Applied Catalysis A: General 245 (2003) 137147

Hydroxyapatite as a novel support for gold and ruthenium catalysts

Behaviour in the water gas shift reaction
Akula Venugopal1 , Mike S. Scurrell
Molecular Sciences Institute, School of Chemistry, University of Witwatersrand, PO Wits, 2050 Johannesburg, South Africa
Received 27 June 2002; received in revised form 2 December 2002; accepted 3 December 2002

Abstract
Novel catalysts comprising gold or ruthenium supported on hydroxyapatite are prepared by a depositionprecipitation
method and examined for their behaviour in the water gas shift reaction at various reaction temperatures and at atmospheric pressure. The physicochemical properties of the catalysts were characterized using BET-surface area (BET-SA), XRD, TPR, TPD
of NH3 and CO2 . High WGS activities were observed over Au/HAP compared with Ru/HAP catalyst. The Ru/HAP catalyst showed methanation activity at temperatures above 300 C, caused by a tendency for the dissociative chemisorption of CO to occur, though this process can be suppressed to some extent by an increase in the partial pressure of water under reaction conditions.
2002 Elsevier Science B.V. All rights reserved.
Keywords: Hydroxyapatite; Gold; Ruthenium; Water gas shift

1. Introduction
Most of the interest in gold catalysis [1] has involved work in which reducible or partially reducible
metal oxides such as iron oxide [2], ZnO [3] TiO2 [4]
and cobalt oxide [5] have been used for the removal
of carbon monoxide in various industrial and domestic applications. There is relatively little work reported
on the behaviour of gold on non-reducible supports
such as Al2 O3 , SiO2 [6] and zeolite molecular sieves
[79]. There appears to have been no reports to date
on the use of hydroxyapatite as a support material for
gold. We have found this support to be particularly
attractive in that gold deposited on this material is ex Corresponding author. Tel.: +27-11-717-6716;
fax: +27-11-717-6748.
E-mail addresses: akula@iict.ap.nic.in (A. Venugopal),
scurrell@aurum.wits.ac.za (M.S. Scurrell).
1 Present address: Catalysis Section, Indian Institute of Chemical
Technology, Hyderabad 500007, India.

ceedingly active for the water gas shift reaction at low

temperatures. In this paper we report for the first time
the low temperature water gas shift activity over novel
catalysts comprising gold supported on hydroxyapatite prepared by a depositionprecipitation method.
The Au/hydroxyapatite (Au/HAP) showed exceptionally high activity when compared with Ru/HAP. Some
of the catalysts were characterized using BET-surface
area, XRD, TPR, TPD of NH3 /CO2 and the WGS activities were measured at various temperatures ranged
from 100 to 320 C.

2. Experimental
2.1. Preparation of hydroxyapatite and
metal/AP catalysts
The hydroxyapatite was prepared according to
published procedures [10,11]. In a typical experiment

0926-860X/02/$ see front matter 2002 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0926-860X(02)00647-6

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A. Venugopal, M.S. Scurrell / Applied Catalysis A: General 245 (2003) 137147

a solution of calcium nitrate tretrahydrate (32.6

102 mol) in 200 ml water was brought to pH 1112
with concentrated (25%) ammonia solution) and
thereafter diluted to 500 ml. A solution of diammonium hydrogenphosphate (31.8 102 mol) in 300 ml
water was brought to a pH of 1112 with concentrated (25%) ammonia solution and thereafter diluted
to 600 ml. Under vigorous stirring the phosphate solution was added drop wise to the solution of the
calcium salt over a period of ca. 2 h to produce a
milky white precipitate, which was then stirred and
boiled for 30 min. After filtration, the precipitate was
washed thoroughly and dried at 100 C overnight
and then calcined at 500 C for 3 h. The calcined
hydroxyapatite is hereafter denoted as HAP.
The Au and Ru supported on HAP catalysts are
prepared by a depositionprecipitation method using the diluted aqueous solutions of hydrogen tetrachloroaurate, HAuCl4 xH2 O, or ruthenium trichloride,
RuCl3 3H2 O using ammonium hydroxide as the precipitating agent. In a typical preparation, the required
amount of calcined HAP was dispersed in 200 ml of
water with continuous stirring for 3 h. To this solution the equivalent amounts of metal precursor solutions were added dropwise under vigorous stirring
along with diluted ammonium hydroxide until the pH
reached a value of 8.68.8 at ambient temperatures.
The precipitates were subsequently stirred for 3 h then
filtered, washed thoroughly with hot distilled water
until no chloride ions were found in the filtrate (visual
observations using silver nitrate as a test reagent).
Care has been taken to wash the gels until the pH of
the filtrate reached a value of 7.0. The cakes were then
carefully dried at 120 C for 16 h and subsequently
calcined in air at 400 C for 3 h using a temperature
ramping rate of 5 C/min. All the precursors for the
preparation of catalysts used were of analytical grade.
2.2. Characterization of the catalysts
The BET-surface areas of the catalysts were obtained by means of dinitrogen physisorption at ca.
77 K using a Micromeritics ASAP 2000 instrument.
Prior to the measurements all the catalysts were degassed at 120 C for 30 min. The X-ray diffraction
analysis of the 3 wt.% Au and 3 wt.% Ru supported
on HAP catalysts were measured in the 2 range from
10 to 80 using a Phillips PW Diffractometer and

employed Ni filtered Cu K radiation at 40 kV and

30 mA. The XRD patterns were compared with the
ICDD 1999 (Powder Diffraction File Release 1999
Data Sets 149 plus 7086 PDF) and ASTM data. The
temperature programmed reduction (TPR) investigations and temperature programmed desorption (TPD)
of ammonia or carbon dioxide were carried out using a purpose built reactor system connected to a
thermal conductivity unit. A calibrated furnace and
temperature programmer was used for the TPR/TPD
analysis and the accuracy of the temperature measurement is 2 C. For TPR analyses a 5% dihydrogen in argon was used. The water gas shift (WGS)
activities of the samples were measured in a flow
microreactor at atmospheric pressure. In a typical experiment about 0.420.44 cm3 of the calcined catalyst was pretreated in air at 400 C for 1 h and then
cooled to the reaction temperature in a flow of helium.
The flow rates of CO = 82.3 cm3 /h and the water
vapour flow rate, which not exceed 921.5 cm3 /h were
maintained throughout the studies. The WGS activities
were recorded only after 3 h of continuous operation.
Conversions were calculated based on the degree of
CO conversion and again checked by carbon balance
from the formation of CO2 . The CO reactant gas mixture contained 5.1 vol.% CO, with the balance being
helium. The activity measurements were carried out
with a glass microreactor interfaced to a gas chromatograph equipped with TCD analysis using a Carbosieve
column. The gas hourly space velocity (GHSV) was
ca. 5900 h1 for these studies. The experimental error
in the evaluation of catalytic activities was less than
2%, unless otherwise mentioned.
3. Results and discussion
The BET-surface area of the fresh Au/HAP catalyst was found to be 54 m2 g1 and decreased slightly
to 45 m2 g1 in the spent system (Table 1). However, a still lower surface area of 34 m2 g1 was observed when the catalyst had been on stream for 16 h
at 300 C.
3.1. XRD analysis
X-ray diffraction analysis (Fig. 1) revealed the
presence of the Ca10 (PO4 )6 (OH)2 phase in all fresh

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139

Fig. 1. XRD patterns of the (1) 3% Au/HAP spent, (2) 3% Au/HAP fresh, (3) 3% Ru/HAP spent, (4) 3% Ru/HAP fresh, (5) HAP spent
and (6) HAP fresh catalysts.

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A. Venugopal, M.S. Scurrell / Applied Catalysis A: General 245 (2003) 137147

3.2. TPR analysis

Table 1
Specific surface areas obtained for the various catalysts
Catalyst

HAP
3% Ru/HAP
3% Au/HAP

SBET (m2 /g)

Fresh

Spent

56
48
54

54
44
45; 34a

a BET-surface area of the spent Au/HAP catalyst after the

continuous operation of 16 h at 300 C.

and spent samples of pure hydroxyapatite, Au/HAP

and Ru/HAP. The reflections due to the hydroxyapatite phase were observed at 2 values of 31.82, 32.9,
43.05 and 49.46 , with corresponding d values of
0.281, 0.272, 0.2631 and 0.1841 nm. It was difficult
to distinguish the metallic Au phases in Au/HAP catalyst since the Au peaks overlap the reflections due to
the hydroxyapatite phase. No reflections attributable
to either metallic ruthenium or to ruthenium dioxide
phases were observed in Ru/HAP fresh and spent
forms.

The TPR traces of the pure Ca10 (PO)6 (OH)2 ,

Au/HAP and Ru/HAP are shown in Fig. 2. No signals due to the reduction of gold species in Au/HAP
catalyst were found. From the TPR results alone we
could speculate that Au may be in highly dispersed
state and/or interacting strongly with the support or
stabilized in the metallic state. Park and Lee [12] reported that the phase transition of gold particles from
Au(OH)3 through Au2 O3 to metallic gold is observed
with increase in calcination temperatures with Au irrespective of the support used. It therefore seems likely
that gold is autoreduced in the Au/HAP samples during preparation, drying and/or calcination. In the case
of Ru/HAP, two distinct peaks with Tmax at 135 C
and centered at ca. 290 C were observed. The metal
support interactions play a major role in stabilizing
the active component and thereby influence the reduction behaviour of the metal catalysts [13]. In the
comparative study of XPS characterization and TPR
behaviour of Au/Fe2 O3 catalysts, Hao et al. reported
that the higher the oxidation state of gold the lower is

Fig. 2. TPR pattern of the pure HAP, 3% Au/HAP and 3% Ru/HAP catalysts.

A. Venugopal, M.S. Scurrell / Applied Catalysis A: General 245 (2003) 137147

the reduction peak temperature of gold and the greater

is the reduction peak area [14]. In our earlier studies
on Au/Fe2 O3 we found reduction signals due to Au as
well as Fe2 O3 species [15] for Au/iron oxide samples
which were prepared by a depositionprecipitation

141

method similar to that employed in the present study.

Clearly, higher oxidation states of gold seem to be
stabilized by interaction with a reducible oxide such
as ferric oxide (haematite), but such a stabilization
option is not offered by a support such as HAP.

Fig. 3. TPD of NH3 patterns of the pure HAP, 3% Ru/HAP and 3% Au/HAP.

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3.3. TPD analysis

From Fig. 3 it is quite clear that the desorption
of ammonia commenced at 155 C in all the catalysts. However, the peak maxima are in significantly
different positions and suggest that the strengths of
acid sites present in these samples are found to follow the order. Au/HAP
HAP > Ru/HAP. From
the relative intensities of the desorption curves the
concentration of acid sites appears to also follow the
same order: Au/HAP
HAP > Ru/HAP. From

the TPD of CO2 analysis (Fig. 4) it is also observed

that Au/HAP contains sites exhibiting greater basicity
compared with those present on the Ru/HAP catalyst. The order of basicities follows the sequence:
Au/HAP > Ru/HAP > HAP.
3.4. Water gas shift activity measurements
The application of WGSR in various industrial processes is very well documented over supported noble
and base metal catalysts [7,1619]. In this investiga-

Fig. 4. TPD of CO2 patterns of the pure HAP, 3% Ru/HAP and 3% Au/HAP.

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143

Fig. 5. Temperature dependence of the WGSR of 3% Au/HAP and 3% Ru/HAP catalysts.

tion we report the studies on novel hydroxyapatite as

support for Au and Ru catalysts. It should be noted
here that neither water gas shift activity nor methanation behaviour is found over pure hydroxyapatite even
for reaction temperatures up to 400 C.
Fig. 5 shows the temperature dependence of the
WGSR activities. From Fig. 5 it is clearly seen that
the Au supported on hydroxyapatite (HAP) catalyst
has much higher activity compared with that of the
Ru/HAP system, particularly at lower temperatures.
Relative conversion levels are typically ca. 15 or
higher for reaction temperatures of 100120 C. Maximum conversions up to ca. 95% are observed at a
reaction temperature of 260 C over Au/HAP catalyst.
The conversion is increased with increase in reaction
temperature up to 260 C from there onwards it is
almost constant. From the time on stream analysis
(Fig. 6) it is quite evident that the WGS activity is
stable at 100 C for 16 h of continuous operation.
However, activity dropped slightly at a reaction
temperature of 300 C. The Ru/HAP started showing
methanation activity (Fig. 7) at above 300 C in contrast to the lack of methanation found with Au/HAP. It
is a known fact that supported Ru catalysts are found to
exhibit methanation activity at high reaction temperatures [20]. However, in the present study Ru supported

on HAP has been undertaken to examine water gas

shift properties since supported Pt-Ru [21] and potentially Au-Ru [15] catalysts could be employed in the
fuel cell and low temperature WGS applications. The
level of methanation activity over Ru/HAP is found
(Fig. 8) to be less than 4% even up to a reaction temperature of 400 C under similar conditions adopted
for both of the catalyst systems. However, varying
H2 O partial pressures have significant effect on the
WGSR behaviour on Ru/HAP catalyst at high reaction
temperatures. It is interesting to note that the methanation activity of Ru/HAP (Fig. 9) is increased with
decrease in the partial pressure of water vapour. Since
there is the potential for undesirable side reactions to
occur under WGS conditions, namely CO methanation
and CO disproportionation we investigated further
the nature of Ru/HAP for WGSR and methanation
behaviour at higher reaction temperatures. However,
none of the catalysts studied were found to have any
carbon or coke depositions in the spent forms.
3.5. Methanation activity of Ru/HAP catalyst
The nature of the support plays an important role in
governing the CO adsorption behaviour of noble metal
catalyst systems. Stubenrauch and Vohs observed

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A. Venugopal, M.S. Scurrell / Applied Catalysis A: General 245 (2003) 137147

Fig. 6. Time on stream analysis of WGSR activities over 3% Au/HAP catalyst.

the formation of adsorbed carbon and oxygen atoms

produced by the dissociation of CO over the Rh/CeO2
(1 1 1) system [22]. Kahlich et al. observed the
methanation activities over Ru/-Al2 O3 during the
preferential oxidation of CO at above 200 C [20].

However, in this investigation the Au/HAP did not

show any methanation activity and this might be due
to the weaker chemisorption of CO. Similarly, we
could not detect the formation of methanol either
due to CO hydrogenation and/or WGS reactions

Fig. 7. WGSR over Ru/HAP at higher temperatures.

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145

Fig. 8. Temperature dependence of CH4 formation over Ru/HAP.

on both Au/HAP and Ru/HAP catalysts. Niwa et al.

have observed the selective formation of CH4 over a
rhodium-Y zeolite catalyst in the WGS reaction [23].
At high reaction temperatures (above 300 C) both
WGS reaction and CO methanation to produce CH4
were observed over Ru/HAP. Erdohelyi et al. [17] and
Solymosi et al. [24] observed the formation of CH4

over supported iridium and Rh/TiO2 catalysts during

the water gas shift reaction. The formation of methane
can be explained by the hydrogenation of adsorbed
carbon C formed through the dissociative chemisorption of CO, this being favoured over the Ru/HAP
catalyst. TPR analysis of pure HAP did not show
any reduction signals up to 500 C confirming the

Fig. 9. Methanation activity over Ru/HAP at 400 C and CO flow rate = 82.3 cm3 /h.

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A. Venugopal, M.S. Scurrell / Applied Catalysis A: General 245 (2003) 137147

non-reducible character of HAP. An increase in the

partial pressure of water vapour decreased the formation of methane over Ru/HAP. An increase in the
reaction temperature increased the methanation activity, and there was a fall in carbon dioxide formation.
From the carbon balance analysis we also observed
that the decrease in CO2 levels at the point where
methane starts being generated in the reaction. This
further suggests that the formation of methane is at the
cost of some part of CO conversion via dissociative
chemisorption and C formation. Solymosi et al. [25]
also reported the formation of Rh-carbonyl-hydride
on supported Rh, which dissociates to form surface
carbon and subsequently the surface formed carbon
was hydrogenated to CH4 . At low partial pressures of
water vapour methanation is significant but at higher
water partial pressures methane production is greatly
decreased. This result could be due to the inhibition
of CO dissociation by water over Ru/HAP at high reaction temperatures.
Further studies on the extraordinarily high activity
of Au/HAP and the methanation behaviour of Ru/HAP,
and the possible role of the catalysts acidbase surface properties in relation to the WGS reaction are in
progress.

4. Conclusions
Metallic gold phases were found in both fresh and
spent Au/HAP catalysts. However, no Ru containing
species were detectable by means of XRD in either
fresh or spent Ru/HAP.
TPD analysis of ammonia or carbon dioxide revealed the higher amounts of surface concentrations of
acid or base sites on Au/HAP compared with Ru/HAP
catalyst.
No methanation activity is observed over Au/HAP
even up to 380 C; this could be due to the supported
Au catalysts having a low ability to dissociatively
chemisorb CO or H2 .
Au/HAP is more active than Ru/HAP for the water
gas shift reaction by a factor of at least 15 (on a catalyst
mass basis) for temperatures of 110120 C.
The activities for the water gas shift reaction of
Au/HAP and Ru/HAP become closer at higher reaction temperatures, but with the Ru/HAP catalyst
methanation represents a serious side reaction.

Methanation on Ru/HAP can be suppressed by

operating with a higher partial pressure of water
vapour.
Pure hydroxyapatite did not show either WGSR or
methanation activities even up to 400 C.

Acknowledgements
One of us (AV) acknowledges the award of a Postdoctoral Fellowship by the University of the Witwatersrand. Additional financial assistance made available
by Anglogold is gratefully acknowledged.

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