Strongly Coupled Ni ₁₂ P ₅ @NCNT Bifunctional Electrocatalysts for Efficient CO ₂ Reduction and Glycerol Oxidation

Renewable-powered electrochemical CO2 reduction (ECO2R) provides a sustainable route to convert CO2 into valuable fuels and chemicals. However, conventional ECO2R systems face high energy costs due to the sluggish oxygen evolution reaction (OER) at the anode. Replacing the OER with biomass electrooxidation (e.g., glycerol oxidation reaction, GOR) can lower energy consumption while coproducing high-value chemicals. However, the construction of an efficient and cost-effective bifunctional catalyst remains a challenge. Herein, we design a low-cost, bifunctional Ni12P5@NCNT catalyst with a bamboo-like nanotube morphology for coupled ECO2R and GOR. The Ni12P5@NCNT exhibits exceptional performance, achieving 82% CO selectivity at −0.7 V vs RHE in ECO2R and a 95% Faradaic efficiency for formate production in GOR. The integrated system significantly reduces overpotential (219 mV) compared to conventional ECO2R //OER setups. Experiments reveal that the strong electronic interaction between Ni12P5 and NCNT enhances the CO2/glycerol adsorption and accelerates charge transfer, boosting both ECO2R and GOR activity. This work provides a promising strategy for co-upgrading CO2 and glycerol into valuable products using nonprecious metal catalysts.