Mechanism study of reduction of CO_2 into formic acid by in-situ hydrogen produced from water splitting with Zn: Zn/ZnO interface autocatalytic role  

作　　者：Yi Le Heng Zhong Yang Yang Runtian He Guodong Yao Fangming Jin 

机构地区：[1]School of Environmental Science and Engineering, State Key Lab of Metal Matrix Composites, Shanghai Jiao Tong University [2]Research Institute for Chemical Process Technology, National Institute of Advanced Industrial Science and Technology (AIST) [3]Graduate School of Environmental Studies, Tohoku University

出　　处：《Journal of Energy Chemistry》2017年第5期936-941,共6页能源化学（英文版）

基　　金：the financial support of the National Natural Science Foundation of China (No. 21277091 & 51472159);the State Key Program of National Natural Science Foundation of China (No. 21436007);the Key Basic Research Projects of Science and Technology Commission of Shanghai (No. 14JC1403100);the Chenxing-SMG Young Scholar Project of Shanghai Jiao Tong University

摘　　要：We have previously developed a new process of highly efficient conversion of COand water into formic acid with metallic Zn without the addition of catalyst, however, its mechanism is not clear, particularly in the catalytic role of Zn/ZnO interface. Herein, the autocatalytic role of Zn/ZnO interface formed in situ during the reduction of COinto formic acid with Zn in water was studied by combining high resolution transmission electron microscopy（HRTEM）, X-ray diffraction（XRD） and X-ray photoelectron spectroscopy（XPS） techniques and experimental data. The electron microscope results show that possible defects or dislocations formed on Zn/ZnO interface, in which plays a key role for Zn H-formation. Further XPS analyses indicate that oxygen vacancies on Zn/ZnO interface increased at short reaction times（less than 10 min）. These analyses and experimental results suggest that a highly efficient and rapid conversion of COand water into formic acid should involve an autocatalytic role of the Zn/ZnO interface formed in situ, particularly at the beginning of the reaction.We have previously developed a new process of highly efficient conversion of CO_2 and water into formic acid with metallic Zn without the addition of catalyst, however, its mechanism is not clear, particularly in the catalytic role of Zn/ZnO interface. Herein, the autocatalytic role of Zn/ZnO interface formed in situ during the reduction of CO_2 into formic acid with Zn in water was studied by combining high resolution transmission electron microscopy(HRTEM), X-ray diffraction(XRD) and X-ray photoelectron spectroscopy(XPS) techniques and experimental data. The electron microscope results show that possible defects or dislocations formed on Zn/ZnO interface, in which plays a key role for Zn H-formation. Further XPS analyses indicate that oxygen vacancies on Zn/ZnO interface increased at short reaction times(less than 10 min). These analyses and experimental results suggest that a highly efficient and rapid conversion of CO_2 and water into formic acid should involve an autocatalytic role of the Zn/ZnO interface formed in situ, particularly at the beginning of the reaction.

关 键 词：MECHANISM CO2 reduction ZINC Water dissociation Interface catalysis 

分 类 号：O643.12[理学—物理化学]