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<p>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 <i>N</i>-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 <i>N</i>-methylhydroxylamine adsorption to promote N‒O 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 1.5 mol of methylamine alongside easy product purification, gram-scale synthesis of deuterated methylamine and drugs, and hydrogenolysis of other N‒O bonds. This work offers a promising, general approach to alkyl N–O bond hydrogenolysis that could compete with traditional thermochemical routines.</p><p></p>

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

  • 期刊论文

  • 发表日期：

    2025年7月21日

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

摘要

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 N‒O 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 1.5 mol of methylamine alongside easy product purification, gram-scale synthesis of deuterated methylamine and drugs, and hydrogenolysis of other N‒O bonds. This work offers a promising, general approach to alkyl N–O bond hydrogenolysis that could compete with traditional thermochemical routines.