Selective electrosynthesis of hydroxylamine from aqueous nitrate/nitrite by suppressing further reduction

Abstract The electrocatalytic reduction of nitrogenous waste offers a sustainable approach to producing nitrogen-containing chemicals. The selective synthesis of high-value hydroxylamine (NH2OH) is challenging due to the instability of NH2OH as an intermediate. Here, we present a rational electrocat...

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Main Authors: Yirong Tang, Zhan Jiang, Yubo Yuan, Li Xu, Chuyao Jin, Bulin Chen, Zhichao Lin, Jie Zao, Jianwei Du, Xiao Zhang, Xiang Gao, Yongye Liang
Format: Article
Language:English
Published: Nature Portfolio 2024-11-01
Series:Nature Communications
Online Access:https://doi.org/10.1038/s41467-024-54204-2
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Summary:Abstract The electrocatalytic reduction of nitrogenous waste offers a sustainable approach to producing nitrogen-containing chemicals. The selective synthesis of high-value hydroxylamine (NH2OH) is challenging due to the instability of NH2OH as an intermediate. Here, we present a rational electrocatalyst design strategy for promoting NH2OH electrosynthesis by suppressing the competing pathways of further reduction. We screen zinc phthalocyanines (ZnPc) with a high energy barrier for NH2OH reduction by regulating their intrinsic activity. Additionally, we discover that carbon nanotube substrates exhibit significant NH3-producing activity, which can be effectively inhibited by the high coverage of ZnPc molecules. In-situ characterizations reveal that NH2OH and HNO are generated as intermediates in nitrate reduction to NH3, and NH2OH can be enriched in the ZnPc electrode. In the H-cell, the optimized ZnPc catalyst demonstrates a Faradaic efficiency (FE) of 53 ± 1.7% for NH2OH with a partial current density exceeding 270 mA cm−2 and a turnover frequency of 7.5 ± 0.2 s−1. It also enables the rapid electrosynthesis of cyclohexanone oxime from nitrite with a FE of 64 ± 1.0%.
ISSN:2041-1723