Solid State Ionics 177 (2006) 803 – 811

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Synthesis of alumina supported nickel nanoparticle catalysts and evaluation

of nickel metal dispersions by temperature programmed desorption
Subramani Velu, Santosh K. Gangwal ⁎
Center for Energy Technology, Research Triangle Institute (RTI), 3040 Cornwallis Road, Research Triangle Park, NC 27709, USA
Received 19 October 2005; received in revised form 19 January 2006; accepted 20 January 2006

Abstract

The purpose of this study was to synthesize highly dispersed Ni/Al2O3 catalysts and to develop a suitable hydrogen-temperature programmed
desorption (H2-TPD) method for the determination of nickel metal surface area, dispersion, and crystallite sizes. Several highly dispersed Ni/
Al2O3 catalysts with a Ni loading between 15 and 25 wt.% were synthesized. The reducibility of catalysts was determined by temperature
programmed reduction (TPR) experiments. All catalysts exhibited a single reduction peak with a maximum rate of H2 consumption (Tmax in TPR)
occurring below 450°C. Three different H2-TPD methods were employed to determine the amount of H2 chemisorbed. In TPD-1, a 10% H2/Ar
mixture was used for catalyst pre-reduction and surface saturation by cooling down from Tmax in TPR to room temperature. In TPD-2, the catalyst
surface after pre-reduction was flushed with Ar at Tmax in TPR + 10 °C. The TPD-3 was similar to the TPD-2, but used 100% H2 instead of 10%
H2/Ar mixture. In all three TPD methods, the profiles exhibited 2 domains of H2 desorption peaks, one below 450°C, referred to as type-1 peaks,
and attributed to H2 desorbed from exposed fraction of Ni atoms, and the other above 450°C, denoted as type-2 peaks, and assigned to the
desorption of H2 located in the subsurface layers and/or to spillover H2. Flushing the reduced catalyst surface in Ar at Tmax in TPR + 10 °C in TPD-
2 and TPD-3 removed most of the H2 located in the subsurface layers/ spillover H2. The amount of H2 chemisorbed to form a monolayer on the
reduced Ni/Al2O3 catalysts was determined quantitatively from the TPD peak areas of type-1 peaks in TPD-1, and from both type-1 and type-2
peaks in TPD-2 and TPD-3. The Ni metal surface area, dispersions and crystallite sizes were calculated from the chemisorption data and the values
were compared with those obtained using the static chemisorption method. Both TPD-2 and TPD-3 gave chemisorption results similar to that
obtained from the static method.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Nanomaterial; Nanoparticle; Ni catalyst; Supported catalysts; Chemisorption; Temperature programmed desorption; Metal surface area; Metal dispersion

1. Introduction completely reduce the Ni(II) cations to metallic nickel particles

Nickel-based supported catalysts have been widely
employed in various industrially important chemical processes,
including hydrogenation, reforming, methanation, desulfuriza-
tion, dechlorination and so on [1–10]. These catalysts are
generally synthesized by impregnation of nickel nitrate on a
support. The major problem encountered in the preparation of
these catalysts is the formation of mixed oxides of nickel and
the support, especially at nickel loadings N 10 wt.%. As a
consequence, higher temperatures (N 600 °C) are required to
⁎ Corresponding author. Tel.: +1 919 541 8033.
E-mail address: skg@rti.org (S.K. Gangwal).
0167-2738/$ - see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.ssi.2006.01.031
and this leads to sintering of the metal.
Several alternative approaches such as ion-exchange, depo-
sition–precipitation of nickel–chelate complexes, citrate meth-
od, etc have been reported recently for the synthesis of highly
dispersed nickel-based supported catalysts [11–16]. However,
most of these studies have been devoted to the synthesis of Ni/
SiO2 catalysts while the studies on the similar Ni/Al2O3 system
are scarce. Recently, Lok has reported the synthesis of Ni/Al2O3
catalysts by deposition–precipitation of nickel amine complex
on a transition alumina using basic nickel carbonate as a
precursor for nickel [11]. Shido, et al., [1] and Hoffer, et al., [2]
have recently reported the characterization of new generation Ni/
Al2O3 proprietary catalysts referred to as HTC-100 to HTC-500,
without fully disclosing their preparation methods.
804 S. Velu, S.K. Gangwal / Solid State Ionics 177 (2006) 803–811

We have been working on developing highly dispersed Ni/
Al2O3 hydrogenation catalysts by employing a simple recipe
and readily existing nickel precursor [17]. A number of catalysts
have been synthesized with a nickel loading between 15 and
25 wt.% using several methods. Their physicochemical proper-
ties are being evaluated by various analytical and spectroscopic
methods.
The determination of nickel metal surface area, dispersion
and crystallite sizes is of utmost importance in developing a
highly efficient catalytic system. These parameters are generally
determined either by static or dynamic chemisorption of H2 on
the catalyst surface. The advantage of static chemisorption
method is that the system reaches catalyst–adsorbate equilib-
rium conditions. However, the method requires a high vacuum
system, long lasting measurements and, consequently, higher
instrumentation and operating costs. On the other hand,
dynamic/flow methods such as pulse chemisorption or
temperature programmed desorption (TPD) are performed at
atmospheric pressure, and therefore, they are faster and less
costly [18]. Furthermore, the TPD method, being a transient
technique, can provide useful information on solid surfaces,
their interactions with adsorbed gas molecules, and thermal
stability of surface desorption states. Since most of the catalytic
reactions are performed at atmospheric or elevated pressure
rather than under vacuum conditions, a good correlation could
be expected between chemisorption data obtained from TPD
and catalytic performance.
A review of recent literature on the chemisorption of H2 on
various Ni-based catalysts summarized in Table 1 suggests that
static chemisorption method has been widely employed to
determine the nickel metal surface area, dispersion and
crystallite size of Ni/Al2O3 catalysts. The dynamic pulse
chemisorption and TPD methods have been employed mostly
for supports other than Al2O3. Furthermore, in most of these
studies, the catalysts have been pre-reduced at an arbitrary
temperature irrespective of the catalyst reducibility. Pre-
reduction of catalysts at a temperature lower than the required
temperature could result in reduction of only part of the NiO
phase in the catalyst. This would lead to either underestimate or
overestimate the Ni metal surface area and dispersion. On the
other hand, pre-reduction of catalysts at a temperature higher
than the required temperature could lead to sintering of the
metal particles, which would underestimate the nickel metal
surface area and dispersion.
Earlier studies on the H2-TPD over Ni-based catalysts
indicate that the amount of H2 desorbed is generally higher than
the amount chemisorbed [12]. This is because, during pre-
reduction of the catalyst, part of H2 molecules dissociated on the
Ni surfaces are migrated to subsurface layers and/or to the
support, a phenomenon known as spillover effect [4,22]. These
H2 species are also desorbed at higher temperature during TPD.
Thus, an appropriate TPD method should be employed in order
to apply H2-TPD as a versatile method for the quantitative
determination of chemisorbed H2 on Ni-based catalysts.
The objective of the present study was therefore to develop
an optimized TPD method for the quantitative determination of
chemisorbed H2 to rapidly determine the nickel metal surface
area, dispersion and crystallite sizes of Ni-based supported
catalysts. The H2 chemisorption data for a few highly dispersed
Ni/Al2O3 catalysts developed in our laboratory have been
determined by three different H2-TPD methods and the data
have been compared with those obtained from static chemi-
sorption experiments. Based on the comparison of static and
TPD methods, an appropriate TPD method is suggested.
2. Experimental
2.1. Materials' synthesis
A series of highly dispersed Ni/Al2O3 catalysts with a nickel
loading between 15 and 25 wt.% were synthesized by different
methods. One method involves heterogeneous precipitation

Table 1
H2 Chemisorption experiments performed over supported Ni catalysts known in the literature
Catalyst Chemisorption method Tmax in TPR (°C) Pre-reduction conditions Chemisorption conditions Parameters reported Ref.
Ni/Al2O3 Static NR 100% H2 @ 400 °C/2h 100% H2 @ 25°C Ni SA [3]
Ni/Al2O3 Static ≈400 100% H2 @ 252 °C/2h 100% H2 @ RT Ni SA [2]
Ni/Al2O3 Static NR NR NR Ni SA [1]
Ni/Al2O3 Static NR 450 °C/2h 100% H2 @ RT D and MCS [19]
Ni/Al2O3 Dynamic, pulse ≈500 100% H2 @ 350 °C/6h 100% H2 @ RT Ni SA [4]
Ni/Al2O3 Dynamic, TPD NR 100% H2 @ 600 °C/3h 100% H2 @ 25°C Ni SA [5]
Ni/SiO2 Dynamic, TPD NR 100% H2 @ 300 °C/2h 100ppm H2, Pulse @ RT H2 uptake [12]
Ni/MgO Static ≈350 100% H2 @ 400 °C/6h 100% H2 @ RT Ni SA [6]
Ni/SiO2 Dynamic, TPD NR 100% H2 @ 400 °C/2h 100ppm H2 D and MCS [20]
Ni/SiO2 Dynamic, TPD NR 100% H2 @ 400 °C 100ppm H2 @ RT H2 uptake [13]
Ni/MCM-41 Dynamic, TPD 580 100% H2 @ 350 °C 100ppm H2 @ RT D and MCS [7]
Ni/RHA Dynamic, TPD NR 100% H2 500°C NR D [21]
Ni/CeO2/ZrO2 Dynamic, pulse NR 5% H2 @ 700°C/3h 5% H2 @ 50°C Ni SA [8]
Ni/CeO2–ZrO2 Dynamic, pulse ≈350 100% H2 @ 500 °C/1h 100% H2 @ 40°C D [9]
NR = not reported.
Ni SA = Ni metal surface area.
D = dispersion.
MCS = mean crystallite size.
 S. Velu, S.K. Gangwal / Solid State Ionics 177 (2006) 803–811
(HP) wherein commercially available NiO nanoparticles
(Aldrich) with average particle sizes in the range between 10
and 20 nm was used as a nickel source and an aqueous solution
of Al(NO3)3 salt was used as aluminum source [23]. In a
typical synthesis process, 55.17 g of Al(NO3)3 was dissolved in
1 L of de-ionized (DI) water. To this solution, 3.2 g of
polyethylene glycol (PEG: MW = 1500) was added and the
solution was made up to 2L under vigorous stirring. Then,
3.19 g of nano-NiO powder was dispersed in the solution. The
PEG acts as a dispersant to prevent the nanoparticles of NiO
from agglomeration. To this solution, 1 M aqueous NH3
solution was added dropwise at room temperature under
vigorous stirring until the pH of the slurry becomes 9. The
added NH3 precipitates aluminum as aluminum hydroxide on
the NiO nanoparticles. The resulting slurry was aged at room
temperature for 1h under stirring and then filtered and washed
with excess DI water. The precipitate was dried at 70 °C/24 h
and calcined at 450°C for 5 h in air to obtain nano-dispersed
NiO/Al2O3 catalyst. The other method of preparation involves
deposition-precipitation (DP) of nickel on a transitional
alumina support [24].
2.2. Materials' characterizations
The nickel content in the calcined catalysts was determined
by inductively coupled plasma atomic emission spectrometer
(ICP-AES). The BET surface areas of the samples were
Fig. 1. Schematic representation of different temperature programmed desorption (TPD) methods employed in the present study.
805
determined by N2 adsorption at liquid N2 temperature on a
Micromeritics Gemini 2360 Surface area analyzer.
TPR experiments were conducted on a Micromeritics
AutoChem II 2920 TPD/TPR instrument. About 100mg of
the sample was loaded in a quartz reactor and heated in the
temperature range between 30 and 800 °C at a heating rate of
5°C/min in a stream of 10% H2 in Ar with a flow rate of 50cc/
min. The outlet gas was passed through a cold trap to remove
the moisture produced during reduction. The hydrogen
consumption due to the reduction of NiO was then monitored
by a thermal conductivity detector (TCD) and a computer data
acquisition system. The TCD signals were calibrated using
Ag2O as a standard.
The nickel metal surface area and metal dispersion were
calculated from TPD studies using H2 gas as a probe
molecule (H2-TPD) on the same Micromeritics instrument
that was used for TPR studies. Three different TPD methods,
as illustrated schematically in Fig. 1, were employed using
about 100mg of the catalyst. The samples were pre-reduced
at Tmax in TPR. The H2 gas desorbed during TPD experiment
was monitored by the thermal conductivity detector (TCD)
and data acquisition system. In the TPD-1, the area under the
TPD curve below 450 °C was used for the calculation of
volume of H2 chemisorbed, while the entire area under the
TPD curve obtained from TPD-2 and TPD-3 were used for
the quantitative estimation. The TCD area was calibrated by
running TPR experiment on a standard Ag2O sample
806 S. Velu, S.K. Gangwal / Solid State Ionics 177 (2006) 803–811

Table 2 (STEM) which was equipped with a Kevex Sigma model

Preparation method employed and physical properties of highly dispersed Ni/ energy-dispersive X-ray spectrometer (EDXS). The samples
Al2O3 catalysts in their oxidized state
were prepared for electron microscopy by placing a sub-sample
Catalyst Method of preparation Ni loading BET surface of the material in a small beaker, adding 10 ml of isopropanol,
(wt.%)a area (m2/g)b
and ultrasonicating for five min using a Fisher model 60 high-
Ni(25)/Al2O3-HP Heterogeneous precipitation 25.5 298 power ultrasonic dismembrator. A small aliquot of the
Ni(25)/Al2O3-DP Deposition–precipitation 21.1 165
suspension was withdrawn using a micropipette and deposited
Ni(15)/Al2O3-DP Deposition–precipitation 15.6 166
Commercial Unknown 15.2 131 on a carbon-coated copper grid, and allowed to dry for analysis.
a Particles were examined at a variety of magnifications at
Determined by ICPES.
b
Determined by N2 adsorption. 100kV. The pre-reduction was performed in the TPR instrument
following the same TPR procedure, cooled down to room
temperature and then the reduced sample was immediately
transferred into a vial containing isopropanol.
acquired from Micromeritics. The Ni metal surface area,
dispersion and crystallite sizes were calculated from the 3. Results and discussion
volume of H2 chemisorbed using the following simplified
equations: 3.1. Structural and textural properties
Ni metal surface area:
The physicochemical properties of some of the highly
Vad
SANi ðm2 =gCat:Þ ¼  SF  N  RA ð1Þ dispersed Ni/Al2O3 catalysts synthesized in the present study
Ws  Wm are summarized in Table 2. For the purpose of comparison, the
Ni metal specific surface area: data of a commercial Ni/Al2O3 catalyst containing 15.2 wt.% Ni
is also included. The catalyst, Ni(25)/Al2O3-HP synthesized by
SANi ðm2 =g  NiÞ ¼ SAðm2 =gÞ=FNi ð2Þ the HP method exhibits a high BET surface area of about
300m2/g while those synthesized by DP method show a lower
Ni dispersion (D) BET surface area of about 165m2/g, close to that of the
commercial catalyst.
Vad FWNi  SF
Dð%Þ ¼   100 ð3Þ
Ws FNi  Vm

Ni metal crystallite size (MCS)

325

MCSðnmÞ ¼ 6  103 =SANi ðm2 =g  NiÞ  dNi ð4Þ

where, Vad = volume of H2 chemisorbed at STP (mL) to form a

Ni(15)/Al2O3-HP
monolayer, Ws = weight of the sample (g), Vm = molar volume
of H2 gas (22414 mL/mol), SF = stoichiometric factor, i.e. Ni : H
440

ratio in the chemisorption, which is taken as 1, N = 6.023 × 1023

TCD Signal (a.u)

Ni atoms/mol, RA is the atomic cross sectional area of Ni,

which is 0.0649nm2, FNi = weight fraction of Ni in the sample
as determined by ICP-AES, FWNi = formula weight of Ni
(58.71 g/mol) and dNi = density of Ni metal (8.9 g/cm3).
450

In order to validate the TPD method developed, the Ni Ni(15)/Al2O3-DP

surface area and dispersion of selected samples were also
evaluated independently by static chemisorption methods at two
425

different research laboratories in the USA. The static method-1 Ni(15)/Al2O3-DP

(Static-I) and method-II (Static-II) were performed at Clemson
University, and a Catalyst Company, respectively. In Static-I,
the catalysts were pre-reduced at the Tmax in TPR for 2 h and
evacuated at the same temperature. On the other hand, in Static-
II the catalysts were pre-reduced at a fixed temperature of Commercial
450 °C rather than Tmax in TPR and evacuated at Tmax in TPR +
10 °C. The total amount of reduced Ni was calculated by O2
titration. 100 200 300 400 500 600 700 800
The Transmission electron micrograms of unreduced and Temperature (°C)
pre-reduced Ni/Al2O3 samples were recorded on a Hitachi H-
7000 model scanning transmission electron microscope Fig. 2. Temperature programmed reduction profiles of Ni/Al2O3 catalysts.
 S. Velu, S.K. Gangwal / Solid State Ionics 177 (2006) 803–811 807

Ni(25)/Al2O3-HP
made it difficult to precisely determine the NiO particle sizes in
these catalysts.
The existence of a single reduction peak without any
additional peak at temperature above 500 °C in all these
catalysts implies that the catalysts are composed of mainly
NiO species dispersed on the Al2O3 support and does not
contain any NiAl2O spinel or a phase wherein NiO has very
strong interaction with the Al2O3 support [22,26]. It should be
TCD signal (a.u.)

(a) noted that the formation of NiAl2O4 spinel or strongly

interacting NiO-Al2O3 phase is generally observed in most of
(b) the Ni/Al2O3 catalysts with higher nickel loadings [14,26].

3.3. H2 chemisorption by TPD

H2-TPD experiments have been performed over these

(c) catalysts in order to obtain information on the surface structure
as well as to quantitatively determine the amount of
chemisorbed hydrogen, which in turn is a good estimate of
the metal dispersion and surface area. The H2-TPD profiles of
Ni(25)/Al2O3-HP, Ni(25)/Al2O3-DP, Ni(15)/Al2O3-DP and
(d)
Commercial Ni/Al2O3 catalyst obtained by different TPD
methods are shown in Figs. 3–6, respectively. The profiles, in
general, show two domains of H2 desorption peaks, one below
100 200 300 400 500 600 700 800 450°C referred to as type-1 peaks and the other above 450 °C
denoted as type-2 peaks. The low temperature type-1 peaks are
Temperature (°C)
generally attributed to H2 desorbed from the metal particles and
Fig. 3. Temperature programmed desorption profiles of Ni(25)/Al2O3-HP indicates the exposed fraction of Ni atoms [4,12,13,20,22]. The
collected using different TPD methods. (a) TPD-1, (b) TPD-2 wherein the
sample was pre-reduced at 450°C, (c) TPD-3, and (d) TPD-3 wherein the
sample was pre-reduced at 450 °C. Ni(25)/Al2O3-DP

3.2. Redox properties

TPR experiments have been performed on all the catalysts in

order to determine a suitable pre-reduction temperature of the
catalyst before H2 chemisorption experiments in TPD or static
(a)
TCD Signal (a.u.)

method. Fig. 2 displays TPR profiles of catalysts of the present

study. As can be seen, all catalysts exhibit a single reduction
peak centering below 460 °C, and this corresponds to the
reduction of NiO species supported on Al2O3. The catalysts, Ni
(25)Al2O3-DP and Ni(15)Al2O3-DP display a broad reduction
profile between 300 and 600°C with the Tmax in TPR occurring
around 450 °C. The commercial sample containing 15.2wt.% (b)
Ni also exhibits a similar TPR profile with the Tmax in TPR
occurring slightly at lower temperature, around 425°C. In
contrast, the sample, Ni(25)/Al2O3-HP exhibits the Tmax in TPR
at much lower temperature, around 325°C and the peak is
relatively narrow compared to other samples. It should be noted
that the Tmax in TPR for pure NiO occurs around 370°C [25]. (c)
Thus, the lower Tmax in TPR of Ni(25)/Al2O3-HP could be due
to large crystallite sizes of NiO particles because nano-NiO with
10–20nm size has been used as a source of nickel. On the other 100 200 300 400 500 600 700 800
hand, the NiO particle sizes in Ni(25)/Al2O3-DP and Ni(15)/
Temperature (°C)
Al2O3-DP should be relatively smaller, leading to a stronger
interaction between NiO species and the Al2O3 support [26], Fig. 4. Temperature programmed desorption profiles of Ni(25)/Al2O3-DP
similar to that in the commercial catalyst. The partial over- collected using different TPD methods. (a) TPD-1, (b) TPD-2, and (c) TPD-3.
lapping of NiO peaks with that of Al2O3 in X-ray diffraction Samples were pre-reduced at Tmax in TPR.
808 S. Velu, S.K. Gangwal / Solid State Ionics 177 (2006) 803–811

Ni(15)/Al2O3-DP Ni(25)/Al2O3-DP and Ni(15)/Al2O3-DP (see Figs. 4 and 5)

indicating that the catalysts consist of large amount of exposed
Ni atoms on the surface. Furthermore, the profiles collected in
TPD-1 exhibit a broad doublet below 450 °C. This doublet
becomes a single sharp peak, and the type-2 peak becomes very
weak upon flushing the catalyst with Ar at the Tmax in TPR +
(a) 10°C irrespective of whether 10% H2/Ar or 100% H2 is used for
the catalyst pre-reduction and surface saturation. This shows
that flushing the catalyst with Ar at the Tmax in TPR + 10 °C
removes majority of H2 migrated to the subsurface layers and/or
TCD Signal (a.u.)

spillover H2. The commercial Ni/Al2O3 catalyst containing

about 15 wt.% Ni also exhibits similar TPD profiles in the TPD
methods employed in the present study, implying that the
surface structures of Ni(25)/Al2O3-DP and Ni(15)/Al2O3-DP
(b) catalysts are similar to that of the commercial catalyst.
The Ni metal surface areas, dispersion and crystallite sizes
have been calculated from these TPD curves and the results are
compared to those obtained from static chemisorption methods
in Table 3. Since these parameters are determined from the
amount of H2 chemisorbed to form a monolayer on the catalyst
surface, only those H2 species interacting weakly and desorbed
at relatively lower temperature should be considered for
(c) quantitative estimation. Accordingly, the area of only type-1
peak appearing below 400 °C in the catalyst Ni(25)/Al2O3-HP
has been used for the calculation of monolayer chemisorption of
100 200 300 400 500 600 700 800 H2. As discussed above, the TPD profiles of this catalyst exhibit
Temperature (°C)

Fig. 5. Temperature programmed desorption profiles of Ni(15)/Al2O3-DP Commercial

collected using different TPD methods. (a) TPD-1, (b) TPD-2 and (c) TPD-3.
Samples were pre-reduced at Tmax in TPR.

high temperature type-2 peaks are attributed to the H2 located in

the subsurface layers and/or to spillover H2. The relative
intensity of peaks in these two domains and their positions vary
with respect to the nature of catalyst and the TPD method
TCD Signal (a.u.)

employed.
The type-1 peak is much weaker than type-2 peak in Ni(25)/ (a)
Al2O3-HP irrespective of the TPD method employed. The
position of type-1 peak is shifted slightly toward lower
temperature and the intensity ratio of type-1 peak to type-2
peak increases when 100% H2 is used for pre-reduction
followed by flushing with Ar at Tmax in TPR + 10 °C. This
indicates that flushing with Ar gas at higher temperature
removes some strongly interacting H2 species. It is also
interesting to note that the intensities of both type-1 and type-
2 peaks decrease dramatically when the sample is reduced at (b)
450 °C instead of Tmax in TPR, which is 325°C. This indicates
that sintering of Ni occurs at higher reduction temperatures
leading to decrease in the amount of chemisorbed H2. The
existence of type-2 peak even after flushing the catalyst in Ar at 100 200 300 400 500 600 700 800
Tmax in TPR + 10 °C clearly indicates that the catalyst consists of
Temperature (°C)
large amount of strongly interacting H2 at the subsurface layers
or spillover H2. Fig. 6. Temperature programmed desorption profiles of a commercial Ni/Al2O3
In contrast to that observed in Ni(25)/Al2O3-HP, the type-1 catalyst collected using different TPD methods. (a) TPD-1, (b) TPD-3. Samples
peaks below 450 °C is much stronger than type-2 peaks in were pre-reduced at Tmax in TPR.
 S. Velu, S.K. Gangwal / Solid State Ionics 177 (2006) 803–811 809

Table 3
Hydrogen chemisorption data of highly dispersed Ni/Al2O3 catalysts determined by H2-TPD and static chemisorption methods
H2 chemisorption Catalyst
Method Parameter Ni(25)/Al2O3-1 Ni(25)/Al2O3-2 Ni(15)/Al2O3-1 Commercial
2
TPD-1 Ni surface area (m /g-cat.) 8.7 27.1 18.2 14.2
Ni Specific surface area (m2/g-Ni) 41.0 106.1 116.7 97.0
Dispersion (%) 6.2 15.9 17.5 15.0
Crystallite size (nm) 16.4 6.4 5.8 7.0
TPD-2 Ni surface area (m2/g-cat.) (3.4) 31.0 27.6 ND
Ni Specific surface area (m2/g-Ni) (16.3) 121.5 176.7 ND
Dispersion (%) (2.5) 18.2 26.5 ND
Crystallite size (nm) (41.4) 5.6 3.8 ND
TPD-3 Ni surface area (m2/g-cat.) 7.7 (2.4) 33.4 26.5 16.7
Ni Specific surface area (m2/g-Ni) 36.4 (11.5) 130.8 170.0 110.0
Dispersion (%) 5.5 (1.7) 19.6 25.5 16.5
Crystallite size (nm) 18.5 (58.5) 5.2 4.0 6.1
Static-I Ni surface area (m2/g-cat.) 9.9 33.6 ND ND
Ni Specific surface area (m2/g-Ni) 47.0 131.8 ND ND
Dispersion (%) 7.1 19.8 ND ND
Static-II Ni surface area (m2/g-cat.) 5.4 21.3 13.3 16.9
Ni Specific surface area (m2/g-Ni) 26.0 132.8 132.6 ND
Dispersion (%) 3.9 19.9 19.9 16.0
ND = not determined.
Data in parentheses are obtained after pre-reduction of catalyst at 450°C instead of Tmax in TPR, i.e. 325°C.
Static-I was performed at Clemson University, USA.
Static-II was performed at a catalyst company, USA.

an intense type-2 peak attributed to the desorption of subsurface
layer H2 or spillover H2. Consequently, the area under the type-
2 peak appearing above 400 °C cannot be considered for the
determination of monolayer coverage of chemisorbed H2. The
Ni surface area (7.7–9.0 m2/g-cat.) and dispersion (≈ 6%) of this
catalyst (see Table 3) considering only type − 1 peak in TPD-1
and TPD-3 are very close to that obtained from static − 1
(9.9 m2/g-cat. and 7%, respectively), validating the calculation
method employed in the present study. However, the data
obtained from static-II are significantly lower than the above
values because the catalyst in this method has been pre-reduced
at 450°C instead of the Tmax in TPR, which is 325 °C. The
higher temperature reduction would have caused sintering of the
Ni nanoparticles.
In order to understand the effect of pre-reduction temperature
on H2 chemisorption properties in TPD of Ni(25)/Al2O3-HP, the
profiles have been obtained after pre-reducing the catalyst at
450 °C. As can be seen from the data shown in parentheses (see
Table 3), the pre-reduction of this catalyst at 450 °C decreases
the Ni metal surface area and dispersion by a factor of about 3
and the observed values (Ni surface area ∼3 m2/g-cat. and
dispersion ∼3%) are close to that obtained in static-II (5.4 m2/g-
cat. and 4%, respectively). From these results it can be
concluded that in the H2 chemisorption experiments over Ni-
based catalysts, the catalysts should be pre-reduced at the Tmax
in TPR rather than at a fixed temperature.
The profiles obtained from TPD-1 for Ni(25)/Al2O3-DP,
Ni(15)/Al2O3-DP and the commercial Ni/Al2O3 catalyst exhibit
peaks corresponding to both monolayer chemisorbed H2 and
subsurface layer and/or spillover H2. Similar to that discussed
above for the catalyst Ni(25)/Al2O3-HP, only the type-1 peaks
appearing below 450 °C have been considered for the
monolayer chemisorption of H2 in Ni(25)/Al2O3-DP, Ni(15)/
Al2O3-DP and the commercial Ni/Al2O3 catalyst as well.
However, since the type-1 peaks change into a sharp single peak
and the intensity of type-2 peak decreased dramatically in both
TPD-2 and TPD-3, it is presumed that the H2 desorbed in these
TPD methods correspond to mainly the monolayer chemisorbed
H2. The majority of subsurface layer and/or spillover H2 have
already been removed during the Ar flush at Tmax in TPR +
10°C. Consequently, the entire areas of the TPD curves have
been taken for the determination of the monolayer chemisorbed
H2 on these catalysts.
The Ni metal specific surface area, dispersion and crystallite
sizes calculated from TPD curves of Ni(25)/Al2O3-DP, Ni(15)/
Al2O3-DP are included in Table 3 together with that of the
commercial Ni/Al2O3 catalyst. A comparison of data obtained
from TPD and static methods reveal that both TPD-2 and TPD-
3 provide Ni metal specific surface area and dispersion close to
those obtained from static methods. These results reveal that
flushing of catalyst surface in an inert gas at Tmax in TPR + 10 °C
is important to remove significant amount of subsurface layer
and/or spillover H2. The concentration of H2 gas used for pre-
reduction and surface saturation does not appear to have any
significant impact on the chemisorption properties of Ni-based
catalysts.
3.4. Transmission electron microscopy
In order to further substantiate the TPD results, the best
sample, Ni(15)/Al2O3-DP, which showed the highest Ni metal
surface area of about 170m2/g-Ni and the highest Ni metal
dispersion of about 26% was also analyzed by TEM and the
micrograms are presented in Fig. 7. The pictures show highly
810 S. Velu, S.K. Gangwal / Solid State Ionics 177 (2006) 803–811
(a)
(b)
Fig. 7. Transmission electron micrographs of Ni(15)/Al2O3-DP. (a) Unreduced
and (b) pre-reduced at Tmax in TPR for 1h and stored in 2-propanol.
dispersed Ni particles, especially in the reduced sample (see Fig.
7 (b) wherein individual particles are clearly seen). The average
particle sizes vary between 5 and 10 nm, supporting the TPD
data, which shows the presence of nano-dispersed Ni with a Ni
crystallite size of about 4 nm in this sample. It should be noted,
however, that unlike TPD, wherein pre-reduction has been
performed in situ, the samples have been pre-reduced and stored
in 2-propanol for TEM measurements, during which particle
agglomeration could occur. Further work on the detailed
characterization and catalytic studies in the hydrogenation of
aromatics and sugars is currently in progress and will be
reported in the near future.
4. Conclusions
The present study leads to the following conclusions:
1. In measuring the hydrogen chemisorption properties of Ni-
based catalysts by TPD, the catalysts should be pre-reduced
at the Tmax in TPR as a “signature reduction” rather than at a
fixed temperature chosen arbitrarily as a “blanket reduction”.
2. Since in Ni-based catalysts, a part of H2 migrates to
subsurface layer or to the support as spillover H2, the
amount of H2 desorbed in TPD generally exceeds the
monolayer chemisorbed H2, exhibiting TPD profiles over the
entire temperature range. In such case, the TPD area in the
low temperature range (below 450°C) should be used for the
determination of monolayer chemisorbed H2.
3. Flushing the pre-reduced catalyst surface by an inert gas at
slightly elevated temperature, at least 10 °C, above the pre-
reduction temperature removes most of the subsurface layer
H2 and/or spillover H2. Surface saturation of such a fresh
catalyst with H2 at room temperature forms a monolayer of
chemisorbed H2. In such case, the entire TPD area should be
used for the quantitative estimation.
4. In this study, new series of highly dispersed Ni/Al2O3
catalysts containing 15 to 25 wt.% Ni with a high Ni metal
surface area and smaller crystallite size have been developed.
The Ni/Al2O3 catalyst containing about 15 wt.% Ni exhibited
higher Ni metal specific surface area of about 170 m2/g-Ni
and high metal dispersion of about 26% compared to a
commercial Ni/Al2O3 catalyst containing the same metal
loading, which exhibits Ni metal specific surface area and
dispersion of about 110 m2/g-Ni and 16%, respectively.
Acknowledgements
The authors wish to acknowledge the Research Triangle
Institute (RTI) for funding this work. Helpful discussions were
held with Prof. Jim Goodwin of Clemson University, USA and
subsequent static chemisorption data. The alumina samples
were supplied by Almatis AC Inc., LA, USA. Thanks are also
due to Dr. Raghubir Gupta, the research director of the Center
for Energy Technology for his encouragement and support to
this work.
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