Bisulfate as a redox-active ligand in vanadium-based electrocatalysis for CH4 functionalization

The roles of unforgiving H2SO4 solvent in CH4 activation with molecular catalysts have not been experimentally well-illustrated despite computational predictions. Here, we provide experimental evidence that metal-bound bisulfate ligand introduced by H2SO4 solvent is redox-active in vanadium-based electrocatalytic CH4 activation discovered recently. Replacing one of the two terminal bisulfate ligands with redox-inert dihydrogen phosphate in the pre-catalyst vanadium (V)-oxo dimer completely quenches its activity towards CH4, which may inspire environmentally benign catalysis with minimal use of H2SO4.

Automated summary

The redox-active metal-bound bisulfate ligand introduced by H2SO4 solvent plays a crucial role in vanadium-based electrocatalytic CH4 activation. This finding could potentially lead to environmentally benign catalysis with minimal use of H2SO4.