Modulating the Nitrate Reduction Pathway on Unconventional Phase Ultrathin Nanoalloys for Selective Ammonia Electrosynthesis
Journal
Journal of the American Chemical Society
Journal Volume
147
Journal Issue
26
Start Page
23226
End Page
23238
ISSN
0002-7863
1520-5126
Date Issued
2025-06-20
Author(s)
Zhou, Jingwen
Liu, Fu
Xu, Zhihang
Yin, Jian-An
Guo, Liang
Hao, Fengkun
Wang, Yunhao
Xiong, Yuecheng
Zhou, Xichen
Wang, Cheng
Ma, Yangbo
Meng, Xiang
Lu, Pengyi
Yin, Jinwen
Zhang, An
Wang, Jie
Ye, Chenliang
Li, Qiang
Ling, Chongyi
Chen, Hsiao-Chien
Zhu, Ye
Lu, Jian
Fan, Zhanxi
Abstract
Ammonia (NH3) electrosynthesis from nitrate-polluted wastewater is a challenging but meaningful technique for the future green chemical and sewage disposal industries. The dominant difficulties lie in how to realize a highly selective, low-overpotential, and rapid electrocatalytic nitrate reduction reaction (NO3RR). Herein, we propose a catalyst crystal phase and electrode/electrolyte interface dual engineering strategy to enhance the neutral NO3RR performance of ultrathin alloy nanostructures. The obtained unconventional 2H-RhCu not only shows higher intrinsic NH3 selectivity than its traditional face-centered cubic and amorphous/crystalline counterparts but also delivers superior Faradaic efficiency and yield rate toward NH3 in K+-based electrolyte over those in Li+/Na+-based ones. In situ studies and theoretical calculations reveal that the faster generation/conversion kinetics of key intermediates, weaker N–N recombination, and unique *NObri adsorption configuration at electrode/electrolyte interfaces account for this significant enhancement. In addition, rechargeable Zn-nitrate/methanol flow batteries with 2H-RhCu were constructed as a demonstration of potential applications.
Publisher
American Chemical Society (ACS)
Type
journal article