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Applied Catalysis A - General Volume 245 Issue 1 2003 (Doi 10.1016 - s0926-860x (02) 00647-6) Akula Venugopal Mike S. Scurrell - Hydroxyapatite As A Novel Support For Gold and Ruthenium Catalysts
Applied Catalysis A - General Volume 245 Issue 1 2003 (Doi 10.1016 - s0926-860x (02) 00647-6) Akula Venugopal Mike S. Scurrell - Hydroxyapatite As A Novel Support For Gold and Ruthenium Catalysts
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.
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
138
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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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Table 1
Specific surface areas obtained for the various catalysts
Catalyst
HAP
3% Ru/HAP
3% Au/HAP
Spent
56
48
54
54
44
45; 34a
Fig. 2. TPR pattern of the pure HAP, 3% Au/HAP and 3% Ru/HAP catalysts.
141
Fig. 3. TPD of NH3 patterns of the pure HAP, 3% Ru/HAP and 3% Au/HAP.
142
Fig. 4. TPD of CO2 patterns of the pure HAP, 3% Ru/HAP and 3% Au/HAP.
143
144
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Fig. 9. Methanation activity over Ru/HAP at 400 C and CO flow rate = 82.3 cm3 /h.
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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.
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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