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Artificial Cu-Ni catalyst towards highly efficient nitrate-to-ammonia conversion

Cu-Ni催化剂助力高效电化学反硝化合成氨

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Abstract

Accelerated industrialization disrupts the global nitrogen cycle, resulting in alarmingly increased nitrate in groundwater. Electrocatalytic nitrate reduction (ECNR) with high automation can effectively convert nitrate to ammonia, simultaneously achieving nitrate removal and decentralized ammonia fabrication. However, realizing highly efficient nitrate reduction toward ammonia has proven challenging due to the complex reaction steps and sluggish kinetics. Here we report that Cu-Ni alloys enable stable and highly efficient nitrate-to-ammonia conversion, and the reduction of nitrate and the selectivity for ammonium can reach 83.87% and 93.6% in 4 h, respectively. The best reaction condition is obtained by adjusting pH and applied potential (Eh) according to the sequential proton-electron transfer theory. The introduction of Ni is identified to be conducive to the upshifted d-band center of the catalyst, enhancing the adsorption of nitrate and the corresponding intermediates. The reaction intermediates and mechanistic pathways of the nitrate-to-ammonia process are elucidated by rotating disk electrode (RDE) and in-situ Fourier-transform infrared spectroscopy. This work provides a new idea for the synergistic mechanism of bimetallic denitrification and puts forward a reaction path of nitrate on bimetallic catalysts for ammonia production from nitrate.

摘要

工业化的快速发展破坏了全球氮循环平衡, 导致地下水中硝酸 盐含量迅速增加. 电催化硝酸根还原(ECNR)可以有效地将硝酸盐转化 为氨, 同步实现硝酸盐去除和氨的合成. 然而反硝化合成氨过程步骤复 杂且动力学缓慢, 因此高效的硝酸盐还原为氨仍面临挑战. 本文报道了 一种基于电化学沉积方法制备的Cu-Ni合金, 可实现稳定、高效的硝态 氮向氨氮转化, 硝态氮的还原率和氨氮的选择性在四小时内分别达到 83.87%和93.6%. 根据质子耦合-电子转移理论, 通过调节电解液酸碱度 pH和加载电势Eh可得到最佳反应条件. 研究表明Ni的引入有利于催化 剂d带中心的上移, 促进硝酸盐和相应中间体的吸附. 另外, 本文采用旋 转圆盘电极和原位傅里叶变换红外光谱技术揭示了硝酸盐制氨过程的 反应中间体演化和反应机理. 本研究为理解双金属脱硝的协同机理提 供了新思路, 并提出了硝酸盐在双金属催化剂上的反应路径.

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Acknowledgements

This work was supported by the Natural Science Foundation of China (52101279), the Natural Science Foundation of Hunan Provience (2020JJ5688), the Science Research Initiation Fund of Central South University (202045012), the Scientific Research Project of Education Department of Hunan Province (21B000), Jiangsu Key Laboratory for Carbon-Based Functional Materials & Devices, Soochow University, and the Fundamental Research Funds for the Central Universities of Central South University (2020zzts753).

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Authors and Affiliations

  1. School of Minerals Processing and Bioengineering, Central South University, Changsha, 410083, China

    Zehui Bai  (白泽惠), Xin Li  (李鑫), Le Ding  (丁乐), Yansen Qu  (曲衍森) & Xinghua Chang  (常兴华)

  2. Key Laboratory for Mineral Materials and Application of Hunan Province, Central South University, Changsha, 410083, China

    Xinghua Chang  (常兴华)

Authors
  1. Zehui Bai  (白泽惠)
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  2. Xin Li  (李鑫)
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  3. Le Ding  (丁乐)
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  4. Yansen Qu  (曲衍森)
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  5. Xinghua Chang  (常兴华)
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Contributions

Bai Z performed the experiments, processed and analyzed the data, and wrote the original manuscript. Li X and Qu Y investigated the relevant literature and designed the experiments. Ding L reviewed and modified the manuscript. Chang X supervised the research, revised the manuscript and provided the experiment guidance. All authors discussed the results and provided their approval for the final version.

Corresponding author

Correspondence to Xinghua Chang  (常兴华).

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Conflict of interest

The authors declare that they have no conflict of interest.

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Experimental details and supporting data are available in the online version of the paper.

Zehui Bai received her BS degree in mineral resources engineering from Guangxi University in 2020. She is now pursuing her MS degree majored in resources and environment, at Central South University. Her current research interests are focused on bimetallic catalyst materials for nitrate reduction and their catalytic mechanism.

Xinghua Chang is currently an associate professor at the School of Minerals Processing and Bioengineering, Central South University. He received his PhD in physical chemistry from Peking University in 2018. His current research focuses on non-ferrous metal-based energy conversion and environmental catalytic materials and devices.

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Bai, Z., Li, X., Ding, L. et al. Artificial Cu-Ni catalyst towards highly efficient nitrate-to-ammonia conversion. Sci. China Mater. 66, 2329–2338 (2023). https://doi.org/10.1007/s40843-022-2392-8

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  • DOI: https://doi.org/10.1007/s40843-022-2392-8

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