
2000 ppm by volume nor water vapour up to 1000
ppm in the argon atmosphere of the glove box
affected the threshold cracking stress. However,
significant increases in weld width were observed
with increased gas impurity levels, an effect attrib-
uted to changes in the surface tension of the liquid.
The test was also used to evaluate the weldability
of alloys with Ce or both Ce and Th at levels (in
atom fraction) up to 100 ppm (54). An alloy with
50 ppm Ce and alloys with 40 ppm Ce and 10 ppm
Th or 30 ppm Ce and 20 ppm Th all showed
threshold cracking stresses of 170 MPa or greater.
A number of other alloys with boron and Y addi-
tions exhibited low threshold cracking stresses.
The performance of welded Ir crucibles has
also been characterised. Crucibles fabricated by
welding of electron beam melted Ir have shown
longer service life than those made by powder met-
allurgy (55). Grain growth during service at
temperatures of 1800 to 2400 K resulted in large
grains, up to 10 mm in size. Crucible failures were
Platinum Metals Rev., 2008, 52, (3)
attributed to segregation of impurities at these
boundaries. One unusual application is the autoge-
nous welding of an entire wrought Ir crucible, with
a goal of increasing crucible life (56). The grains in
the welded structure, although large by normal
standards, can impede further grain growth and
delay crucible failure.
Nondestructive examination of Ir welds and
base metal has been performed using both dye
penetrant and ultrasonic methods. Fluorescent dye
methods have been used for deep drawn cups (57).
Ultrasonic inspection methods initially used in the
1980s (38, 58) have been further developed to pro-
vide better sensitivity and diagnostic capability (59).
Deposition Processes
Deposition processes for Ir include electrolytic
deposition, chemical and physical vapour deposi-
tion and melt deposition. Each of these methods
has advantages and limitations depending on the
requirements of the application. The plating of Ir
from aqueous solutions has been the subject of a
recent review (60). Plating of Ir from Ir chloride
solutions with sulfamic acid produces deposits up
to 25 μm thick, although the deposits exhibit
cracks. Plating of Ir from solution in hydrobromic
acid produces crack-free deposits of up to 1 μm
thick using a plating rate of about 1 μm per hour.
Improved plating efficiencies and decreased crack-
ing of the coating were reported for sodium
hexabromoiridate(III) baths with additions of
oxalic acid. While typical thicknesses of Ir plating
of 1 μm or less can minimise corrosion and serve
for many electronic applications, thicker coatings
are necessary for use at elevated temperature.
Electrodeposition from molten salts has been
used to produce coatings of Ir up to 0.4 mm thick,
and net shape components up to 3 mm thick.
Initial work on electrodeposition demonstrated
that Ir plating could be performed in a bath of
fused sodium cyanide or a mixture of sodium
cyanide and potassium cyanide under inert atmos-
phere at rates up to 10 μm h–1 (61). Coatings up to
0.125 mm thick were produced in a single coating
cycle (62) and coatings up to 0.4 mm were
produced in multiple cycles with intermediate sur-
face removal (63). Later work demonstrated that
192
deposition of Ir coating from fused chlorides was
also possible, with thicknesses up to 350 μm
deposited at temperatures of 800 to 920 K (64).
Coatings have been made using a ternary eutectic
molten salt bath of NaCl-KCl-CsCl containing 2 to
7 wt.% Ir (65). This bath composition has also
been used to electroform crucibles by deposition
of thick deposits on to a graphite mandrel that is
later removed (66). Deposition rates up to 100 μm
h–1 were reported. The grain size was 10 to 15 μm
for direct current deposits with a thickness of
200 μm. The grain size was about 70 μm using
intermittent current reversal. Electrodeposition
has been used for a variety of other components,
including crucibles, tubes, nozzles and jewellery
Fig. 4 Iridium products produced by electrodeposition
(6, 67). Some examples are shown in Figure 4. from a molten salt bath (Reproduced with permission
The chemical vapour deposition (CVD) pro- from (6))
cessing of Ir has progressed significantly in recent inner liner with a CVD Ir coating (71).
years, particularly for very high-temperature appli- The range of methods reported for CVD of Ir
cations. Ir was first applied by CVD to rhenium was recently reviewed (72). Ir hexafluoride can be
rocket thruster chambers for high-temperature used to produce non-porous coatings at rates of up
oxidation protection in 1986, and a 490 N cham- to 10 μm h–1, but the compound requires high
ber was flight-qualified in 1997 (68). Ir coatings are deposition temperatures and is corrosive. Organic
deposited by CVD to a thickness of about 50 μm complexes of Ir offer the potential for lower depo-
onto a Mo or graphite mandrel of the appropriate sition temperatures. Ir acetylacetonate has been
shape, and Re, to a thickness of about 2 mm, is used to produce Ir coatings up to 50 μm thick at
subsequently deposited over the Ir by CVD and rates up to 25 μm h–1, although these deposits con-
machined (69), as shown schematically in Figure 5. tain up to 20% carbon by weight. Controlled
Typical deposition rates are about 10 μm h–1 for Ir additions of oxygen can produce essentially
and 40 μm h–1 for Re at a temperature stated to be carbon-free coatings, but deposition rates are
about 1475 K (70). Further performance improve- about 0.2 μm h–1. A variety of carbonyl, allyl and
ments and weight savings are reported using a cyclooctadienyl complexes of Ir have been
carbon/carbon composite outer shell and CVD Re evaluated for CVD of Ir coatings. Temperatures

Coat mandrel Overcoat with Remove

with iridium rhenium mandrel

Mandrel Iridium Rhenium Completed

(oxidation (structure) iridium/rhenium
Fig. 5 Schematic diagram of the
protection) combustion chamber
production of an iridium-coated rhenium
nozzle by chemical vapour deposition
(Reproduced with permission from (69))

Platinum Metals Rev., 2008, 52, (3) 193

for decomposition are in the range of 400 to 760 K
and oxygen or hydrogen is generally added to con-
trol the carbon content of the coating. A
methylcyclopentadienyl complex of Ir,
Ir(COD)(MeCp) (COD = 1,5-cyclooctadiene) has
been used to produce coatings of 1 to 2 μm thick-
ness, of good purity, at temperatures in the range
573 to 673 K, but with low deposition rates of
0.25 μm h–1 or less (73).
Physical vapour deposition methods for Ir
include both thermal evaporation and sputtering.
Electron beam vapour deposition (EBVD) has
been used to produce thin coatings on mirrors for
infrared telescopes (74). Ir alloys have been
deposited by EBVD for use as diffusion barriers
on coated Ni-base superalloys (75). Pulsed laser
vaporisation of Ir has also been studied (76).
Studies of coatings of Ir for high-temperature oxi-
dation protection of carbon materials showed that
continuous coatings were produced via radio-fre-
quency magnetron sputtering, but not with direct
current sputtering methods (77).
A number of melt deposition processes have
been investigated for Ir component production.
The production of near-net shape parts with Ir by
directed light fabrication has shown some promise
(78). In this method metal powder is transported in
a stream of inert gas and fused to a surface in the
focus of a high-power laser beam, to form fully
fused near-net-shaped components. Initial work
on this process indicates that porosity originating
from gases during melting and solidification is an
issue. Plasma spray, and, in particular, vacuum
plasma spray or low-pressure plasma spray of Ir
has been proposed as a method for achieving high-
density coatings. While there is little published
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The Author
Dr Evan K. Ohriner is a Distinguished Development Staff
member in the Materials Science and Technology Division of
the Oak Ridge National Laboratory, U.S.A. His main interest
is in processing of refractory metals and alloys. In 2005 Dr
Ohriner was honoured by ASM International as an ASM
Fellow ‘for the development of iridium alloys and high-
temperature and wear-resistant materials used in space
exploration and energy generation and transmission’.

Platinum Metals Rev., 2008, 52, (3) 197

DOI: 10.1595/147106708X327428
Platinum 2008
Johnson Matthey published its latest market
survey of the platinum group metals (pgms) in
May 2008. “Platinum 2008” covers supply and
demand for the whole calendar year 2007, and
provides a short-term outlook on the status of
the pgm market and pgm prices into 2008.
Platinum
Platinum Market Deficit for 2007
“Platinum 2008” reports a market deficit of
480,000 oz of platinum for 2007. Production in
South Africa was disrupted by a series of
unscheduled smelter closures, safety problems
and a difficult industrial relations climate. As a
result, South African supplies fell by 4.9 per cent
to 5.04 million oz, and this drove global plat-
inum supplies down to 6.55 million oz. At the
same time, rising purchases of platinum for
autocatalysts and industrial use caused demand
to rise by 8.6 per cent to 7.03 million oz. In
response, the price of platinum rose almost 35
per cent, hitting a series of record highs.
Johnson Matthey’s expectations are for the mar-
ket to remain in deficit in 2008, and for price
volatility to persist.
Record Demand for Autocatalysts
Production of light-duty diesel vehicles grew
during 2007. Many of these vehicles were fitted
with a platinum-based oxidation catalyst and a
platinum-coated particulate filter to comply with
emissions legislation, especially in Europe where
Strong growth in the flat panel display and fibre glass
(shown above) markets in Asia boosted platinum
demand last year (Courtesy of Owens Corning)
Platinum Metals Rev., 2008, 52, (3), 198–199
the Euro 4 legislation has been in place since
2006. Car production in Asia also increased,
including both gasoline and diesel vehicles for
domestic use or export, most of which were fit-
ted with autocatalysts. There is an increasing
requirement that heavy-duty diesel vehicles
meet tightening emissions legislation around the
world, leading to the fitment of platinum-based
exhaust aftertreatment to many of these vehicles.
Substitution of platinum by palladium continued
in some gasoline and diesel catalysts, but pur-
chases of platinum by the autocatalyst sector still
rose by 8.2 per cent to 4.23 million oz in 2007.
Strong Industrial Demand
Purchases of platinum for industrial applica-
tions rose to 1.94 million oz in 2007. Increasing
demand for data storage for electronic devices
led to higher production of hard disks. The aver-
age platinum content of a hard disk rose to
increase storage capacity. However, the growing
share of the inherently higher capacity perpen-
dicular magnetic recording hard disk moderated
the rise in platinum demand. Overall, platinum
demand by the electronics sector rose to 425,000
oz. Increased demand for flat panel glass result-
ed in rising demand for platinum for LCD glass
manufacture, particularly in Asia. High oil prices
and high demand for oil products led to an
increase in platinum use for petroleum refining,
which rose by 13.9 per cent to 205,000 oz.
Platinum requirements in the chemical sector fell
slightly to 390,000 oz, although demand from
the silicones industry remained steady, with
increasing demand offsetting reduced levels of
catalyst in individual products. From nitric acid
producers, platinum demand rose. Net demand
for the dental sector fell to 105,000 oz due to
price sensitivity and increased recycling.
Little Price Impact on Jewellery Demand
Jewellery demand for platinum fell only mar-
ginally to 1.59 million oz, although there was
growth in some markets. European demand rose
by 7.7 per cent to 210,000 oz, and in China
demand rose by 20,000 oz to 780,000 oz.
198
 Chinese manufacture of platinum Olympic
memorabilia ahead of the Beijing games con-
tributed to demand, and is expected to boost
platinum demand in 2008. Demand in Japan was
lower than previous estimates, at 280,000 oz, due
to increased recycling; and in North America
demand fell to 240,000 oz.
Palladium
Palladium Market in Surplus
Supplies of palladium rose to a total of 8.59
million oz, with slightly decreased primary pro-
duction from Russia at 3.05 million oz, and
substantial sales of Russian State stocks at 1.49
million oz. South African production was down
to 2.77 million oz, while output from North
America, Zimbabwe and elsewhere rose to 1.28
million oz. Demand reached a total of 6.84 mil-
lion oz, up 3.5 per cent. Overall the market
showed a surplus of 1.75 million oz.
Rising Use of Palladium in Autocatalysts
Strong growth in vehicle production led to a
rise in autocatalyst demand for palladium of 10.8
per cent to 4.45 million oz. Car manufacturers
continued to use palladium in place of platinum
in a typical gasoline autocatalyst, and as a minor
component in some diesel autocatalysts. The
total worldwide amount of palladium used
in light-duty diesel catalysts was less than
300,000 oz.
Strong Growth in Electronics Demand
Demand for palladium grew strongly in the
electronics sector, increasing by 6.6 per cent to
1.29 million oz. This was largely due to the use
of palladium in multilayer ceramic capacitors,
Platinum Metals Rev., 2008, 52, (3)
with more capacitors per device and increasing
sales of electronic goods outweighing the effects
of miniaturisation and the slowly increasing use
of nickel. Use of palladium in the dental sector
also rose by 15,000 oz to 635,000 oz, after sever-
al years of decline.
Jewellery Demand Falling
Overall demand for palladium for jewellery
fell to 740,000 oz in 2007. However, demand
rose in some markets, notably Europe and
North America where combined demand
reached 95,000 oz. The Chinese jewellery
requirement for new metal was down to 500,000
oz, with increased use of recycled metal, particu-
larly Pd950 pieces which were being returned for
remanufacture into higher purity Pd990 alloys.
Special Features
“Platinum 2008” carries three Special
Features: ‘South African PGM Production’,
which includes a map showing the South African
pgm mines; ‘The Russian PGM Industry’ and
‘Exchange Traded Funds’. The last describes the
two new investment funds, backed by physical
pgms, which were launched in 2007.
Availability and Contact
Information
“Platinum 2008” is available to download free
of charge as a PDF file from the Platinum Today
website: http://www.platinum.matthey.com/.
Alternatively, a printed copy can be requested
from Johnson Matthey PLC, Precious Metals
Marketing, Orchard Road, Royston,
Hertfordshire SG8 5HE, U.K., or by E-mail:
ptbook@matthey.com.
Johnson Matthey is the first western
autocatalyst manufacturer to establish a
plant in Russia. The facility shown is in
Krasnoyarsk and started operations in
the first half of 2008
199
DOI: 10.1595/147106708X331810
ABSTRACTS
CATALYSIS – APPLIED AND
PHYSICAL ASPECTS
Kinetics of o-Chlorotoluene Hydrogenolysis in the
Presence of 3%, 5% and 10% Pd/C Catalysts
T. JANIAK, Appl. Catal. A: Gen., 2008, 335, (1), 7–14
The kinetics of o-chlorotoluene hydrogenolysis in
the presence of 3%, 5% and 10% Pd/C (1) were stud-
ied in an alkaline–n-heptane–H2(g) system. The main
product of hydrogenolysis was toluene. The extent of
dechlorination increased with time and temperature,
and depended on the amount of (1).
Gas-Phase Thermochemistry of Ruthenium
Carbene Metathesis Catalysts
S. TORKER, D. MERKI and P. CHEN, J. Am. Chem. Soc., 2008,
130, (14), 4808–4814
Quantitative energy-resolved collision-induced dis-
sociation cross-sections by tandem ESI-MS gave
absolute thermochemical data for phosphine binding
energies in first- and second-generation Ru metathe-
sis catalysts of 33.4 and 36.9 kcal mol–1, respectively.
A study of RCM in the second-generation system to
liberate norbornene by forming the 14-electron reac-
tive intermediate from the intramolecular π-complex
allowed an estimate of the olefin binding energy to
the 14-electron complex of ~ 18 kcal mol–1, assuming
a loose transition state.
CATALYSIS – INDUSTRIAL PROCESS
Development of a Robust Ring-Closing Metathesis
Reaction in the Synthesis of SB-462795, a
Cathepsin K Inhibitor
H. WANG, S. N. GOODMAN, Q. DAI, G. W. STOCKDALE and W.
M. CLARK, Jr., Org. Process Res. Dev., 2008, 12, (2), 226–234
RCM with Hoveyda’s second-generation catalyst can
be used to synthesise SB-462795. With pure diene pre-
cursor (1), very low loadings (0.1–0.2 mol %) of the Ru
catalyst are required; however, the reaction conversion
decreased when (1) is of reduced purity. Projection
methods were applied to historical data to identify the
main sources of variation in starting material quality,
and to determine the main detrimental impurities.
CATALYSIS – REACTIONS
Dendritic SBA-15 Supported Wilkinson’s Catalyst
for Hydroformylation of Styrene
P. LI and S. KAWI, Catal. Today, 2008, 131, (1–4), 61–69
PAMAM dendrimers were grown in mesoporous
SBA-15. RhCl(PPh3)3 precursor was then tethered on
these supports. The silanols outside the SBA-15 pores
could be passivated. The Rh catalysts supported in
the pore channels of this passivated SBA-15 showed
positive dendritic effects in enhancing the catalytic
activity, regioselectivity and stability of the catalyst by
minimising the leaching of the Rh complex catalyst.
Platinum Metals Rev., 2008, 52, (3), 200–202
A Versatile Iridium Catalyst for Aldehyde
Reduction in Water
X. WU, C. CORCORAN, S. YANG and J. XIAO, ChemSusChem,
2008, 1, (1–2), 71–74
Ir-N-tosyldiamine complexes catalysed the reduc-
tion of a wide range of aldehydes, including aromatic,
aliphatic, heterocyclic and α,β-unsaturated aldehydes,
in H2O. The hydrogenations were fast and chemo-
selective. The reactions proceeded without the need
for added organic cosolvents.
EMISSIONS CONTROL
Role of Zeolite Structure on NO Reduction with
Diesel Fuel over Pt Supported Zeolite Catalysts
A. SULTANA, M. HANEDA, T. FUJITANI and H. HAMADA,
Microporous Mesoporous Mater., 2008, 111, (1–3), 488–492
The selective catalytic reduction of NO with diesel fuel
over Pt/zeolites was investigated under simulated
exhaust conditions. Pt/MOR was the most active, giving
90% NO conversion at 300ºC, however Pt/FER showed
a desirable low temperature window, giving 77% NO
conversion at < 260ºC. Over ZSM-5, BEA and Y with
3D pore structures, extensive carbonaceous deposits
were observed. FER having a 1D pore structure did not
allow extensive coke formation, resulting in low temper-
ature NO conversion. It is suggested that NO reduction
takes place mainly near the zeolite pore opening.
A New Route for Degradation of Volatile Organic
Compounds under Visible Light: Using the
Bifunctional Photocatalyst Pt/TiO2–xNx in H2–O2
Atmosphere
D. LI, Z. CHEN, Y. CHEN, W. LI, H. HUANG, Y. HE and X. FU,
Environ. Sci. Technol., 2008, 42, (6), 2130–2135
N-doped and Pt-modified TiO2 was used to obtain
Pt/TiO2–xNx (1) by wet impregnation of TiO2 xero-
gel. Superior photocatalytic activity and catalytic
stability of (1) for decomposing benzene were
achieved under visible light in a H2–O2 atmosphere.
(1) also successfully decomposed other VOCs such as
toluene, ethylbenzene, cyclohexane and acetone.
Modification of Pd/Al2O3 Catalyst to Improve the
Catalytic Reduction of NO in Waste Incineration
Processes
J. C. CHEN, F. Y. CHANG and M.Y. WEY, Catal. Commun., 2008,
9, (6), 1106–1110
Na, Cu, Ni and Co were used to modify Pd/Al2O3
catalysts (1) for NO reduction with CO reductant in
a simulated flue gas containing 6% O2. Na addition
was very effective in promoting the NO conversion
of (1) at 300–400ºC with the concentration ratio of
CO:NO = 1. Adding Cu improved the NO conver-
sion at 250–300ºC. Ni or Co slightly improved the
NO conversion at 150ºC, but maintained good cat-
alytic activity on the CO oxidation.
200
FUEL CELLS
Crystallographic Characteristics of Nanostructured
Thin-Film Fuel Cell Electrocatalysts: A HRTEM
Study
L. GANCS, T. KOBAYASHI, M. K. DEBE, R. ATANASOSKI and A.
WIECKOWSKI, Chem. Mater., 2008, 20, (7), 2444–2454
The structure of nanostructured thin film (NSTF)
electrocatalysts supported on PR149 (N,N-di(3,5-
xylyl)perylene-3,4:9,10-bis(dicarboximide))-crystalline
organic whiskers was investigated by HTREM.
Common trends in the electrocatalyst crystallography,
morphology and surface characteristics were observed
for Pt, PtRu and PtNiFe NSTFs. Specific details of the
electrocatalyst particles’ growth mechanisms, mor-
phology and support interactions were established.
A High-Throughput Study of PtNiZr Catalysts for
Application in PEM Fuel Cells
J. F. WHITACRE, T. I. VALDEZ and S. R. NARAYANAN, Electrochim.
Acta, 2008, 53, (10), 3680–3689
Pure Pt or PtNiZr alloys (not exceeding 11 at.% Zr)
were fabricated using cosputter deposition. A high-
throughput fabrication approach was used wherein 18
thin film ORR electrocatalyst alloy samples were
deposited onto a large-area substrate. A multichannel
pseudo-potentiostat enabled the simultaneous quanti-
tative study of catalytic activity for all of the
electrodes in a single test bath. The best performing
catalyst was Pt59Ni39Zr2.
In Situ and Real-Time Visualisation of Oxygen
Distribution in DMFC Using a Porphyrin Dye
Compound
J. INUKAI, K. MIYATAKE, Y. ISHIGAMI, M. WATANABE, T.
HYAKUTAKE, H. NISHIDE, Y. NAGUMO, M. WATANABE and A.
TANAKA, Chem. Commun., 2008, (15), 1750–1752
A film of the luminescent dye [tetrakis(pentafluo-
rophenyl)porphyrinato]platinum dispersed in
poly(1-trimethylsilyl-1-propyne) was coated onto a
transparent separator on the cathode side of a DMFC to
visualise O distribution under operating conditions by
analysing emission from the dye. Higher O consump-
tion due to MeOH crossover occured for a fluorinated
membrane than for a hydrocarbon membrane.
Improved Performance of Pd Electrocatalyst
Supported on Ultrahigh Surface Area Hollow
Carbon Spheres for Direct Alcohol Fuel Cells
F. P. HU, Z. WANG, Y. LI, C. LI, X. ZHANG and P. K. SHEN, J. Power
Sources, 2008, 177, (1), 61–66
Hollow C spheres (HCSs) were prepared using glu-
cose as the C source and polystyrene spheres as the
template. Combined methods of hydrothermal and
intermittent microwave heating were employed. The
addition of PEG-block-PPG-block-PEG during the
hydrothermal process greatly increased the surface
area of the HCS, mainly from the huge micropores.
The catalytic activity of Pd/HCSs is 3 times higher
than Pd/Vulcan XC-72 C at the same Pd loadings.
Platinum Metals Rev., 2008, 52, (3)
METALLURGY AND MATERIALS
Hydrogen Absorption in the Core/Shell Interface of
Pd/Pt Nanoparticles
H. KOBAYASHI, M. YAMAUCHI, H. KITAGAWA, Y. KUBOTA, K.
KATO and M. TAKATA, J. Am. Chem. Soc., 2008, 130, (6),
1818–1819
From the results of H2 pressure-composition
isotherm and solid-state 2H NMR measurements, it
was shown that Pd/Pt bimetallic nanoparticles (1)
with a Pd core/Pt shell structure can absorb H2. Most
of the absorbed H atoms were situated around the
interfacial region between the Pd core and the Pt shell.
This indicates that the core/shell boundary plays a key
role in the formation of the hydride phase of (1).
Hydrogen Storage Properties of Pd
Nanoparticle/Carbon Template Composites
R. CAMPESI, F. CUEVAS, R. GADIOU, E. LEROY, M. HIRSCHER,
C. VIX-GUTERL and M. LATROCHE, Carbon, 2008, 46, (2),
206–214
A C/Pd composite was prepared by chemical
impregnation of an ordered porous C template (CT)
with a H2PdCl4 solution followed by a reduction treat-
ment. 10 wt.% of Pd clusters (2 nm in size) were
introduced in the C porosity. At room temperature
and moderate pressure (0.5 MPa), the filling of the
CT with nanocrystalline Pd resulted in an H2 uptake
eight times larger than that of the Pd-free CT.
APPARATUS AND TECHNIQUE
Gas Sensing Properties of Nano SnO2 Based Thick
Films Prepared by Dip Coating Method with Effect
of Molarity of PtCl2 Solution
A. D. GARJE and R. C. AIYER, J. Mater. Sci.: Mater. Electron.,
2008, 19, (6), 547–552
The title films modified by dip coating in PtCl2 solu-
tions (0.05–0.2 M) were tested for 400 ppm
concentration of H2, CO and LPG. Sensors dip coated
with 0.15 M solution of PtCl2 showed the highest sen-
sitivity which is ten times higher than undoped SnO2
sensors. The sensors have fast response time of 10 s to
all the gases with a minimum detection limit of 10 ppm.
Micro Coulter Counters with Platinum Black
Electroplated Electrodes for Human Blood Cell
Sensing
S. ZHENG, M. LIU and Y.-C. TAI, Biomed. Microdevices, 2008,
10, (2), 221–231
Two designs of micro Coulter counter were fabri-
cated using integrated parylene and soft lithography
technologies. Pt black enhanced detection in the
intermediate frequency range (~ 100 Hz to 7 MHz).
Polystyrene beads were used to validate the opera-
tion of the devices, and using excitation frequency of
10 kHz, the signal magnitude was found to be corre-
lated with the volume of the individual bead. Human
blood cell sensing was then demonstrated with dilut-
ed whole blood and leukocyte rich plasma under the
same excitation frequency.
201
CHEMISTRY
Structure of a Crystalline Vapochromic
Platinum(II) Salt
L. J. GROVE, A. G. OLIVER, J. A. KRAUSE and W. B. CONNICK,
Inorg. Chem., 2008, 47, (5), 1408–1410
Square-planar cations of the orange form of
[Pt(Me2bzimpy)Cl](PF6)·DMF (Me2bzimpy = 2,6-
bis(N-methylbenzimidazol-2-yl)pyridine) stack along
the b axis in a head-to-tail arrangement with short
interplanar spacings (3.35 and 3.39 Å). The DMF sol-
vent molecules line channels parallel to c, which may
provide a channel for vapour absorption. Crystals
were shown to be vapochromic, changing from
orange to violet upon exposure to MeCN vapour.
Synthesis and Dynamic Structure of Multinuclear
Rh Complexes of Porphyrinoids
J. SETSUNE, M. TODA and T. YOSHIDA, Chem. Commun., 2008,
(12), 1425–1427
Multinuclear Rh complexes of the large porphy-
rinoids expanded rosarin and octaphyrin having the
1,4-phenylene spacers where the Rh(CO)2 group
passes through the macrocycle were synthesised. The
Rh3 complex of the expanded rosarin exists as the
C3v-isomer in CH2Cl2 as well as in the crystal state.
Relatively slow metal transposition passing through
macrocycle was observed in toluene solution to cause
interchange between the C3v-isomer and the Cs-iso-
mer. Four metals are fixed in the Rh4 complex of the
expanded octaphyrin.
ELECTRICAL AND ELECTRONICS
Nanomechanical and Nanotribological
Characterization of Noble Metal-Coated AFM Tips
for Probe-Based Ferroelectric Data Recording
M. PALACIO and B. BHUSHAN, Nanotechnology, 2008, 19, (10),
105705 (9 pages)
Nanoindentation experiments were carried out to
evaluate the mechanical properties of Pt, Pt-Ni, Au-
Ni and Pt-Ir deposited on AFM probes. The Pt-Ir
coating exhibited the highest hardness, highest elastic
modulus and lowest creep resistance. Nanoscratch
studies revealed that the noble metal coatings are
removed primarily by plastic deformation.
ELECTROCHEMISTRY
Degradation Characteristics of IrO2-type DSA® in
Methanol Aqueous Solutions
J.-M. HU, X.-J. SUN, Y.-Y. HOU, J.-Q. ZHANG and C.-N. CAO,
Electrochim. Acta, 2008, 53, (7), 3127–3138
A comparative study was done on the long-term sta-
bility and deactivation characteristics of Ti/IrO2-type
dimensionally stable anodes (1) in acidic solutions in
the absence and the presence of MeOH, respectively.
The service life increased and then decreased as the
calcination temperature of the as-prepared (1) was
increased. The lifetime was shortened by the addition
of MeOH into the testing solution.
Platinum Metals Rev., 2008, 52, (3)
PHOTOCONVERSION
The Influence of Platinum on UV and ‘Visible’
Photocatalysis by Rutile and Degussa P25
T. A. EGERTON and J. A. MATTINSON, J. Photochem. Photobiol.
A: Chem., 2008, 194, (2–3), 283–289
The influence of Pt on the UV photocatalytic degra-
dation of the dichloroacetate anion (DCA) by rutile and
the P25 form of TiO2 was investigated. The Pt was
deposited photochemically. Although the catalytic
activity of rutile was much less than that of the P25,
the effect of Pt addition was so much greater on rutile
than on P25 that the activities of the Pt-treated tita-
nias were similar. Visible light irradiation of Pt/rutile
oxidised the DCA.
Single Dopant White Electrophosphorescent Light
Emitting Diodes Using Heteroleptic Tris-
Cyclometalated Iridium(III) Complexes
J. H. SEO, I. J. KIM, Y. K. KIM and Y. S. KIM, Thin Solid Films,
2008, 516, (11), 3614–3617
A single dopant single emissive layer white organic
electroluminescent (EL) device (1) was based on
Ir(dfppy)2(pq) (dfppy = 2-(2,4-difluorophenyl)pyri-
dine, pq = 2-phenylquinoline) as the guest and
1,4-phenylenebis(triphenylsilane) as the host. The
maximum luminous and power efficiencies of (1)
were 11.00 cd A–1 (J = 0.05 mA cm–2) and 5.60 lm W–1
(J = 0.001 mA cm–2), respectively. The CIE coordi-
nates of (1) are (0.443, 0.473) and the EL spectrum of
(1) shows emission bands at 473 and 544 nm, at the
applied voltage of 12 V.
Exploitation of the Dual-emissive Properties of
Cyclometalated Iridium(III)-Polypyridine
Complexes in the Development of Luminescent
Biological Probes
K. K.-W. LO, K. Y. ZHANG, S.-K. LEUNG and M.-C. TANG, Angew.
Chem. Int. Ed., 2008, 47, (12), 2213–2216
In polar and nonpolar media the title complexes
show green and orange-yellow emission, respectively.
The incorporation of biological substrates into this
system results in luminescent probes that exhibit pro-
nounced changes in their emission profiles upon
binding to their specific receptors. Novel luminescent
biological probes for avidin, oestrogen receptor α and
human serum albumin have been developed.
SURFACE COATINGS
The Electrodeposition and Electrocatalytic
Properties of Copper–Palladium Alloys
C. MILHANO and D. PLETCHER, J. Electroanal. Chem., 2008,
614, (1–2), 24–30
The codeposition of Cu and Pd from CuSO4 and
PdSO4 in HClO4 was investigated using microdisc
voltammetry. Good quality coatings of CuPd were
deposited. The composition of the coatings was con-
trolled either through the deposition potential or the
Cu(II):Pd(II) ratio in solution.
202
DOI: 10.1595/147106708X321938
NEW PATENTS
CATALYSIS – APPLIED AND
PHYSICAL ASPECTS
Self-Adjusting Propellant Decomposition Catalyst
A. J. FORTINI et al. U.S. Appl. 2008/0,064,913
A self-adjusting catalyst for decomposing high-
energy chemical propellants is formed from a Pt
group metal, preferably Ir, Ru or their alloys, support-
ed on a second catalyst selected from Ba oxide, metal
chromites, metal hafnates, metal zirconates other
than Ca zirconate, or hydrates or mixtures thereof.
The Pt group metal catalyst is present in 15–30 wt.%.
Platinum Polymerisation Catalyst
WACKER CHEMIE AG U.S. Appl. 2008/0,103,322
Pt 1,3-diketo compounds are prepared by stirring a
dichloroplatinum compound containing an aliphatic
or cyclic diolefin radical such as norbornadiene or
cyclooctadiene, with a diketo compound in a keto sol-
vent at < 10ºC for 5–90 minutes, then isolating the
reaction product. Purity of the obtained Pt compound
is > 95% and it is suitable for use as a catalyst for poly-
mer preparation for the medical and food industries.
Fibrous Protein-Supported Osmium Catalyst
WAKO PURE CHEM. IND. LTD Japanese Appl. 2008-006,349
The title catalyst is prepared by supporting Os on a
fibrous protein such as silk fibroin, in which S-con-
taining amino acid residues are present in ≤ 1 wt.%.
The catalyst can be used for oxidation of alkenyl com-
pounds, or for selective reduction of a carbonyl group
in a compound containing a C=C or a C≡C bond in
the presence of H2(g).
CATALYSIS – REACTIONS
Rhodium Complexes as Hydrosilylation Catalysts
UNIW. ADAMA MICKIEWICZA World Appl. 2008/033,043
Heterogenised Rh(I) complexes [(≡SiO)(L)Rh(diene)]
immobilised on a silica support are claimed, where
diene = cyclooctadiene, norbornadiene or tetrafluo-
robenzobarrelene; L = a ≡SiOX unit on the silica
substrate where X = H or Si, or alternatively L = PR3,
where R = an alkyl, cycloalkyl or phenyl group. The
complexes can be used to catalyse a hydrosilylation
reaction between alkenes or functionalised alkenes
having a terminal C=C bond and silanes, (poly)silox-
anes or (poly)carbosiloxanes containing a Si=H bond.
Iminosugar Glycoconjugates
TECH. UNIV. GRAZ European Appl. 1,903,034
The title compounds are N-alkylated 1,5-dideoxy-
1,5-iminohexitol or 1,5-dideoxy-1,5-iminopentitol
derivatives with a very stable linkage between the car-
bohydrate and the peptide component. The
compounds are synthesised by catalytic intramolecular
reductive amination of dicarbonyl sugars with partial-
ly protected amino acids, using H2(g) and a catalyst
selected from Pearlman’s catalyst (Pd(OH)2/C) and
Pd or Pt on activated C, at atmospheric pressure or
higher and room temperature in MeOH and/or H2O.
Platinum Metals Rev., 2008, 52, (3), 203–204
EMISSIONS CONTROL
Thermally Regenerable Nitric Oxide Adsorbent
JOHNSON MATTHEY PLC World Appl. 2008/047,170
A method for reducing NOx in a lean gas stream
includes adsorbing NO on an adsorbent containing
Pd and a Ce oxide at < 200ºC, thermally desorbing
NO at > 2000ºC, and catalytically reducing NOx on
a catalyst other than the NO adsorbent using a hydro-
carbon or nitrogenous reductant, H2 or a mixture.
The NO adsorbent may optionally be combined with
a thermally regenerable NOx adsorbent containing Pt
and a metal oxide such as Al2O3, CeO2 or ZrO2.
NOx Reducing Catalyst System
FORD GLOBAL TECHNOL. LLC British Appl. 2,441,623
An exhaust system includes a first emissions control
device having two regions containing Pt, Pd, Rh, Ir,
Ru, Os, Re, Ag or Au or a mixture, preferably Pt, and
a NOx sorbent such as BaO. The second region is
physically segregated from the first and partially
downstream of it, and contains more NOx sorbent. A
second emissions control device downstream of the
first includes a selective catalytic reduction catalyst.
FUEL CELLS
Gold-Platinum Nanoparticle Electrocatalysts
BROOKHAVEN SCI. ASSOC. World Appl. 2008/033,113
An O2-reducing electrocatalyst is formed from par-
ticles with an electrocatalytically active core and an
atomically thin outer shell of Au or Au alloy, on a sup-
port. The core may contain one or more of Pt, Pd, Rh,
Ir, Ru, Os and Re, with optionally Au, in a homoge-
neous or heterogeneous composition. Preferred core
compositions are Pt or Pt and Pd, which may have an
inner subcore of Pd and an outer subshell of Pt.
Palladium Electrocatalyst
SHANGHAI INST. MICROSYST. INFORM. TECHNOL.
Chinese Appl. 1,083,325
An electrocatalyst is formed of nanoparticulate C-
supported Pd or Pd-Pt alloy containing 10–100 at.%
Pd, prepared from an aqueous solution of a Pd salt
and optionally a Pt salt. The C carrier is present in
20–80 wt.%. Particle size is controllable in the range
1.8–20 nm, with narrow size distribution. The catalyst
can be used for the anode of a DFAFC or as a
MeOH-tolerant cathode catalyst for a DMFC.
METALLURGY AND MATERIALS
Ornamental Platinum Alloy
KYOCERA CORP Japanese Appl. 2007-291,492
A Pt alloy for ornamental use includes a first phase
of Pt, a second phase of Cu and optionally a third
phase between the first two and containing an inter-
metallic compound of Pt and Cu. Total content of Pt
is 40–75 wt.%. Maximal reflectivity of light from the
surface is in the range 560–640 nm, the alloy has a
pink colour and has excellent corrosion resistance.
203
APPARATUS AND TECHNIQUE
Ruthenium-Containing Electrode
CHLORINE ENG. CORP LTD European Appl. 1,916,320
An electrode for H2 generation can maintain low H2
overvoltage for a long time under conditions of both
low and high current density. The electrode includes a
coating layer containing Ru and La, prepared by ther-
mal decomposition in an O2-containing atmosphere of
a Cl-free material prepared from a nitric acid solution
of a La carboxylate and Ru(NO3)2, on a conductive
base member. Atomic ratio Ru:La is 30:70–90:10. The
coating material may optionally include a Cl-free Pt
compound with atomic ratio Pt:La ≥ 0.005.
Platinum Apparatus for Glass Manufacture
ASAHI GLASS CO LTD U.S. Appl. 2008/0,050,609
A Pt or Pt alloy structure for use in a high-temper-
ature environment is formed into a hollow tube body
with a flange on its outer periphery, which is provid-
ed with a stress-strain absorbing structure. The flange
may have a disc shape and may incorporate a concen-
tric flexible portion. The structure can be used as a
conduit tube for molten glass in a vacuum degassing
apparatus for glass production.
BIOMEDICAL AND DENTAL
Osmium Compounds for Cancer Treatment
UNIV. WARWICK World Appl. 2008/017,855
Os(II) compounds containing an arene moiety; a
halogen or donor ligand; a bidentate ligand optional-
ly linked to the arene moiety and containing O, N or
S; and optionally a counter ion can be used in a phar-
maceutical composition for the treatment of cancer.
Solvates, prodrugs or physiologically active deriva-
tives of the Os compounds are also claimed.
Palladium-Cobalt Dental Alloys
IVOCLAR VIVADENT AG European Appl. 1,900,836
Alloys for dental articles such as crowns and bridges
contain (in wt.%): 20–90 Pd, 10–80 Co, plus 0–20 Al,
B, Cr, Ga, Li, Re, Ru, Si, Ta, Ti and/or W. Coefficient
of thermal expansion is ~ 14.0–15.2 between
25–500ºC. Alternative compositions contain (in
wt.%): 10–80 Pd, 80–10 Co, plus 0–30 Au, Pt, Cr,
Mo, W, Fe, Al, Si, Mn, Ga, Ta, Ti, Ru and/or Re, with
coefficient of thermal expansion 14.0–15.5 between
25–500ºC.
CHEMISTRY
Ruthenium Compounds for Decontamination of Water
U.S. EPA U.S. Patent 7,335,307
Ru compounds selected from RuO2·xH2O or
oxides, oxyhydroxides or hydroxides of Ru-Fe,
Ru-Mn or Ru-Al can be used to remove biological
and chemical contaminants from water, soil and sed-
iments. Both positively and negatively charged ionic
or polar contaminants can be sorbed, and the sorbed
material is then removed. The Ru compound may
optionally be coated onto or complexed with sand,
silica, zeolites, nylon, polystyrene or cellulose.
Platinum Metals Rev., 2008, 52, (3)
ELECTRICAL AND ELECTRONICS
Iridium Encased Metal Interconnects
INTEL CORP U.S. Appl. 2008/0,045,013
A semiconductor substrate with a trench etched
into a dielectric layer is cleaned and then a chelating
group layer is deposited. An Ir species layer is deposit-
ed, activated and then a Cu seed layer is applied by an
electroless deposition process. Finally a layer of bulk
Cu is deposited using an electroplating process. The
Ir species layer may be deposited by immersing the
substrate in a solution containing Ir species or by an
atomic layer deposition or CVD process.
Palladium-Containing Magnetic Recording Medium
HITACHI MAXELL LTD Japanese Appl. 2007-305,261
High output and excellent short wavelength record-
ing characteristics are claimed for a magnetic
recording medium made from a spherical or elliptical
magnetic powder containing Pd, Fe and N. Content
of each element is (in at.%): 0.1–10.0 Pd, 1.0–20.0 N,
plus optionally 0.05–20.0 Y or Sa and/or 0.1–20.0 Si
and/or Al, with the balance Fe. The average particle
size is 5–30 nm and a Fe16N2 phase is present.
Platinum Etching For Capacitor Manufacture
HYNIX SEMICONDUCTOR INC
Korean Appl. 2007-0,089,573
Pt can be etched using a mixed gas including a F-
containing gas, preferably SF6(g), and an inert gas,
preferably Ar(g), using an electron cyclotron reso-
nance etching apparatus. Flow rate of SF6(g) is ≥ 50%.
A capacitor is fabricated by etching Pt layers to form
an upper and a lower electrode with a dielectric layer
in between. The etched Pt is claimed to be free of
fencing or tapering and to have suitable surface
roughness for capacitor electrodes.
SURFACE COATINGS
Electrodeposition of Palladium Layers
ENTHONE INC World Appl. 2008/023,339
Pd or Pd alloy can be deposited from an electrolytic
solution containing a source of Pd such as PdCl2; a
sulfonic or sulfuric acid or a mixture; and a surfactant.
There may optionally be a source of alloying metal
such as Cu. Electric current at a density of 0.25–1.0 A
dm–2, preferably 0.3–0.8 A dm–2, is applied at 20–45ºC
to deposit the Pd or Pd alloy layer on a substrate. The
solution may further include a S-containing amino
acid to enable the deposition of dark Pd layers.
Rhodium Sulfate Plating Solution
FORMFACTOR INC U.S. Appl. 2008/0,063,594
A Rh salt cake (for example Rh(SO4)2) for prepara-
tion of a Rh plating bath is prepared by mixing a basic
and an acidic solution containing Rh to form a col-
loidal suspension of Rh salt, then removing the liquid.
Mixing is carried out at constant pH and temperature,
and Rh polymers are < 1% of Rh in the cake.
Increased shelf life is claimed for the plating bath and
Rh platings are claimed to have low or no dendrites,
lower internal stress and less susceptibility to cracking.
204
DOI: 10.1595/147106708X333836
Accurate and Precise Determination
of Platinum in Solution by ICPES
It is widely recognised that Wendt and Fassel
(1) and Greenfield et al. (2) were the first to
describe the technique of inductively coupled plas-
ma emission spectrometry as a means of analysis.
The technique has a number of acronyms, with
ICPES being favoured over ICP-OES (where the
O stands for optical) and ICP-AES (where the A
stands for atomic). In the forty or so years since
the inception of the technique, ICPES instrumen-
tation has developed in sophistication and usability
and is now to be found in most laboratories where
simultaneous compositional analysis of a number
of elements is required.
Application for Elemental
Analysis
In recent years, the ICPES technique has been
increasingly used as the method of choice for the
quantitative determination of many metals, includ-
ing platinum and the other platinum group metals
(pgms). The reference methods remain in the
domain of classical gravimetry, where precision in
the order of 0.1% relative standard deviation
(RSD) can be achieved. However, gravimetric
methods are relatively slow and require complex
sequential chemical separations before an element
can be determined. In complex samples this
degrades the optimum precision and accuracy
obtainable. ICPES is capable of achieving preci-
sion of < 1% RSD with fast simultaneous
determination of each of the elements present. To
achieve the best precision and accuracy in deter-
mining Pt and the other pgms in samples, several
factors must be considered.
Nature of the Sample
Samples for Pt analysis are almost invariably in
solid form when received by the laboratory. Pt
loadings may range from low mg kg–1 (for example
in emission control catalysts) to high percentage
levels (for example in fuel cell catalysts). The sub-
Platinum Metals Rev., 2008, 52, (3), 205–206
FINAL ANALYSIS
ject of dissolution of the pgms for analysis has
been covered in many other texts by many other
authors (see, for example, (3)). To achieve
optimum precision and accuracy in determination,
the Pt concentration in the solution presented
should fall in the range 10 to 1000 mg l–1, with not
more than 50 g l–1 in total of dissolved solids.
Sample Introduction
The sample is introduced into the plasma via
nebulisation. In this process, a fine spray of the
sample is carried to the plasma by the injector gas.
In the experience of laboratories analysing Pt solu-
tions, the concentric-type nebulisers give good
precision when coupled with a tortuous path for
the nebulised spray. The classical ‘double pass’
type and newer ‘Twister cyclonic’ nebulisers have
both found utility within leading Pt assay labora-
tories. A range of concentric glass nebulisers are
available on the open market, for example (4). The
sample is delivered to the nebuliser by a peristaltic
pump. Where poor precision and accuracy occur
in ICPES determination, they are often attribu-
table to the sample introduction system. In most
expert laboratories the standard set-up consists of
humidified injector gas, and a 30 rpm eight-roller
peristaltic pump delivering the sample at a rate of
1 ml min–1 to a glass concentric nebuliser in a dou-
ble pass spray chamber.
Calibration
ICPES is often quoted as having a wide linear
response range, covering five to seven orders of
magnitude in concentration. Nevertheless, a good
calibration strategy is still important in achieving
ultimate accuracy and precision. Common practice
is to limit the concentration range to 10 to
1000 mg l–1 via manipulation of the sample dis-
solution and dilution strategy. Under these
circumstances a good match of the calibration
solutions with the samples can be achieved.
205
Matching the major base metal composition of the
sample solution in the calibration solutions
requires some planning, but can still allow
simultaneous analysis of each of the sample con-
stituents. Importantly, acid concentrations in
solution should be matched between samples,
standards and solutions used for flushing between
intermediate samples.
For ultimate accuracy and precision, a weight-
based approach to solution preparation over
standard volumetric glassware has begun to find
favour. Good traceability and reliable calculation
can be achieved through integration of laboratory
balances, with instrumental systems reducing
errors attributable to manual transcription and
data entry (5).
Internal Standardisation
While internal standards can partially correct
for matrix differences between sample and stan-
dard, their best use is in precision improvement.
In common use are yttrium (321.7 nm), scandium
(357.6 nm) and indium (451.1 or 303.9 nm).
Measuring the ratios of intensities for the analyte
and internal standard filters out imprecision
caused by noise at mid-range frequencies
(~ 1 kHz). An accurate match of the signal count-
ing parameters is necessary to achieve the best
performance.
In the final analysis, optimising the analytical
method according to the above parameters offers
routine Pt determinations of high accuracy and
precision. PETER ASH

Spectrometers, Detectors and

References
Lines 1 R. H. Wendt and V. A. Fassel, Anal. Chem., 1965, 37,
One major improvement in ICPES technology (7), 920
of the last fifteen years has been the introduction 2 S. Greenfield, I. Ll. Jones and C. T. Berry, Analyst,
of solid-state detector systems. The low cost of the 1964, 89, (1064), 713
3 J. C. Van Loon and R. R. Barefoot, “Determination
detector elements has allowed true simultaneous of the Precious Metals”, Wiley, Chichester, 1991
measurement of peak and background intensities. and references therein
Line selection is the subject of much discussion in 4 Glass Expansion, ICP/ICP-MS Sample
the standard texts. However, for Pt, the leading Introduction Systems: www.geicp.com
5 L. R. Guy, Johnson Matthey, Analytical
laboratories will select Pt lines at wavelengths of Laboratories, Brimsdown, U.K., personal communi-
265.9, 214.4, 299.8, 306.4 and 203.6 nm. cation

The Author

Dr Peter Ash is manager of the Analytical Group at the

Johnson Matthey Technology Centre, Sonning
Common, U.K. Since joining Johnson Matthey in
1989, he has specialised in platinum group metals
assaying method development and has been involved
in a number of inter-laboratory assay comparison
exercises.

Platinum Metals Rev., 2008, 52, (3) 206

 Platinum Metals Review
Johnson Matthey Plc, Precious Metals Marketing, Orchard Road, Royston, Hertfordshire SG8 5HE, U.K.
E-mail: jmpmr@matthey.com
http://www.platinummetalsreview.com/

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