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Nano Research 2017, 10(6): 2181-2191 https://doi.org/10.1007/s12274-017-1514-6
Research Article | Issue | Published: 04 April 2017

Switchable CO2 electroreduction via engineering active phases of Pd nanoparticles

Show Author's Information 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.

Keywords:
active phase, Pd nanoparticles, carbon-dioxide electroreduction, selectivity fluctuation
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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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Abstract Full text Electronic supplementary material About this article

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.


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Electronic supplementary material
About this article

Switchable CO2 electroreduction via engineering active phases of Pd nanoparticles

Show Author's information 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.

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

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Publication history
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Acknowledgements

Publication history

Received: 07 December 2016
Revised: 17 January 2017
Accepted: 04 February 2017
Published: 04 April 2017
Issue date: June 2017

Copyright

© Tsinghua University Press and Springer-Verlag Berlin Heidelberg 2017

Acknowledgements

Acknowledgements

We gratefully acknowledge financial support from the National Basic Research Program of China (Nos. 2016YFB0600901 and 2013CB733501), the National Natural Science Foundation of China (Nos. 21136001, 21573222, 91545202 and 91334103), and the Strategic Priority Research Program of the Chinese Academy of Sciences (No. XDB17020200). We thank staff at the BL14W1 beamline of Shanghai Synchrotron Radiation Facility (SSRF) for the kind help during XAFS measurements. G. X. W. also thanks the financial support from CAS Youth Innovation Promotion Association.

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