Bus Eveline, Miller Jeffrey T, van Bokhoven Jeroen A
Institute for Chemical and Bioengineering, Swiss Federal Institute of Technology, ETH, CH-8093 Zurich, Switzerland.
J Phys Chem B. 2005 Aug 4;109(30):14581-7. doi: 10.1021/jp051660z.
Hydrogen is dissociatively adsorbed on the gold particles in Au/Al(2)O(3) catalysts, as demonstrated by a combination of in-situ X-ray absorption spectroscopy, chemisorption, and H/D exchange experiments. This chemisorption of hydrogen induces changes in the Au L(3) and L(2) X-ray absorption near-edge structures. The gold atoms on corner and edge positions dissociate the hydrogen, which does not spill over to the face sites. Therefore, the average number of adsorbed hydrogen atoms per surface gold atom increases with decreasing particle size. With temperature, the hydrogen uptake by supported gold increases or remains constant, whereas it decreases for platinum. Furthermore, in H/D exchange experiments, the activity of Au/Al(2)O(3) increases strongly with temperature. Thus, the dissociation and adsorption of hydrogen on gold is activated.
原位X射线吸收光谱、化学吸附和H/D交换实验相结合表明,氢气在Au/Al₂O₃催化剂的金颗粒上发生解离吸附。氢气的这种化学吸附会引起金L₃和L₂ X射线吸收近边结构的变化。位于边角位置的金原子使氢气解离,且不会溢流到面心位置。因此,随着颗粒尺寸减小,每个表面金原子吸附的氢原子平均数量增加。随着温度升高,负载型金对氢气的吸收增加或保持不变,而铂对氢气的吸收则减少。此外,在H/D交换实验中,Au/Al₂O₃的活性随温度强烈增加。因此,氢气在金上的解离和吸附是活化的。