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

Renewable-powered electrochemical CO 2 reduction (ECO 2 R) provides a sustainable route to convert CO 2 into valuable fuels and chemicals. However, conventional ECO 2 R 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 Ni 12 P 5 @NCNT catalyst with a bamboo-like nanotube morphology for coupled ECO 2 R and GOR. The Ni 12 P 5 @NCNT exhibits exceptional performance, achieving 82% CO selectivity at −0.7 V vs RHE in ECO 2 R and a 95% Faradaic efficiency for formate production in GOR. The integrated system significantly reduces overpotential (219 mV) compared to conventional ECO 2 R //OER setups. Experiments reveal that the strong electronic interaction between Ni 12 P 5 and NCNT enhances the CO 2 /glycerol adsorption and accelerates charge transfer, boosting both ECO 2 R and GOR activity. This work provides a promising strategy for co-upgrading CO 2 and glycerol into valuable products using nonprecious metal catalysts.