Light-Driven C−C Coupling for Targeted Synthesis of CH3COOH with Nearly 100 % Selectivity from CO2
Jinyu Ding
Key Laboratory of Synthetic and Biological Colloids, Ministry of Education, School of Chemical and Material Engineering, Jiangnan University, 214122 Wuxi, China
These authors contributed equally to this work.
Search for more papers by this authorPeijin Du
Key Laboratory of Synthetic and Biological Colloids, Ministry of Education, School of Chemical and Material Engineering, Jiangnan University, 214122 Wuxi, China
These authors contributed equally to this work.
Search for more papers by this authorJuncheng Zhu
Hefei National Research Center for Physical Sciences at Microscale, National Synchrotron Radiation Laboratory, University of Science and Technology of China, 230026 Hefei, China
These authors contributed equally to this work.
Search for more papers by this authorQing Hu
Key Laboratory of Synthetic and Biological Colloids, Ministry of Education, School of Chemical and Material Engineering, Jiangnan University, 214122 Wuxi, China
Search for more papers by this authorDongpo He
Key Laboratory of Synthetic and Biological Colloids, Ministry of Education, School of Chemical and Material Engineering, Jiangnan University, 214122 Wuxi, China
Search for more papers by this authorYang Wu
Hefei National Research Center for Physical Sciences at Microscale, National Synchrotron Radiation Laboratory, University of Science and Technology of China, 230026 Hefei, China
Search for more papers by this authorWenxiu Liu
Hefei National Research Center for Physical Sciences at Microscale, National Synchrotron Radiation Laboratory, University of Science and Technology of China, 230026 Hefei, China
Search for more papers by this authorDr. Shan Zhu
State Grid Anhui Electric Power Research Institute, 230601 Hefei, China
Search for more papers by this authorProf. Wensheng Yan
Hefei National Research Center for Physical Sciences at Microscale, National Synchrotron Radiation Laboratory, University of Science and Technology of China, 230026 Hefei, China
Search for more papers by this authorDr. Jun Hu
Hefei National Research Center for Physical Sciences at Microscale, National Synchrotron Radiation Laboratory, University of Science and Technology of China, 230026 Hefei, China
Search for more papers by this authorProf. Junfa Zhu
Hefei National Research Center for Physical Sciences at Microscale, National Synchrotron Radiation Laboratory, University of Science and Technology of China, 230026 Hefei, China
Search for more papers by this authorCorresponding Author
Prof. Qingxia Chen
Key Laboratory of Synthetic and Biological Colloids, Ministry of Education, School of Chemical and Material Engineering, Jiangnan University, 214122 Wuxi, China
Search for more papers by this authorCorresponding Author
Prof. Xingchen Jiao
Key Laboratory of Synthetic and Biological Colloids, Ministry of Education, School of Chemical and Material Engineering, Jiangnan University, 214122 Wuxi, China
Search for more papers by this authorCorresponding Author
Prof. Yi Xie
Hefei National Research Center for Physical Sciences at Microscale, National Synchrotron Radiation Laboratory, University of Science and Technology of China, 230026 Hefei, China
Search for more papers by this authorJinyu Ding
Key Laboratory of Synthetic and Biological Colloids, Ministry of Education, School of Chemical and Material Engineering, Jiangnan University, 214122 Wuxi, China
These authors contributed equally to this work.
Search for more papers by this authorPeijin Du
Key Laboratory of Synthetic and Biological Colloids, Ministry of Education, School of Chemical and Material Engineering, Jiangnan University, 214122 Wuxi, China
These authors contributed equally to this work.
Search for more papers by this authorJuncheng Zhu
Hefei National Research Center for Physical Sciences at Microscale, National Synchrotron Radiation Laboratory, University of Science and Technology of China, 230026 Hefei, China
These authors contributed equally to this work.
Search for more papers by this authorQing Hu
Key Laboratory of Synthetic and Biological Colloids, Ministry of Education, School of Chemical and Material Engineering, Jiangnan University, 214122 Wuxi, China
Search for more papers by this authorDongpo He
Key Laboratory of Synthetic and Biological Colloids, Ministry of Education, School of Chemical and Material Engineering, Jiangnan University, 214122 Wuxi, China
Search for more papers by this authorYang Wu
Hefei National Research Center for Physical Sciences at Microscale, National Synchrotron Radiation Laboratory, University of Science and Technology of China, 230026 Hefei, China
Search for more papers by this authorWenxiu Liu
Hefei National Research Center for Physical Sciences at Microscale, National Synchrotron Radiation Laboratory, University of Science and Technology of China, 230026 Hefei, China
Search for more papers by this authorDr. Shan Zhu
State Grid Anhui Electric Power Research Institute, 230601 Hefei, China
Search for more papers by this authorProf. Wensheng Yan
Hefei National Research Center for Physical Sciences at Microscale, National Synchrotron Radiation Laboratory, University of Science and Technology of China, 230026 Hefei, China
Search for more papers by this authorDr. Jun Hu
Hefei National Research Center for Physical Sciences at Microscale, National Synchrotron Radiation Laboratory, University of Science and Technology of China, 230026 Hefei, China
Search for more papers by this authorProf. Junfa Zhu
Hefei National Research Center for Physical Sciences at Microscale, National Synchrotron Radiation Laboratory, University of Science and Technology of China, 230026 Hefei, China
Search for more papers by this authorCorresponding Author
Prof. Qingxia Chen
Key Laboratory of Synthetic and Biological Colloids, Ministry of Education, School of Chemical and Material Engineering, Jiangnan University, 214122 Wuxi, China
Search for more papers by this authorCorresponding Author
Prof. Xingchen Jiao
Key Laboratory of Synthetic and Biological Colloids, Ministry of Education, School of Chemical and Material Engineering, Jiangnan University, 214122 Wuxi, China
Search for more papers by this authorCorresponding Author
Prof. Yi Xie
Hefei National Research Center for Physical Sciences at Microscale, National Synchrotron Radiation Laboratory, University of Science and Technology of China, 230026 Hefei, China
Search for more papers by this authorGraphical Abstract
The CO2 photoreduction towards CH3COOH with nearly 100 % selectivity is realized over a catalyst with charge asymmetric metal pair sites, wherein the metal charge asymmetric active sites induced by doping engineering can boost the C−C coupling of double COOH* intermediates.
Abstract
Targeted synthesis of acetic acid (CH3COOH) from CO2 photoreduction under mild conditions mainly limits by the kinetic challenge of the C−C coupling. Herein, we utilized doping engineering to build charge-asymmetrical metal pair sites for boosted C−C coupling, enhancing the activity and selectivity of CO2 photoreduction towards CH3COOH. As a prototype, the Pd doped Co3O4 atomic layers are synthesized, where the established charge-asymmetrical cobalt pair sites are verified by X-ray photoelectron spectroscopy and X-ray absorption near edge spectroscopy spectra. Theoretical calculations not only reveal the charge-asymmetrical cobalt pair sites caused by Pd atom doping, but also manifest the promoted C−C coupling of double *COOH intermediates through shortening of the coupled C−C bond distance from 1.54 to 1.52 Å and lowering their formation energy barrier from 0.77 to 0.33 eV. Importantly, the decreased reaction energy barrier from the protonation of two*COOH into *CO intermediates for the Pd-Co3O4 atomic layer slab is 0.49 eV, higher than that of the Co3O4 atomic layer slab (0.41 eV). Therefore, the Pd-Co3O4 atomic layers exhibit the CH3COOH evolution rate of ca. 13.8 μmol g−1 h−1 with near 100% selectivity, both of which outperform all previously reported single photocatalysts for CO2 photoreduction towards CH3COOH under similar conditions.
Open Research
Data Availability Statement
Research data are not shared.
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