title: Effect of the components' interface on the synthesis of methanol over Cu/ZnO from CO2/H2: a microkinetic analysis based on DFT + U calculations.
abstract: The elucidation of chemical reactions occurring on composite systems (e.g., copper (Cu)/zincite (ZnO)) from first principles is a challenging task because of their very large sizes and complicated equilibrium geometries. By combining the density functional theory plus U (DFT + U) method with microkinetic modeling, the present study has investigated the role of the phase boundary in CO2 hydrogenation to methanol over Cu/ZnO. The absence of hydrogenation locations created by the interface between the two catalyst components was revealed based on the calculated turnover frequency under realistic conditions, in which the importance of interfacial copper to provide spillover hydrogen for remote Cu(111) sites was stressed. Coupled with the fact that methanol production on the binary catalyst was recently believed to predominantly involve the bulk metallic surface, the spillover of interface hydrogen atoms onto Cu(111) facets facilitates the production process. The cooperative influence of the two different kinds of copper sites can be rationalized applying the Brönsted-Evans-Polanyi (BEP) relationship and allows us to find that the catalytic activity of ZnO-supported Cu catalysts is of volcano type with decrease in the particle size. Our results here may have useful implications in the future design of new Cu/ZnO-based materials for CO2 transformation to methanol.
authors.affiliation: Department of Applied Chemistry, School of Advanced Materials and Nanotechnology, Xidian University, No. 2 South Taibai Road, Xi'an 710071, People's Republic of China. qltang@xidian.edu.cn.
authors.forename: Qian-Lin
authors.initials: QL
authors.lastname: Tang
authors.forename: Wen-Tian
authors.initials: WT
authors.lastname: Zou
authors.forename: Run-Kun
authors.initials: RK
authors.lastname: Huang
authors.forename: Qi
authors.initials: Q
authors.lastname: Wang
authors.forename: Xiao-Xuan
authors.initials: XX
authors.lastname: Duan
mesh_terms: D000327:Adsorption; D002245:Carbon Dioxide / Q000737:chemistry*; D002384:Catalysis; D060326:Chemistry Techniques, Synthetic; D003300:Copper / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry*; D006865:Hydrogenation; D007700:Kinetics; D000432:Methanol / Q000138:chemical synthesis* / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D011789:Quantum Theory; D015034:Zinc Oxide / Q000737:chemistry*
chemical_list: D002245:Carbon Dioxide; D003300:Copper; D006859:Hydrogen; D015034:Zinc Oxide; D000432:Methanol