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Switchable CO2 electroreduction via engineering active phases of Pd nanoparticles

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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 PdH x @PdH x ) 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 PdH x @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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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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Authors and Affiliations

  1. State Key Laboratory of Catalysis, CAS Center for Excellence in Nanoscience, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, China

    Dunfeng Gao, Fan Cai, Xiaoqi Chen, Fan Yang, Shu Miao, Guoxiong Wang & Xinhe Bao

  2. College of Chemical Engineering, Zhejiang University of Technology, Hangzhou, 310032, China

    Hu Zhou & Jianguo Wang

  3. Canadian Light Source Inc., University of Saskatchewan, 44 Innovation Boulevard, Saskatoon, Saskatchewan, S7N 2V3, Canada

    Dongniu Wang & Yongfeng Hu

  4. 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

    Bei Jiang & Wen-Bin Cai

  5. Shanghai Synchrotron Radiation Facility, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai, 201204, China

    Rui Si

  6. University of Chinese Academy of Sciences, Beijing, 100039, China

    Fan Cai

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  1. Dunfeng Gao
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  2. Hu Zhou
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  3. Fan Cai
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  4. Dongniu Wang
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  6. Bei Jiang
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  7. Wen-Bin Cai
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  8. Xiaoqi Chen
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  9. Rui Si
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  10. Fan Yang
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  11. Shu Miao
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  12. Jianguo Wang
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  13. Guoxiong Wang
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  14. Xinhe Bao
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Correspondence to Jianguo Wang, Guoxiong Wang or Xinhe Bao.

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Gao, D., Zhou, H., Cai, F. et al. Switchable CO2 electroreduction via engineering active phases of Pd nanoparticles. Nano Res. 10, 2181–2191 (2017). https://doi.org/10.1007/s12274-017-1514-6

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