Insight into CH4 dissociation on NiCu catalyst: A first-principles study

A density-functional theory method has been conducted to investigate the dissociation of CH4 on NiCu (1 1 1) surface. Two models: uniform surface slab model (Model A) and Cu-rich surface slab model (Model B) have been constructed to represent the NiCu (1 1 1) surface, in which the ratio of Ni/Cu is unit. The obtained results on the two models have been compared with those obtained on pure Ni (1 1 1) and Cu (1 1 1). It is found that the adsorption of CHx(x = 1–3) on Model B are weaker than on Model A. The rate-determining steps of CH4 dissociation on Model A and B both are the dissociation of CH, and the corresponding activation barriers are 1.37 and 1.63 eV, respectively. Obviously, it is approximately equal on Model A to that on pure Ni (1 1 1) [H. Liu, R. Zhang, R. Yan, B. Wang, K. Xie, Applied Surface Science 257 (2011) 8955], while it is lower by 0.58 eV on Model B compared to that on pure Cu (1 1 1). Therefore, the Cu-rich surface has better carbon-resistance ability than the uniform one. Those results well explain the experimental facts that NiCu/SiO2 has excellent catalytic performance and long-term stability [H.-W. Chen, C.-Y. Wang, C.-H. Yu, L.-T. Tseng, P.-H. Liao, Catalysis Today 97 (2004) 173], however, there is serious carbon deposition on NiCu/MgO–Al2O3 in CO2 reforming of methane [J. Zhang, H. Wang, A. K. Dalai, Journal of Catalysis 249 (2007) 300].