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Nano Research

Article Title

Switchable CO2 electroreduction via engineering active phases of Pd nanoparticles

Authors

Dunfeng Gao, State Key Laboratory of Catalysis, CAS Center for Excellence in Nanoscience, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China
Hu Zhou, College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310032, China
Fan Cai, State Key Laboratory of Catalysis, CAS Center for Excellence in Nanoscience, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China University of Chinese Academy of Sciences, Beijing 100039, China
Dongniu Wang, Canadian Light Source Inc., University of Saskatchewan, 44 Innovation Boulevard, Saskatoon, Saskatchewan S7N 2V3, Canada
Yongfeng Hu, Canadian Light Source Inc., University of Saskatchewan, 44 Innovation Boulevard, Saskatoon, Saskatchewan S7N 2V3, Canada
Bei Jiang, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Collaborative Innovation Center of Chemistry for Energy Materials, Department of Chemistry, Fudan University, Shanghai 200433, China
Wen-Bin Cai, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Collaborative Innovation Center of Chemistry for Energy Materials, Department of Chemistry, Fudan University, Shanghai 200433, China
Xiaoqi Chen, State Key Laboratory of Catalysis, CAS Center for Excellence in Nanoscience, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China
Rui Si, Shanghai Synchrotron Radiation Facility, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201204, China
Fan Yang, State Key Laboratory of Catalysis, CAS Center for Excellence in Nanoscience, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China
Shu Miao, State Key Laboratory of Catalysis, CAS Center for Excellence in Nanoscience, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China
Jianguo Wang, College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310032, China
Guoxiong Wang, State Key Laboratory of Catalysis, CAS Center for Excellence in Nanoscience, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China
Xinhe Bao, State Key Laboratory of Catalysis, CAS Center for Excellence in Nanoscience, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China

Keywords

carbon-dioxide electroreduction, Pd nanoparticles, active phase, selectivity fluctuation

Abstract

ABSTRACT Active-phase engineering is regularly utilized to tune the selectivity of metal nanoparticles (NPs) in heterogeneous catalysis. However, the lack of understanding of the active phase in electrocatalysis has hampered the development of efficient catalysts for CO2 electroreduction. Herein, we report the systematic engineering of active phases of Pd NPs, which are exploited to select reaction pathways for CO2 electroreduction. In situ X-ray absorption spectroscopy, in situ attenuated total reflection-infrared spectroscopy, and density functional theory calculations suggest that the formation of a hydrogen-adsorbed Pd surface on a mixture of the α- and β-phases of a palladium-hydride core (α+β PdHx@PdHx) above −0.2 V (vs. a reversible hydrogen electrode) facilitates formate production via the HCOO* intermediate, whereas the formation of a metallic Pd surface on the β-phase Pd hydride core (β PdHx@Pd) below −0.5 V promotes CO production via the COOH* intermediate. The main product, which is either formate or CO, can be selectively produced with high Faradaic efficiencies (>90%) and mass activities in the potential window of 0.05 to −0.9 V with scalable application demonstration.

Graphical Abstract

Publisher

Tsinghua University Press

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