Electrocatalytic Synthesis of Essential Amino Acids from Nitric Oxide Using Atomically Dispersed Fe on N-doped Carbon

Angew Chem Int Ed Engl. 2023 Jun 26;62(26):e202304007. doi: 10.1002/anie.202304007. Epub 2023 May 5.

Abstract

How to transfer industrial exhaust gases of nitrogen oxides into high-values product is significantly important and challenging. Herein, we demonstrate an innovative method for artificial synthesis of essential α-amino acids from nitric oxide (NO) by reacting with α-keto acids through electrocatalytic process with atomically dispersed Fe supported on N-doped carbon matrix (AD-Fe/NC) as the catalyst. A yield of valine with 32.1 μmol mgcat -1 is delivered at -0.6 V vs. reversible hydrogen electrode, corresponding a selectivity of 11.3 %. In situ X-ray absorption fine structure and synchrotron radiation infrared spectroscopy analyses show that NO as nitrogen source converted to hydroxylamine that promptly nucleophilic attacked on the electrophilic carbon center of α-keto acid to form oxime and subsequent reductive hydrogenation occurred on the way to amino acid. Over 6 kinds of α-amino acids have been successfully synthesized and gaseous nitrogen source can be also replaced by liquid nitrogen source (NO3 - ). Our findings not only provide a creative method for converting nitrogen oxides into high-valued products, which is of epoch-making significance towards artificial synthesis of amino acids, but also benefit in deploying near-zero-emission technologies for global environmental and economic development.

Keywords: Amino Acid Synthesis; Electrocatalysis; Hydroxylamine; Metal-Organic Frameworks; Nitrogen Oxide.

MeSH terms

  • Amino Acids
  • Amino Acids, Essential*
  • Carbon
  • Gases
  • Hydrogenation
  • Keto Acids
  • Nitric Oxide*

Substances

  • Amino Acids, Essential
  • Nitric Oxide
  • Amino Acids
  • Carbon
  • Gases
  • Keto Acids