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Atomically Precise (AgPd)27 Nanoclusters for Nitrate Electroreduction to NH3: Modulating the Metal Core by a Ligand Induced Strategy

Lubing Qin1, Fang Sun2, Meiyin Li3, Hao Fan1, Likai Wang3, Qing Tang2, Chundong Wang4, Zhenghua Tang1,5   

  1. 1 New Energy Research Institute, School of Environment and Energy, South China University of Technology, Guangzhou Higher Education Mega Center, Guangzhou 510006, China;
    2 School of Chemistry and Chemical Engineering, Chongqing Key Laboratory of Theoretical and Computational Chemistry, Chongqing University, Chongqing 401331, China;
    3 School of Chemistry and Chemical Engineering, Shandong University of Technology, Zibo 255049, Shandong Province, China;
    4 School of Integrated Circuits, Wuhan National Laboratory for Optoelectronics, Huazhong University of Science and Technology, Wuhan 430074, China;
    5 Key Laboratory of Functional Inorganic Material Chemistry(Heilongjiang University), Ministry of Education, Haerbin 150001, China
  • 收稿日期:2024-03-11 修回日期:2024-04-25 录用日期:2024-04-25
  • 通讯作者: Zhenghua Tang, Qing Tang E-mail:zhht@scut.edu.cn;qingtang@cqu.edu.cn
  • 基金资助:
    The study is supported by the open funds of Key Laboratory of Functional Inorganic Material Chemistry (Heilongjiang University), Ministry of Education, China. Z.T. acknowledges the funding from Guangdong Natural Science Funds (2023A0505050107). Q.T. acknowledges the support by the Chongqing Science and Technology Commission (cstc2020jcyj-msxmX0382).

Atomically Precise (AgPd)27 Nanoclusters for Nitrate Electroreduction to NH3: Modulating the Metal Core by a Ligand Induced Strategy

Lubing Qin1, Fang Sun2, Meiyin Li3, Hao Fan1, Likai Wang3, Qing Tang2, Chundong Wang4, Zhenghua Tang1,5   

  1. 1 New Energy Research Institute, School of Environment and Energy, South China University of Technology, Guangzhou Higher Education Mega Center, Guangzhou 510006, China;
    2 School of Chemistry and Chemical Engineering, Chongqing Key Laboratory of Theoretical and Computational Chemistry, Chongqing University, Chongqing 401331, China;
    3 School of Chemistry and Chemical Engineering, Shandong University of Technology, Zibo 255049, Shandong Province, China;
    4 School of Integrated Circuits, Wuhan National Laboratory for Optoelectronics, Huazhong University of Science and Technology, Wuhan 430074, China;
    5 Key Laboratory of Functional Inorganic Material Chemistry(Heilongjiang University), Ministry of Education, Haerbin 150001, China
  • Received:2024-03-11 Revised:2024-04-25 Accepted:2024-04-25
  • Contact: Zhenghua Tang, Qing Tang E-mail:zhht@scut.edu.cn;qingtang@cqu.edu.cn
  • Supported by:
    The study is supported by the open funds of Key Laboratory of Functional Inorganic Material Chemistry (Heilongjiang University), Ministry of Education, China. Z.T. acknowledges the funding from Guangdong Natural Science Funds (2023A0505050107). Q.T. acknowledges the support by the Chongqing Science and Technology Commission (cstc2020jcyj-msxmX0382).

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摘要： Electrochemical nitrate reduction reaction (eNO3–RR) to synthesize NH3 is a sustainable method to convert environmental contaminants into valuables. Pd based bimetallic nanocatalysts have demonstrated great promise as efficient catalysts, yet modulating the composition and configuration to improve the catalytic performance and achieve comprehensive mechanistic understanding remains challenging. Herein, by employing two ligands with different electron functional groups, we successfully prepared two atomically precise (AgPd)27 bimetallic clusters of Ag18Pd9(C8H4F)24 (Ag18Pd9) and Ag22Pd5(C9H10O2)26 (Ag22Pd5). The two clusters possess markedly different metal core composition and configuration, where Ag18Pd9 has a sandwich metal core structure with 9 Pd atoms located in the middle layer and Ag22Pd5 has a rod-shaped metal core structure composed of the M13 configuration with 5 Pd atoms located at the center and vertices of the M13 configuration. Unexpectedly, Ag22Pd5 exhibited remarkably superior eNO−3RR performance than Ag18Pd9. Specifically, the highest Faradaic efficiency of NH3 (FENH3) and its yield rate can reach 94.42% and 1.41 mmol∙h−1∙mg−1 at −0.6 V vs. RHE for Ag22Pd5, but the largest FENH3 and NH3 yield rate is only 43.86% and 0.41 mmol∙h−1∙mg−1 at −0.5 V vs. RHE for Ag18Pd9. The in situ attenuated total reflection surface enhanced infrared absorption spectroscopy (ATR-SEIRAS) test provides the experimental evidence of the reaction intermediates hence revealing the reaction pathway, also shows that Ag22Pd5 has stronger capability for NO−3 adsorption and NH3 desorption than that of Ag18Pd9. Theoretical calculations indicate that the de-ligated clusters can expose the available AgPd bimetallic sites, synergistically serving as effective active sites and the different configurations result in significantly different catalytic activities, where the active sites in Ag22Pd5 are more favorable for NO−3 adsorption and NH3 desorption to accelerate the catalytic process.

关键词: Electrochemical nitrate reduction reaction, Atomically precise bimetallic cluster, Ag18Pd9(C8H4F)24, Ag22Pd5(C9H10O2)26, In situ attenuated total reflection surface enhanced infrared absorption spectroscopy, Theoretical calculations

Abstract: Electrochemical nitrate reduction reaction (eNO3–RR) to synthesize NH3 is a sustainable method to convert environmental contaminants into valuables. Pd based bimetallic nanocatalysts have demonstrated great promise as efficient catalysts, yet modulating the composition and configuration to improve the catalytic performance and achieve comprehensive mechanistic understanding remains challenging. Herein, by employing two ligands with different electron functional groups, we successfully prepared two atomically precise (AgPd)27 bimetallic clusters of Ag18Pd9(C8H4F)24 (Ag18Pd9) and Ag22Pd5(C9H10O2)26 (Ag22Pd5). The two clusters possess markedly different metal core composition and configuration, where Ag18Pd9 has a sandwich metal core structure with 9 Pd atoms located in the middle layer and Ag22Pd5 has a rod-shaped metal core structure composed of the M13 configuration with 5 Pd atoms located at the center and vertices of the M13 configuration. Unexpectedly, Ag22Pd5 exhibited remarkably superior eNO−3RR performance than Ag18Pd9. Specifically, the highest Faradaic efficiency of NH3 (FENH3) and its yield rate can reach 94.42% and 1.41 mmol∙h−1∙mg−1 at −0.6 V vs. RHE for Ag22Pd5, but the largest FENH3 and NH3 yield rate is only 43.86% and 0.41 mmol∙h−1∙mg−1 at −0.5 V vs. RHE for Ag18Pd9. The in situ attenuated total reflection surface enhanced infrared absorption spectroscopy (ATR-SEIRAS) test provides the experimental evidence of the reaction intermediates hence revealing the reaction pathway, also shows that Ag22Pd5 has stronger capability for NO−3 adsorption and NH3 desorption than that of Ag18Pd9. Theoretical calculations indicate that the de-ligated clusters can expose the available AgPd bimetallic sites, synergistically serving as effective active sites and the different configurations result in significantly different catalytic activities, where the active sites in Ag22Pd5 are more favorable for NO−3 adsorption and NH3 desorption to accelerate the catalytic process.

Key words: Electrochemical nitrate reduction reaction, Atomically precise bimetallic cluster, Ag18Pd9(C8H4F)24, Ag22Pd5(C9H10O2)26, In situ attenuated total reflection surface enhanced infrared absorption spectroscopy, Theoretical calculations