A bioinspired molybdenum-copper molecular catalyst for CO₂ electroreduction.

Area of Science:

• Inorganic Chemistry
• Electrochemistry
• Catalysis

Background:

• Development of non-noble metal molecular catalysts for CO2 electroreduction is crucial for sustainable chemistry.
• Mimicking active sites of enzymes like carbon monoxide dehydrogenase (CODH2) offers a promising strategy for catalyst design.

Purpose of the Study:

• To investigate the electrocatalytic reduction of carbon dioxide (CO2) to formate using a bimetallic Mo-Cu complex.
• To elucidate the catalytic mechanism and identify the active species involved in the CO2 reduction process.

Main Methods:

• Electrochemical reduction of a bimetallic complex, [(bdt)MoVI(O)S2CuICN]2-.
• Infrared spectroelectrochemistry (IR-SEC) for in-situ characterization.
• Density functional theory (DFT) computations to understand reaction pathways.

Main Results:

• The bimetallic complex functions as a pre-catalyst, requiring reduction to generate the active species.
• A Mo-hydride intermediate is formed upon reduction and protonation, which directly reacts with CO2.
• The catalytic cycle involves oxo-transfer and subsequent hydride transfer steps.

Conclusions:

• The study reveals a novel catalytic pathway for CO2 electroreduction mediated by a Mo-Cu complex.
• Findings highlight the potential of metal oxo precursors in designing efficient electrocatalysts for CO2 conversion.
• The identified Mo-hydride intermediate provides insights for future catalyst development.