Constructing Asymmetric Defects Pairs in Electrocatalysts for Efficient Glycerol Oxidation

Area of Science:

• Materials Science
• Electrochemistry
• Catalysis

Background:

• Disrupting catalyst charge distribution aids small molecule electrocatalysis.
• Cleaving C-C bonds in multicarbon molecules like glycerol requires advanced strategies.
• Integrating defect sites and asymmetric electronic perturbations is challenging but promising.

Purpose of the Study:

• To engineer spatially asymmetric defect pairs in spinel CuCo2O4 for enhanced C-C bond cleavage.
• To investigate the role of these defects in modulating local electronic perturbations and charge transfer.
• To evaluate the electrocatalytic performance for glycerol oxidation reaction (GOR).

Main Methods:

• Synthesis of spinel CuCo2O4 with high oxygen vacancy density (HVo).
• Partial refilling of sulfur atoms into HVo sites to create asymmetric defect pairs (Vo-S).
• Electrochemical testing of HVo-S and HVo catalysts for glycerol oxidation.

Main Results:

• The engineered Vo-S defect pairs enhanced local charge transfer and reduced glycerol adsorption energy barriers.
• HVo-S catalysts achieved high Faradaic efficiencies (98.5%) for formic acid production in GOR.
• The strategy demonstrated broad applicability in C-C bond cleavage for ethylene glycol and glucose electrooxidation.

Conclusions:

• Spatially asymmetric defect sites play a crucial role in promoting C-C bond cleavage during GOR.
• The HVo-S catalyst design offers a novel approach for efficient electrocatalytic conversion of polyols.
• This work provides insights for designing advanced electrocatalysts for polyol molecule activation.