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Research Article

Switchable CO2 electroreduction via engineering active phases of Pd nanoparticles

Dunfeng Gao1,§, Hu Zhou2,§, Fan Cai1,6,§, Dongniu Wang3, Yongfeng Hu3, Bei Jiang4, Wen-Bin Cai4, Xiaoqi Chen1, Rui Si5, Fan Yang1, Shu Miao1, Jianguo Wang2( ), Guoxiong Wang1( ), Xinhe Bao1( )
State Key Laboratory of CatalysisCAS Center for Excellence in NanoscienceDalian Institute of Chemical PhysicsChinese Academy of SciencesDalian116023China
College of Chemical EngineeringZhejiang University of TechnologyHangzhou310032China
Canadian Light Source Inc.University of Saskatchewan44 Innovation BoulevardSaskatoonSaskatchewanS7N 2V3Canada
Shanghai Key Laboratory of Molecular Catalysis and Innovative MaterialsCollaborative Innovation Center of Chemistry for Energy MaterialsDepartment of ChemistryFudan UniversityShanghai200433China
Shanghai Synchrotron Radiation FacilityShanghai Institute of Applied PhysicsChinese Academy of SciencesShanghai201204China
University of Chinese Academy of SciencesBeijing100039China

§ These authors contributed equally to this work.

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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.

Keywords

carbon-dioxide electroreductionPd nanoparticlesactive phaseselectivity fluctuation

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Nano Research
Volume 10 Issue 6,
June 2017
Pages 2181-2191
DOI: 10.1007/s12274-017-1514-6
Cite this article:
Gao D, Zhou H, Cai F, et al. Switchable CO2 electroreduction via engineering active phases of Pd nanoparticles. Nano Research, 2017, 10(6): 2181-2191. https://doi.org/10.1007/s12274-017-1514-6

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Received: 07 December 2016
Revised: 17 January 2017
Accepted: 04 February 2017
Published: 04 April 2017
© Tsinghua University Press and Springer-Verlag Berlin Heidelberg 2017
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