Surfactant-enhanced Cu<sup>δ+</sup> and induced electrostatic forces promote the electrocatalytic deuteron-dechlorination of trichloroacetic acid.
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 41286262.
- Also identified by DOI 10.1038/s41467-025-65333-7 and PMC identifier 12644465.
- Licence recorded as CC BY-NC-ND.
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Abstract
Electrocatalytic deuteron-dechlorination of trichloroacetic acid (TCAA) in D<sub>2</sub>O provides a green route to synthesize commercial acetic-d<sub>3</sub> acid-d (AA-d<sub>4</sub>). Synthesizing AA-d<sub>4</sub> with a high Faradaic efficiency (FE) and reaction rate is highly challenging because of the difficult C-Cl bond deuteration of the 2-monochloroacetic-2,2-d<sub>2</sub> acid-d (MCAA-d<sub>3</sub>) intermediate. Here, a quaternary ammonium salt surfactant-modified low-coordination copper electrocatalyst is designed, achieving TCAA-to-AA-d<sub>4</sub> with a 91% selectivity, 91% FE and 0.59 mmol h<sup>-1</sup> reaction rate at -100 mA cm<sup>-2</sup>. Mechanistic and kinetic studies reveal that the surfactant enhances the adsorption of MCAA-d<sub>3</sub> through electrostatic forces and increases the electron deficiency of Cu<sup>δ+</sup> sites, which accelerates electron transfer and promotes C-Cl bond activation, increasing the AA-d<sub>4</sub> selectivity. Surfactant-induced low D<sub>2</sub>O coverage suppresses D<sub>2</sub> formation, improving the FE. AA-d<sub>4</sub> electrosynthesis (1.84 g) with a 30 mmol h<sup>-1</sup> reaction rate and 65% FE at 600 mA cm<sup>-2</sup> and deuterated drug applications demonstrate promising potential.