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PdAg bimetallic electrocatalyst for highly selective reduction of CO2 with low COOH* formation energy and facile CO desorption

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Abstract

For electrocatalytic reduction of CO2 to CO, the stabilization of intermediate COOH* and the desorption of CO* are two key steps. Pd can easily stabilize COOH*, whereas the strong CO* binding to Pd surface results in severe poisoning, thus lowering catalytic activity and stability for CO2 reduction. On Ag surface, CO* desorbs readily, while COOH* requires a relatively high formation energy, leading to a high overpotential. In light of the above issues, we successfully designed the PdAg bimetallic catalyst to circumvent the drawbacks of sole Pd and Ag. The PdAg catalyst with Ag-terminated surface not only shows a much lower overpotential (-0.55 V with CO current density of 1 mA/cm2) than Ag (−0.76 V), but also delivers a CO/H2 ratio 18 times as high as that for Pd at the potential of -0.75 V vs. RHE. The issue of CO poisoning is significantly alleviated on Ag-terminated PdAg surface, with the stability well retained after 4 h electrolysis at -0.75 V vs. RHE. Density functional theory (DFT) calculations reveal that the Ag-terminated PdAg surface features a lowered formation energy for COOH* and weakened adsorption for CO*, which both contribute to the enhanced performance for CO2 reduction.

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Acknowledgements

This work was supported by the National Key R&D Program of China (Nos. 2016YFA0202801 and 2017YFA0700101), the National Natural Science Foundation of China (Nos. 21872076, 21573119, 21590792, 21890383, and 91645203) and Beijing Natural Science Foundation (No. JQ18007). The aberration-corrected TEM studies were conducted at the National Center for Electron Microscopy in Beijing for Information Science and Technology.

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  1. Rui Lin and Xuelu Ma contributed equally to this work.

Authors and Affiliations

  1. Department of Chemistry, Tsinghua University, Beijing, 100084, China

    Rui Lin, Weng-Chon Cheong, Chao Zhang, Hai Xiao, Jun Li, Dingsheng Wang, Qing Peng, Chen Chen & Yadong Li

  2. School of Chemical & Environment Engineering, China University of Mining & Technology, Beijing, 100083, China

    Xuelu Ma

  3. College of Chemical Engineering, Beijing University of Chemical Technology, Beijing, 100029, China

    Wei Zhu, Jiajing Pei & Zhongbin Zhuang

  4. College of Environmental and Energy Engineering, Beijing University of Technology, Beijing, 100124, China

    Kaiyue Zhang & Yuxi Liu

  5. Sinopec Beijing Research Institute of Chemical Industry, Beijing, 100013, China

    Bin Wang

  6. School of Materials Science and Engineering, National Center for Electron Microscopy in Beijing, Tsinghua University, Beijing, 100084, China

    Shiyou Liang & Rong Yu

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  1. Rui Lin
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Correspondence to Hai Xiao or Chen Chen.

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12274_2019_2526_MOESM1_ESM.pdf

PdAg bimetallic electrocatalyst for highly selective reduction of CO2 with low COOH* formation energy and facile CO desorption

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Lin, R., Ma, X., Cheong, WC. et al. PdAg bimetallic electrocatalyst for highly selective reduction of CO2 with low COOH* formation energy and facile CO desorption. Nano Res. 12, 2866–2871 (2019). https://doi.org/10.1007/s12274-019-2526-1

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