4.8 Article

Electrochemical Upgrading of Formic Acid to Formamide via Coupling Nitrite Co-Reduction

Journal

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 144, Issue 35, Pages 16006-16011

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/jacs.2c05660

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Funding

  1. National Natural Science Foundation of China [22101202, 21871206, 22071173]

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This study reports an electrochemical process for converting formic acid and nitrite into formamide with high selectivity under ambient conditions. Isotope-labeled experiments reveal the key bond formation process. This work is significant for upgrading CO2-derived formic acid into high-value compounds.
Formic acid (HCOOH) can be exclusively prepared through CO2 electroreduction at an industrial current density (0.5 A cm(-2)). However, the global annual demand for formic acid is only similar to 1 million tons, far less than the current CO2 emission scale. The exploration of an economical and green approach to upgrading CO2-derived formic acid is significant. Here, we report an electrochemical process to convert formic acid and nitrite into high-valued formamide over a copper catalyst under ambient conditions, which offers the selectivity from formic acid to formamide up to 90.0%. Isotope-labeled in situ attenuated total reflection surface-enhanced infrared absorption spectroscopy and quasi in situ electron paramagnetic resonance results reveal the key C-N bond formation through coupling *CHO and *NH2 intermediates. This work offers an electrochemical strategy to upgrade CO2-derived formic acid into high-value formamide.

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