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Regulating Ni site in NiV LDH for efficient electrocatalytic production of formate and hydrogen by glycerol electrolysis

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Abstract

Energy-saving glycerol electrolysis with lower potential than water spitting endows a promising way for the concurrent production of value-added formate and high-purity hydrogen. However, there is still lack of efficient electrocatalysts at both anode and cathode for glycerol electrolysis. Herein, we report the activation of Ni site in NiV layered double hydroxide (LDH) by electrochemical and N2/H2 plasma regulations for boosting the activity of glycerol oxidation reaction (GOR) and hydrogen evolution reaction (HER), respectively. Specifically, boosted GOR performance with a low overpotential (1.23 V at 10 mA·cm−2) and a high Faradic efficiency (94%) is demonstrated by electrochemically regulated NiV LDH (E-NiV LDH) with elevated valence state of Ni site. In situ Raman spectrum reveals the generation of Ni(III) species by electrochemical regulation, and the highly active Ni(III) can be regenerated with the process of electrochemical oxidation. Additionally, the possible reaction pathway is speculated based on the in situ Fourier transform infrared spectroscopy (FTIR) and high-performance liquid chromatography results. The plasma-regulated NiV LDH (P-NiV LDH) with lower valence state of Ni site exhibits outstanding HER activity, displaying a low overpotential of 45 mV to deliver 10 mA·cm−2. When employing E-NiV LDH and P-NiV LDH as anode and cathode electrocatalyst, respectively, the assembled electrolyzer merely needs 1.25 V to achieve 10 mA·cm−2 for simultaneous production of formate and hydrogen, demonstrating remarkable 320 mV of lower potential than water electrolysis.

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摘要

电解甘油比电解水具有更低的电压‚ 为同时生产高附加值的甲酸和高纯氢气提供了一种有前景的方法。然而‚ 甘油电解的阳极和阴极均缺乏高效的电催化剂。本文报道了电化学和N2/H2等离子体调控NiV LDH 中的Ni位点分别提高甘油氧化反应(GOR)和析氢反应(HER)的活性。经电化学调控的、具有高价镍物种的NiV LDH (E-NiV LDH) 展现出增强的GOR性能‚ 表现出低的过电位(10 mA·cm−2仅需1.23 V)和高的法拉第效率(94%)。原位拉曼光谱揭示了电化学调控过程中Ni(III)物种的生成‚ 并通过电化学氧化过程实现了高活性Ni(III)的再生。此外‚ 根据原位FTIR和高效液相色谱的结果推测了可能的甘油氧化反应途径。经等离子体调控的、含低价镍物种的NiV LDH (P-NiV LDH)表现出优异的HER活性‚ 其实现10 mA·cm−2的电流密度仅需45 mV的低过电位。当E-NiV LDH和P-NiV LDH分别作为阳极和阴极电催化剂时‚ 组装成的电解槽只需1.25 V即可达到10 mA·cm−2电流密度‚ 同时产生甲酸和氢气‚ 比电解水所需的电位低320 mV。

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Acknowledgements

This study was financially supported by the National Science Foundation of China (No. 12075002), the Outstanding Youth Fund of Anhui Province (No. 2008085J21), Anhui Provincial Supporting Program for Excellent Young Talents in Universities (No. gxyqZD2019005), and the Innovation and Entrepreneurship Project of Overseas Returnees in Anhui Province (No. 2019LCX018).

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  1. Lin Dong and Guan-Ru Chang have contributed equally to this work.

Authors and Affiliations

  1. Key Laboratory of Structure and Functional Regulation of Hybrid Materials, Institutes of Physical Science and Information Technology, Anhui University, Ministry of Education, Hefei, 230601, China

    Lin Dong, Guan-Ru Chang & Xin-Yao Yu

  2. Department of Polymer Materials and Engineering, Academy of Chemical Engineering, Hebei University of Technology, Tianjin, 300130, China

    Yi Feng

  3. School of Chemistry and Chemical Engineering, Huangshan University, Huangshan, 245041, China

    Guan-Ru Chang

  4. Ningbo Research Institute of Ecological and Environmental Sciences, Ningbo, 315000, China

    Xian-Zhi Yao

  5. Energy Materials and Devices Key Laboratory of Anhui Province for Photoelectric Conversion, Anhui University, Hefei, 230601, China

    Xin-Yao Yu

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  1. Lin Dong
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Dong, L., Chang, GR., Feng, Y. et al. Regulating Ni site in NiV LDH for efficient electrocatalytic production of formate and hydrogen by glycerol electrolysis. Rare Met. 41, 1583–1594 (2022). https://doi.org/10.1007/s12598-021-01881-3

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