J Hazard Mater. 2009 Apr 30;163(2-3):1332-7. Epub 2008 Jul 31.

A study on N2O catalytic decomposition

over Co/MgO catalysts.
Shen Q, Li L, Li J, Tian H, Hao Z.

Department of Environmental Nano-materials, Research Center for Eco-Environmental

Sciences, Chinese Academy of Sciences, Beijing 100085, PR China.

Different oxide supported cobalt catalysts were prepared by co-precipitation method and
tested for the decomposition of nitrous oxide. Co/MgO with cobalt loading of 15% showed
the best activity and a 100% N(2)O conversion was obtained at temperatures higher than
700 K. The active phase of cobalt species in Co/MgO catalysts was Co(3)O(4) highly
dispersed in the matrices of MgO, based on XRD and XPS results as well as the kinetic
analysis. The existence of NO, O(2) and H(2)O in reaction system showed different
negative effects on N(2)O decomposition. Nevertheless, a 100% N(2)O conversion could
be achieved at 800 K under simulated conditions of tail gas from nitric acid plant.
Moreover, Co/MgO catalyst exhibited quite good durability and no obvious activity loss
was observed in the 100 h stability test.

Chem Commun (Camb). 2002 Apr 21;(8):860-1.

Superior performance of nano-Au

supported over Co3O4 catalyst in direct
N2O decomposition.
Yan L, Zhang X, Ren T, Zhang H, Wang X, Suo J.

State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of
Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, China.

Au nanoparticles supported over Co3O4 lead to a highly active and stable catalyst for N2O
decomposition even in the presence of excess oxygen and steam.

Angew Chem Int Ed Engl. 2004 Aug 13;43(32):4132-40.

N2O reduction by the mu4-sulfide-bridged

tetranuclear CuZ cluster active site.
Chen P, Gorelsky SI, Ghosh S, Solomon EI.

Department of Chemistry, Stanford University, Stanford, California 94305, USA.

Nitrous oxide (N2O) reduction is a chemical challenge both in the selective oxidation of
organic substrates by N2O and in the removal of N2O as a green-house gas. The reduction
of N2O is thermodynamically favorable but kinetically inert, and requires activating
transition-metal centers. In biological systems, N2O reduction is the last step in the
denitrification process of the bacterial nitrogen cycle and is accomplished by the enzyme
nitrous oxide reductase, whose active site consists of a micro4-sulfide-bridged tetranuclear
CuZ cluster which has many unusual spectroscopic features. Recent studies have developed
a detailed electronic-structure description of the resting CuZ cluster, determined its
catalytically relevant state, and provided insight into the role of this tetranuclear copper
cluster in N2O activation and reduction. Copyright 2004 Wiley-VCH Verlag GmbH & Co.

Chemosphere. 2005 May;59(6):887-91. Epub 2004 Dec 21.

Catalytic reduction of N2O over Ag-

Pd/Al2O3 bimetallic catalysts.
Tzitzios VK, Georgakilas V.

Institute of Material Science, N.C.S.R. Demokritos, Agia Paraskevi, 15310 Athens, Greece.
tzitzios@ims.demokritos.gr

A study of the catalytic conversion of N2O to N2 over a bimetallic Ag-Pd catalyst is

described in this article. Several Ag-Pd catalytic systems were prepared supported on
Al2O3 with different ratios and their catalytic activity for the direct decomposition of N2O
and their reduction with CO was measured. Based on the experimental results, it was
observed that Ag-Pd bimetallic catalyst (5-0.5%) was the most active for both nitrous oxide
reduction and direct decomposition. This high activity seems to be connected with a
synergistic effect between Ag and Pd.

Huan Jing Ke Xue. 2006 Feb;27(2):214-8.

[Selective reduction of NO over indium

catalysts prepared by different methods]
[Article in Chinese]

Cui XY, Hao JM, Fu LX, Li JH, Liu ZM.

Department of Environmental Science and Engineering, Tsinghua University, Beijing
100084, China.

Alumina-supported indium catalysts with different metal loadings were prepared by various
methods including impregnation, co-precipitation and sol-gel. Activity tests were carried
out on the selective catalytic reduction (SCR) of NO by propene in excess O2 over the
catalysts. And the effects of oxygen concentration in reaction gas feed on catalytic activities
were examined. The results show that In/Al2O3 catalysts possess high deNO2 activity, and
the preparation methods have obvious effects on catalytic activities. The catalysts prepared
by co-precipitation or sol-gel method exhibited high NO, conversion to N2 about 90%; the
impregnation samples have poor activities, the highest conversion rate not exceeding 60%.
The O2 concentration in gas feed has significant effects on the highest conversion rates of
NOx reduction and the corresponding reaction temperatures. Along with the increasing of
O2 concentration, the temperatures mentioned above declined. The introduction of water
into the gas feed depressed greatly the deNO2 activities of In/Al2O3 catalysts. Compared to
many other metals as active components of deNOx catalysts, indium has a prominent
different behavior that the respective best metal loadings of the catalysts prepared by these
three diverse preparation methods have little difference, being all around 1% to
approximately 2%.

Environ Pollut. 2007 May;147(2):415-21. Epub 2006 Jul 7.

Catalytic performance of Ag/Al2O3-

C2H5OH-Cu/Al2O3 system for the
removal of NOx from diesel engine
exhaust.
Zhang C, He H, Shuai S, Wang J.

State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for
Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing, China.

The selective catalytic reduction (SCR) of NOx by C(2)H(5)OH was studied in excess
oxygen over Ag/Al(2)O(3) catalysts with different Ag loadings at lab conditions. The 4%
Ag/Al(2)O(3) has the highest activity for the C(2)H(5)OH-SCR of NOx with a drawback of
simultaneously producing CO and unburned THC in effluent gases. An oxidation catalyst
10% Cu/Al(2)O(3) was directly placed after the Ag/Al(2)O(3) to remove CO and unburned
THC. Washcoated honeycomb catalysts were prepared based on the 4% Ag/Al(2)O(3) and
10% Cu/Al(2)O(3) powders and tested for the C(2)H(5)OH-SCR of NOx on a diesel engine
at the practical operating conditions. Compared with the Ag/Al(2)O(3) powder, the
Ag/Al(2)O(3) washcoated honeycomb catalyst (SCR catalyst) has a similar activity for
NOx reduction by C(2)H(5)OH and the drawback of increasing the CO and unburned THC
emissions. Using the SCR+Oxi composite catalyst with the optimization of C(2)H(5)OH
aHuan Jing Ke Xue. 2004 Jul;25(4):18-22.

[Selective catalytic reduction of NO on Ag,

Co and Cu/Al2O3 in excess oxygen]
[Article in Chinese]

Cui XY, Hao JM, Fu LX, Li JH, Zhu TL, Liu ZM.

Department of Environmental Science and Engineering, Tsinghua University, Beijing

100084, China.

The catalytic activities of alumina-supported Ag, Co and Cu for selective reduction of NO

with propene as reductant in the presence of excess oxygen were investigated. The catalytic
performances of single-component catalysts with different metal loadings and of samples
prepared by various methods such as mechanical mixing, one-step impregnation, two-step
impregnation, etc. were studied. The experimental results showed that the Ag exhibited the
highest conversion of NO to N2 (approximately 89% with 2% loading, wt.) among single-
component catalysts, the lower was Co, and the lowest was Cu. The sequence of the
temperature for the maximum conversion was on the order of Cu < Co < Ag. For Ag
catalysts, the activities between samples of identical loadings prepared by one-step and
two-step impregnation were almost the same. The activities of mixed samples were not the
simple sum of the single-component catalysts. The mixed Ag-Co sample possessed the
highest activity (80% above). The activities of the combinatorial samples declined
comparatively to some extent. The activities of one-step impregnation samples descended
more markedly and the highest conversion was only over 30%.

Environ Technol. 2003 Mar;24(3):377-82.

Decomposition of NO on the alkalized

Pt/Al2O3.
Huang YJ, Wang HP, Yeh CT, Liu SH, Chang BC.

Department of Environmental Engineering, National Cheng Kung University, Tainan City

70101, Taiwan.

Catalytic decomposition of NO on platinum catalysts at 873-1,173 K was investigated in

the present work. The yield of N2 in the NO decomposition process was significantly
increased on the alkalizing Pt/Al2O3 catalyst. The enhancement may be attributed to a trap
of additional NO molecules by basic sites ofthe alkalized catalyst. The interstitially
adsorbed species (NaOH(NO)Pt) might increase the NO adsorption strength during the
catalytic NO reduction process. Pt on the high acidity HY was also active for catalytic
decomposition of NO. Nevertheless, its activity decreased at higher temperatures (>1,073
K) because of the distortion of the HY framework. Combined results of XPS (X-ray
photoelectron spectra) and TPR (temperature programmed reduction) showed that PtO and
PtO2 were the main active species on the alkalized Al2O3 and HY during NO reduction.

Huan Jing Ke Xue. 2004 Jan;25(1):7-13.

[Catalytic performance of a novel ceramic-

supported vanadium oxide catalyst for NO
reduction with NH3]
[Article in Chinese]

Tian LQ, Ye DQ.

Department of Environmental Science and Engineering, South China University of

Technology, Guzngzhou 510640, China. lqtian@scut.edu.cn

A novel TiO2/Al2O3/ceramic cordierite honeycomb (CC)-supported V2O5-MoO3-WO3

monolithic catalyst was studied for the selective reduction of NO with NH3. The effects of
reaction temperature, space velocity, NH3/NO ratio and oxygen content on selective
catalytic reduction (SCR) activity were evaluated. Two other V2O5-MoO3-WO3
monolithic catalysts supported on Al2O3/CC or TiO2/CC support, two types of pellet
catalysts supported on TiO2/Al2O3 or Al2O3, as well as three types of pellet catalysts
V2O5-MoO3-WO3-Al2O3 and V2O5-MoO3-WO3-TiO2 were tested for comparison. The
experiment results showed that this catalyst had a higher catalytic activity for SCR with
comparison to others. The results of characterization showed, the preparation method of
this catalyst can give rise to a higher Brunauer, Emmett, Teller (BET) surface area and pore
volume, which was strongly related with the highly active performance of this catalyst. At
the same time, the function of the combined carrier of TiO2/Al2O3 cannot be excluded.

J Mol Graph Model. 2007 Jul;26(1):179-86. Epub 2006 Nov 18.

Decomposition of nitrous oxide on carbon

nanotubes.
Namuangruk S, Khongpracha P, Tantirungrotechai Y, Limtrakul J.
Laboratory for Computational and Applied Chemistry, Chemistry Department, Faculty of
Science, Kasetsart University, Bangkok 10900, Thailand.

In this work, we have suggested the possibility of using carbon nanotubes to remove toxic
gas. By taking an advantage of the density functional theory, we have investigated the
decomposition of nitrous oxide (N(2)O) on the sidewalls of the perfect and the Stone-Wales
defect armchair (5,5)-SWNTs at the B3LYP/6-31G(d) level of theory. There are two
reaction mechanisms proposed: stepwise and concerted pathways. Our calculations predict
that the former route is kinetically favored on both the perfect and defect SWNTs with
barrier heights of the rate-determining steps of 37.23 and 34.38 kcal/mol for the perfect and
the defect systems, respectively. In the second pathway, the decomposition of nitrous oxide
gas takes place in a single step with higher reaction barriers of 48.60 and 40.27 kcal/mol on
the sidewalls of the perfect and the defect SWNTs, respectively. Moreover, we also
demonstrated that an encapsulation of electron rich species, such as chloride anion, inside
the channel of the SWNT can boost up the reaction rate of the N(2)O decomposition on the
SWNT. The chloride ion supplies excess electrons to the SWNT for transferring to the NJ
Hazard Mater. 2004 May 20;108(3):189-97.

N2O removal in N2 or air by ArF excimer

laser photolysis at atmospheric pressure.
Tsuji M, Kumagae J, Tsuji T, Hamagami T.

Department of Applied Science for Electronics and Materials, Graduate School of

Engineering Sciences, Kyushu University, Kasuga, Fukuoka 816-8580, Japan.
tsuji@cm.kyushu-u.ac.jp

A photochemical process is proposed as a new efficient N(2)O removal technique in N(2)

or air at atmospheric pressure and room temperature without using any catalysts. N(2)O
diluted in N(2) or air was decomposed into N(2), O(2), and NO by using a 193 nm ArF
excimer laser. The maximum conversion of N(2)O in N(2)O/N(2) or N(2)O/N(2)/O(2)
mixtures was 93% at a laser power of 136 mJ, a repetition frequency of 5 Hz, and an
irradiation time of 30 min. The formation ratios of N(2):O(2):NO in N(2)O/N(2) and
N(2)O/N(2)/O(2) mixtures were 64:31:5.1% and 60:27:13%, respectively. The
decomposition mechanism of N(2)O under 193 nm photolysis was discussed by comparing
experimental data with calculated model using known photochemical and gas kinetic data.

(2)O molecule causing lower reaction barriers in the reaction pathways.

J Colloid Interface Sci. 2006 Mar 1;295(1):165-72. Epub 2005 Sep 1.

The influence of the preparation method

and the Co loading on the structure and
activity of cobalt oxide/gamma-alumina
catalysts for NO reduction by propene.
Sarellas A, Niakolas D, Bourikas K, Vakros J, Kordulis C.

Department of Chemistry, University of Patras, GR-265 00 Patras, Greece.

In the present work we studied the influence of the preparation method and the Co loading
on the physicochemical properties and the catalytic activity of the cobalt oxide/gamma-
alumina catalysts for the reduction of NO by propene under net oxidizing conditions. Two
series of catalysts containing 1 and 5% w/w Co, respectively, were prepared using three
preparation methods, namely, the equilibrium deposition filtration (EDF), the conventional
incipient wetness impregnation (IWI) and the IWI adding nitrilotriacetic acid (nta) in the
impregnating solution (IWInta). The catalysts were tested at various temperatures in the
range 300-550 degrees C using a fixed-bed microreactor for the NO reduction by propene
under lean burn conditions. The evolution of the Co species on the alumina surface was
followed after each preparation step by diffuse reflectance spectroscopy (DRS). It was
found that the catalysts of the first series were more active for the title reaction than those
of the second one. The EDF sample of the first series was proved to be the most active and
selective one followed by the IWI and then the IWInta sample of the same series. The DRS
results indicated that the enhanced activity and selectivity of the EDF sample could be
attributed to the increased concentration of isolated Co(II) inner sphere complexes of
octahedral coordination, which are formed on the support surface by adsorption of the
corresponding aqueous complexes, [Co(H2O)6]2+, being in the impregnating solution.
These inner sphere complexes are transformed upon thermal treatment into a CoAl2O4 like
phase with high dispersion. On the other hand, the [Co(H2O)6]2+(NO3)2- and [Co-nta]-
.NH4+(or H+) and/or [Co-2nta]4+.4NH4+(or 4H+) complex salts, precipitated on the
alumina surface upon drying in the cases of the IWI and IWInta samples, are transformed
upon calcination into CoAl2O4 like phases with lower dispersion. All the samples of the
second series promoted the propene combustion as well as the oxidation of NO and N2,
used as carrier gas, to NO2. DRS results revealed that in all these samples cobalt(III) oxo
species are formed in addition to the CoAl2O4 phase. These species are considered to be
responsible for the enhancement of the rates of the oxidation reactions mentioned above.

J Phys Chem B. 2006 Nov 16;110(45):22586-95.

Mechanism and kinetics of direct N2O

decomposition over Fe-MFI zeolites with
different iron speciation from temporal
analysis of products.
Kondratenko EV, Pérez-Ramírez J.

Leibniz-Institut für Katalyse e. V. an der Universität Rostock, Aussenstelle Berlin, Richard-

Willstätter-Strasse, 12 D-12489 Berlin, Germany. evgenii@aca-berlin.de

The mechanism of direct N(2)O decomposition over Fe-ZSM-5 and Fe-silicate was studied
in the temporal analysis of products (TAP) reactor in the temperature range of 773-848 K at
a peak N(2)O pressure of ca. 10 Pa. Several kinetic models based on elementary reaction
steps were evaluated to describe the transient responses of the reactant and products.
Classical models considering oxygen formation via recombination of two adsorbed
monoatomic oxygen species (*-O + *-O --> O(2) + 2*) or via reaction of N(2)O with
adsorbed monoatomic oxygen species (N(2)O + *-O --> O(2) + N(2) + *) failed to describe
the experimental data. The best description was obtained considering the reaction scheme
proposed by Heyden et al. (J. Phys. Chem. B 2005, 109, 1857) on the basis of DFT
calculations. N(2)O decomposes over free iron sites (*) as well as over iron sites with
adsorbed monoatomic oxygen species (*-O). The latter reaction originates adsorbed
biatomic oxygen species followed by its transformation to another biatomic oxygen species,
which ultimately desorbs as gas-phase O(2). In line with previous works, our results
confirm that the direct N(2)O decomposition is controlled by pathways leading to O(2). Our
kinetic model excellently described transient data over Fe-silicalite and Fe-ZSM-5 zeolites
possessing markedly different iron species. This finding strongly suggests that the reaction
mechanism is not influenced by the iron constitution. The TAP-derived model was
extrapolated to a wide range of N(2)O partial pressures (0.01-15 kPa) and temperatures
(473-873 K) to evaluate its predictive potential of steady-state performance. Our model
correctly predicts the relative activities of two Fe-FMI catalysts, but it overestimates the
absolute catalytic activity for N(2)O decomposition.

J Phys Chem B. 2006 Jun 8;110(22):10691-700.

Role of adsorbed NO in N2O

decomposition over iron-containing ZSM-5
catalysts at low temperatures.
Bulushev DA, Renken A, Kiwi-Minsker L.

Ecole Polytechnique Fédérale de Lausanne, LGRC-EPFL, CH-1015, Lausanne,

Switzerland.

Transient response and temperature-programmed desorption/reaction (TPD/TPR) methods

were used to study the formation of adsorbed NO(x) from N2O and its effect during N2O
decomposition to O2 and N2 over FeZSM-5 catalysts at temperatures below 653 K. The
reaction proceeds via the atomic oxygen (O)(Fe) loading from N2O on extraframework
active Fe(II) sites followed by its recombination/desorption as the rate-limiting step. The
slow formation of surface NO(x,ads) species was observed from N2O catalyzing the N2O
decomposition. This autocatalytic effect was assigned to the formation of NO(2,ads)
species from NO(ads) and (O)(Fe) leading to facilitation of (O)(Fe)
recombination/desorption. Mononitrosyl Fe2+(NO) and nitro (NO(2,ads)) species were
found by diffuse reflectance infrared fourier transform spectroscopy (DRIFTS) in situ at
603 K when N2O was introduced into NO-containing flow passing through the catalyst.
The presence of NO(x,ads) does not inhibit the surface oxygen loading from N2O at 523 K
as observed by transient response. However, the reactivity of (O)(Fe) toward CO oxidation
at low temperatures (<523 K) is drastically diminished. Surface NO(x) species probably
block the sites necessary for CO activation, which are in the vicinity of the loaded atomic
oxygen.

Environ Sci Technol. 2009 Feb 1;43(3):890-5.

Promotion effects and mechanism of alkali

metals and alkaline earth metals on cobalt-
cerium composite oxide catalysts for N2O
decomposition.
Xue L, He H, Liu C, Zhang C, Zhang B.

Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, 18

Shuangqing Road, Beijing 100085, PR China.

A series of alkali metal- and alkaline earth metal-doped cobalt-cerium composite oxide
catalysts were prepared by the citrate method and tested for the decomposition of N20.
Strong promotion effects of alkali and alkaline earth metals on the activity of the catalyst
were obtained in the order Li < Na < K < Rb < Cs and Mg < Ca < Sr, Ba. The promotion
effects of alkaline earth metals were much weaker than the effects of alkali metals. To
investigate the origin of the promotion effect, X-ray diffraction, Brunauer-Emmett-Teller
surface area measurement X-ray photoelectron spectroscopy, temperature-programmed
desorption, and hydrogen temperature-programmed reduction methods were used to
characterize the alkali metal-doped catalyst. The analytical results indicated that alkali
metals improved the redox ability of active site Co2+ by acting as electronic promoters.
Catalytic decomposition of N2O proceeds through an oxidation-reduction mechanism with
participation of electrons from Co2+, thus the increase in the redox ability of Co2+ should
lead to an increase in the activity of the catalyst.

Spectrochim Acta A Mol Biomol Spectrosc. 2006 Jul;64(4):880-5. Epub 2006 May 24.

An infrared study of co-adsorption of N2O

and CO on ZnO.
Hussain G, Rahman MM.

Department of Chemistry, University of Sargodha, Sargodha, Pakistan.

The absorption of N(2)O and CO at room temperature on finely divided ZnO surfaces gives
reversible absorption bands from surface N(2)O species in the 2237-2245, 2265-2285 and
1245-1255 cm(-1) regions. The growth of the first band is at the expense of the second
while its intensity and position depends on the extent of the surface carbonate, formed by
the oxidation of CO by N(2)O. The order of introduction of CO and N(2)O, and whether
the ZnO surface is oxidised or reduced, gave significantly different results in terms of
carbonate formation. The strongest carbonate formation and implied decomposition of
N(2)O, occurs at room temperature when CO is added to preadsorbed N(2)O on an oxidised
ZnO surface. A single bidentate carbonate is formed under these conditions but on heating
in the gas mixture to 200 degrees C an additional, possibly monodentate, carbonate occurs
together with a surface formate species.