近日，天津大学张斌团队研究了实现了强偶极子促进的N-O键氢解进而安培级电合成甲胺。相关论文发表在2025年7月21日出版的《自然-化学》杂志上。

甲基胺是最简单的烷基胺之一，也是最常见的散装化学品，硝基甲烷在水中的电化学氢解为获取甲基胺提供了一条可持续的途径。然而，由于N-甲基羟胺中间体的N-O键激活无效，目前的研究只能实现低于10%的甲胺选择性。

研究组设计了一种具有丰富低配位位的铜电催化剂，使硝基甲烷在低电位下以99%的选择性和97%的法拉第效率转化为甲胺。低配位的铜位在N-甲基羟胺的吸附上诱导了一个大的偶极矩，以促进NO氢解作用。改变pH改变了速率决定步骤，导致甲基胺生产的pH依赖火山趋势。研究组演示了1.5mol的甲基胺，同时易于产品纯化，克级合成氘化甲胺和药物，以及氢解其他NO氢解。这项工作为烷基N-O键氢解提供了一种有前途的通用方法，可以与传统的热化学方法相媲美。

附：英文原文

Title: Strong dipole-promoted N–O bond hydrogenolysis enables ampere-level electrosynthesis of methylamine

Author: Li, Rui, Yang, Rong, Li, Qian, Qin, Mengmei, He, Meng, Liu, Cuibo, Zhang, Bin

Issue&Volume: 2025-07-21

Abstract: The electrochemical hydrogenolysis of nitromethane in water could provide a sustainable route for accessing methylamine, one of the simplest alkyl amines and most commonly used bulk chemicals. However, present efforts achieve only methylamine selectivities below 10% due to the ineffective N–O bond activation of the N-methylhydroxylamine intermediate. Here we design a copper electrocatalyst with abundant low-coordination sites to enable the conversion of nitromethane to methylamine with 99% selectivity and 97% Faradaic efficiency at a low potential. The low-coordination copper sites induce a large dipole moment upon N-methylhydroxylamine adsorption to promote NO hydrogenolysis. Altering the pH changes the rate-determining step, resulting in a pH-dependent volcano trend for methylamine production. We demonstrate ampere-level production of 1.5mol of methylamine alongside easy product purification, gram-scale synthesis of deuterated methylamine and drugs, and hydrogenolysis of other NO bonds. This work offers a promising, general approach to alkyl N–O bond hydrogenolysis that could compete with traditional thermochemical routines.

DOI: 10.1038/s41557-025-01864-2

Source: https://www.nature.com/articles/s41557-025-01864-2