中国科学院上海硅酸盐研究所黄富强研究团队取得新进展，他们开发出定制表面静电电位的铜锌氰酰胺固溶体催化剂促进亚硝酸盐电还原中n中间体的不对称吸附。2025年2月18日出版的《美国化学会杂志》发表了这项成果。

在此，研究小组合成了一种固溶体&铜锌氰酰胺（Cu_0.8Zn_0.2NCN），具有局部结构畸变和定制的表面静电势，允许NO^2-的不对称结合。它表现出优异的NO₂RR性能，法拉第效率为~100%，NH₃产率为22mg h^-1 cm^-2，是同类工艺中最好的。理论计算和原位光谱测量表明，与线极化[NCN]^2-配位的Cu-Zn位点可以将CuNCN-NO^2-中的对称[Cu-O-N-O-Cu]转变为Cu_0.8Zn_0.2NCN-NO^2-中的[Cu-N-O-Zn]不对称构型，从而增强吸附和键解理作用。以Cu_0.8Zn_0.2NCN为阴极的配对电精炼厂在2.36V电压下达到2000mA cm^-2，并在试验级400mA cm^-2下保持完全工作140h， NH₃产率为~30mg_NH3 h^-1 cm^-2。他们的工作开辟了一条剪裁表面静电电位的新途径，为先进的电催化开辟了固溶体策略。

据悉，电催化亚硝酸盐还原（NO₂RR）将含氮污染物在环境条件下转化为高值氨（NH₃）。但由于其多中间体和多电子耦合质子转移过程导致现有电催化剂的活性和NH₃选择性较低。

附：英文原文

Title: A Copper–Zinc Cyanamide Solid-Solution Catalyst with Tailored Surface Electrostatic Potentials Promotes Asymmetric N-Intermediate Adsorption in Nitrite Electroreduction

Author: Jiacheng Jayden Wang, Huong T. D. Bui, Xunlu Wang, Zhuoran Lv, Huashuai Hu, Shuyi Kong, Zhiqiang Wang, Lijia Liu, Wei Chen, Hui Bi, Minghui Yang, Tore Brinck, Jiacheng Wang, Fuqiang Huang

Issue&Volume: February 18, 2025

Abstract: The electrocatalytic nitrite reduction (NO₂RR) converts nitrogen-containing pollutants to high-value ammonia (NH₃) under ambient conditions. However, its multiple intermediates and multielectron coupled proton transfer process lead to low activity and NH₃ selectivity for the existing electrocatalysts. Herein, we synthesize a solid-solution  copper–zinc cyanamide (Cu_0.8Zn_0.2NCN) with localized structure distortion and tailored surface electrostatic potential, allowing for the asymmetric binding of NO^2–. It exhibits outstanding NO₂RR performance with a Faradaic efficiency of ～100% and an NH₃ yield of 22 mg h^–1 cm^–2, among the best for such a process. Theoretical calculations and in situ spectroscopic measurements demonstrate that Cu–Zn sites coordinated with linear polarized [NCN]^2– could transform symmetric [Cu–O–N–O–Cu] in CuNCN-NO2– to a [Cu–N–O–Zn] asymmetric configuration in Cu_0.8Zn_0.2NCN-NO^2–, thus enhancing adsorption and bond cleavage. A paired electro-refinery with the Cu_0.8Zn_0.2NCN cathode reaches 2000 mA cm^–2 at 2.36 V and remains fully operational at industrial-level 400 mA cm^–2 for >140 h with a NH₃ production rate of ～30 mg_NH3 h^–1 cm^–2. Our work opens a new avenue of tailoring surface electrostatic potentials using a solid-solution strategy for advanced electrocatalysis.

DOI: 10.1021/jacs.5c00837

Source: https://pubs.acs.org/doi/full/10.1021/jacs.5c00837