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Processes in Isotopes and Molecules IOP Publishing
Journal of Physics: Conference Series 182 (2009) 012049 doi:10.1088/1742-6596/182/1/012049

Preparation and characterization of nickel based

multicomponent catalysts

Mihaela Lazar, Maria Mihet, Monica Dan, Valer Almasan and Petru Marginean
National Institute for Research and Development of Isotopic and Molecular
Technologies, 65-103 Donath, 400293 Cluj-Napoca, Romania

E-mail: diana.lazar@itim-cj.ro

Abstract Two series of modified alumina supported nickel catalysts were prepared and
characterized. First series consist in bimetallic Ni-Au and Ni-Ag catalysts supported on
alumina; the second series consist in Ni catalysts supported on bicomponent oxides. The
catalysts were prepared by impregnation: Ni/Al2O3, Ni/CeO2-Al2O3 and Ni/La2O3-Al2O3 (10 wt
% Ni and 6 wt % additional oxide) and co-impregnation: Ni-Au/Al2O3 and Ni-Ag/Al2O3 (10 wt
% Ni and 1 wt % Au or Ag). The catalytic surface was characterized by N2 adsorption-
desorption isotherms. The catalytic sites were characterized by hydrogen Thermo Programmed
Desorption (TPD) method.

1. Introduction
The usual catalyst for methane steam reforming is based on Ni as the active element [1]. The main
problem with this type of catalysts is that Ni also favors the formation of graphite, which deactivates
the catalysts and may eventually lead to their destruction. One solution is to selectively change the
surface structure through the formation of a superficial alloy [2]. Metals such as Ag [3] and Au [4] on
Ni substrate have been tested and shown promising for coke minimization in the steam reforming (of)
hydrocarbons. In order to obtain catalysts with high activity and stability, it is fundamental to maintain
the dispersion of the active phase and the stability of the support. Both properties can be induced by
addition of a second oxide to the support. La2O3 is able to stabilize alumina and it can also avoid Pt
agglomeration [5]. The addition of ceria to Pt supported catalysts improves the catalytic properties due
to the formation of a larger Pt-CeO2 interface [6]. Pd/Al2O3 promoted with ceria and lanthana showed
higher activity for steam reforming of methane [7]. In this paper we present the results obtained in
preparation and characterization of Ni/Al2O3 catalysts modified by addition of Ag and Au to Ni and
CeO2 and La2O3 to alumina support.

2. Experimental
For preparation of multicomponent nickel catalysts the wet impregnation method was used. Alumina
supported Ni catalysts (10 wt % Ni) modified with Ag (1 wt %) and Au (1 wt %) were prepared by co-
impregnation of γ-Al2O3 (St = 135 m2/g) with aqueous solutions of Ni(NO3)2·6H2O and AgNO3
(HAuCl4·3H2O respectively). The impregnated samples were dried at room temperature overnight,
calcined under nitrogen at 500°C for 4 h and reduced in H2 at 400°C for 4 h. The mixed supports
containing CeO2 (6 wt %) and La2O3 (6 wt %) loadings were prepared by impregnation of γ-alumina
with aqueous solution of Ce(NO3)2 or La(NO3)3 followed by calcinations in nitrogen at 500°C for 4 h.


c 2009 IOP Publishing Ltd 1
Processes in Isotopes and Molecules IOP Publishing
Journal of Physics: Conference Series 182 (2009) 012049 doi:10.1088/1742-6596/182/1/012049

Nickel (10 wt %) was than added by impregnation of mixed supports with aqueous solutions of
Ni(NO3)2, as described below.
Total surface area (St), pore volume (Vp) and pore radius (rp) of the samples were obtained from N2
adsorption-desorption isotherms. The isotherms were measured using a Sorptomatic 1990 apparatus.
The BET method was used for calculation of St, and the Dollimore-Heal method for determination of
porosity parameters.
The TPD experiments were performed in an installation composed by: gas introduction unit,
tubular reactor and thermal conductivity detector (TCD). The gases used in these experiments were
99.999% purity. An extra-purification was made by passing the gases through a Ni/Cr2O3 catalyst
followed by a molecular sieve, just before entering in the reactor. The catalysts sample was activated
in hydrogen at 350°C and then cooled down. The hydrogen was adsorbed on catalyst’s surface at 0oC
for about 1 h and then Ar was passed through the reactor for about 30 min., at 0oC, in order to remove
the un-chemosorbed hydrogen from the system. The thermodesorption was then started by heating the
sample in argon with heating rate 5°C /min and argon flow 25 ml/min. The desorbed hydrogen was
monitored by TCD.

3. Results and discussions

The surface area and pore volume of the Ni-Me/Al2O3 catalysts have similar values with the simple
Ni/Al2O3. That’s means that the deposed metal nanoparticles are very small and well dispersed on the
support surface, including the pore’s walls. For Ni/MxOy-Al2O3 these values are smaller (table 1)
which lead as to conclusion that either the second oxide deposited on alumina fills some smaller pores,
or the repeated thermal treatment modify the surface area.
Table 1. Total surface area and pore volume for multicomponent nickel catalysts.
Catalysts
Ni/Al2O3 Ni-Ag/Al2O3 Ni-Au/Al2O3 Ni/CeO2-Al2O3 Ni/La2O3-Al2O3
2
St (m /g) 113 115 114 105 109
Vp (cm3/g) 0.151 0.150 0.153 0.145 0.140

The adsorption-desorption isotherms are of type IV which corresponds to mesoporous solids

(figure 1). The pore size distribution is relatively uniform with a medium diameter of 50 Å (figure 2).
The medium size of pores does not differ very much between the 5 catalysts. It is possible that the
additional oxide and/or metal in Ni/MxOy-Al2O3 catalysts to be deposited on the pore’s walls, but to
don’t fill them completely, explaining the slight decrease in total surface area.
.

200 25
adsorption
175
relative volume (%)

desorption 20
150
V ads (cm /g)

125 15
3

100
10
75
50 5
25
0
0
0 25 50 75 100 125 150
0,00 0,25 0,50 0,75 1,00
pore radius (A)
p/p0

Figure 1. Adsorption-desorption isotherms of Figure 2. Pore distribution for Ni/CeO2-

N2 for Ni-Au/Al2O3. Al2O3.

2
Processes in Isotopes and Molecules IOP Publishing
Journal of Physics: Conference Series 182 (2009) 012049 doi:10.1088/1742-6596/182/1/012049

The heterogeneous supported metal catalyst surface includes a number of active sites showing
different adsorptive and catalytic activities. Temperature-programmed desorption is a helpful
technique for investigating these heterogeneous surfaces. The hydrogen atoms are desorbed from the
surface at different temperatures depending on the strength of the hydrogen-metal bond. The addition
of the second metal or the second oxide modifies the surface properties which are reflected in the
modifying of the catalytic sites. Figure 3 presents the TPD plots for the five studied catalysts.

0,02

0,015
Desorbed H2 (a.u)

0,01

0,005

0
0 50 100 150 200 250 300 350 400
-0,005

Temperature (ºC)

Ni/Al2O3

0,02 0,02

0,015 0,015
Desorbed H 2 (a.u)

Desorbed H2 (a.u)

0,01 0,01

0,005 0,005

0
0
0 50 100 150 200 250 300 350 400
0 50 100 150 200 250 300 350 400
-0,005
-0,005
Tem perature (ºC) Temperature (ºC)

Ni/CeO2 – Al2O3 Ni/La2O3 – Al2O3

0,02 0,02
Desorbed H 2 (a.u)

0,015 0,015
Desorbed H2 (a.u)

0,01 0,01

0,005 0,005

0 0
0 50 100 150 200 250 300 350 400 0 50 100 150 200 250 300 350 400
-0,005 -0,005

Temperature (ºC) Temperature (ºC)

Ni – Ag/Al2O3 Ni – Au/Al2O3
Figure 3. Hydrogen thermodesorption spectra for multicomponent nickel catalysts.

The TPD plots show two desorption peaks indicating that hydrogen desorbs from the surface in two
steps. This situation corresponds to the presence of at least two types of active sites on the catalysts
surface. Additional components to Ni/Al2O3 catalyst change the shape of thermodesorption spectra. By
adding the second oxide to the catalyst support, the first desorption peak shifts ~ 20°C to higher
temperatures (from ~ 130°C to ~ 150°C). The nickel supported on mixed oxides adsorb hydrogen
stronger that Ni/Al2O3. The second desorption peak decreases in intensity by adding ceria to alumina
support and increases by adding lanthanum oxide. The silver and gold change dramatically the shape
of TPD plots. By adding Ag, two distinct peaks are obtained: first one having smaller intensity desorbs
at 74°C and the second one, more intense, desorbs at 145°C. Silver decreases very much the

3
Processes in Isotopes and Molecules IOP Publishing
Journal of Physics: Conference Series 182 (2009) 012049 doi:10.1088/1742-6596/182/1/012049

desorption temperature (about 74°C) indicated that a part of adsorbed hydrogen is much weaker
bonded to the catalytic sites. Adding Au to the nickel catalyst, the desorption temperature and the total
amount of desorbed hydrogen are very much decreased. Both these parameters indicate a weaker
capacity of Ni-Au catalysts to adsorb hydrogen comparing to Ni catalysts.

4. Conclusions
Two series of modified alumina supported nickel catalysts were prepared and characterized by N2
adsorption-desorption and hydrogen Thermo Programmed Desorption. The catalysts were prepared by
impregnation: Ni/Al2O3, Ni/CeO2-Al2O3 and Ni/La2O3-Al2O3 and co-impregnation: Ni-Au/Al2O3 and
Ni-Ag/Al2O3. The total surface area and pores volume are not influenced by the addition of Ag and
Au, but decrease at the addition of the transitional oxide. The TPD results are influenced by the
addition of second metal and oxide. The Ni supported on mixed oxides have the desorption peaks at
higher temperature than Ni/Al2O3 indicating stronger hydrogen adsorption sites. The addition of Ag
and Au have the opposite effect decreasing much the desorption temperature and desorbed amount of
hydrogen in the case of gold. These data will be correlated with catalytic activity results in steam
reforming reaction in order to better describe the catalytic mechanism.
Future experiments using different concentration of noble metals and transitional oxides will allow
us to design a catalyst with improved qualities for hydrogen production by methane steam reforming.

Acknowledgements
This research was supported by the Romanian ANCS Department: PN II Program under contract
21004/2007.

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