Palladium oxide(PdOx)and cobalt oxide(Co3O4)are efficient catalysts for methane(CH4)combustion,and Pd‐doped Co3O4catalysts have been found to exhibit better catalytic activities,which suggest synergism between the tw...Palladium oxide(PdOx)and cobalt oxide(Co3O4)are efficient catalysts for methane(CH4)combustion,and Pd‐doped Co3O4catalysts have been found to exhibit better catalytic activities,which suggest synergism between the two components.We carried out first‐principles calculations at the PBE+U level to investigate the Pd‐doping effect on CH4reactivity over the Co3O4catalyst.Because of the structural complexity of the Pd‐doped Co3O4catalyst,we built Pd‐doped catalyst models using Co3O4(001)slabs with two different terminations and examined CH4reactivity over the possible Pd?O active sites.A low energy barrier of0.68eV was predicted for CH4dissociation over the more reactive Pd‐doped Co3O4(001)surface,which was much lower than the0.98and0.89eV that was predicted previously over the more reactive pure Co3O4(001)and(011)surfaces,respectively.Using a simple model,we predicted CH4reaction rates over the pure Co3O4(001)and(011)surfaces,and Co3O4(001)surfaces with different amounts of Pd dopant.Our theoretical results agree well with the available experimental data,which suggests a strong synergy between the Pd dopant and the Co3O4catalyst,and leads to a significant increase in CH4reaction rate.展开更多
基金supported by the National Natural Science Foundation of China(21473233,21403277)the Energy Technologies Institute LLP,UK~~
文摘Palladium oxide(PdOx)and cobalt oxide(Co3O4)are efficient catalysts for methane(CH4)combustion,and Pd‐doped Co3O4catalysts have been found to exhibit better catalytic activities,which suggest synergism between the two components.We carried out first‐principles calculations at the PBE+U level to investigate the Pd‐doping effect on CH4reactivity over the Co3O4catalyst.Because of the structural complexity of the Pd‐doped Co3O4catalyst,we built Pd‐doped catalyst models using Co3O4(001)slabs with two different terminations and examined CH4reactivity over the possible Pd?O active sites.A low energy barrier of0.68eV was predicted for CH4dissociation over the more reactive Pd‐doped Co3O4(001)surface,which was much lower than the0.98and0.89eV that was predicted previously over the more reactive pure Co3O4(001)and(011)surfaces,respectively.Using a simple model,we predicted CH4reaction rates over the pure Co3O4(001)and(011)surfaces,and Co3O4(001)surfaces with different amounts of Pd dopant.Our theoretical results agree well with the available experimental data,which suggests a strong synergy between the Pd dopant and the Co3O4catalyst,and leads to a significant increase in CH4reaction rate.
