Initial Reduction of CO 2 on Pd-, Ru-, and Cu-Doped CeO 2 (111) Surfaces: Effects of Surface Modification on Catalytic Activity and Selectivity

Chen Guo, Shuxian Wei, Sainan Zhou, Tian Zhang, Zhaojie Wang, Siu-Pang Ng, Xiaoqing Lu, Chi-Man Lawrence Wu, Wenyue Guo
ACS Applied Materials & Interfaces 2017 August 9, 9 (31): 26107-26117
Surface modification by metal doping is an effective treatment technique for improving surface properties for CO2 reduction. Herein, the effects of doped Pd, Ru, and Cu on the adsorption, activation, and reduction selectivity of CO2 on CeO2 (111) were investigated by periodic density functional theory. The doped metals distorted the configuration of a perfect CeO2 (111) by weakening the adjacent Ce-O bond strength, and Pd doping was beneficial for generating a highly active O vacancy. The analyses of adsorption energy, charge density difference, and density of states confirmed that the doped metals were conducive for enhancing CO2 adsorption, especially for Cu/CeO2 (111). The initial reductive dissociation CO2 → CO* + O* on metal-doped CeO2 (111) followed the sequence of Cu- > perfect > Pd- > Ru-doped CeO2 (111); the reductive hydrogenation CO2 + H → COOH* followed the sequence of Cu- > perfect > Ru- > Pd-doped CeO2 (111), in which the most competitive route on Cu/CeO2 (111) was exothermic by 0.52 eV with an energy barrier of 0.16 eV; the reductive hydrogenation CO2 + H → HCOO* followed the sequence of Ru- > perfect > Pd-doped CeO2 (111). Energy barrier decomposition analyses were performed to identify the governing factors of bond activation and scission along the initial CO2 reduction routes. Results of this study provided deep insights into the effect of surface modification on the initial reduction mechanisms of CO2 on metal-doped CeO2 (111) surfaces.


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