Construction of bifunctional MOF-based composite electrocatalysts promoting oxygen evolution reaction and glucose oxidation reaction and its kinetic deciphering

Abstract

The climate crisis and the need for green and sustainable energy drive the rapid development of hydrogen production from water electrolysis. Improvements in the kinetics of the anode reaction, which governs the efficiency of water electrolysis, are essential for efficient hydrogen production and key to effectively addressing global environmental and energy challenges. Hence, we focus on improving the kinetics of the anode oxidation reaction. The multi-walled carbon nanotubes coupled with bimetallic organic framework (CoFe-MOF-74) composite electrocatalysts (CoFe-MOF-74@MWCNT) were fabricated for OER and the kinetically more favorable glucose oxidation reaction (GOR). Compared to commercial RuO₂, CoFe-MOF-74@MWCNT showed superior OER catalytic performance, exhibiting a lower overpotential (273 mV) and a lower Tafel slope (55 mV dec^-1) at a current density of 10 mA cm^-2. Moreover, after adding glucose to the anode, the potential required of 10 mA cm^-2 was only 1.291 V (vs. RHE), a reduction of 212 mV compared to the OER potential. This reduction in potential demonstrates the efficiency of our catalysts and signifies significant energy savings. The characterization results and theoretical calculations indicated that the superior OER/GOR performance of CoFe-MOF-74@MWCNT can be ascribed to the synergistic effect between MWCNT and the mixed metal nodes of the bimetallic organic framework. The doping of MWCNT promoted the catalyst charge transfer efficiency (R_ct was only 5.56 Ω) in the OER process. The mixed metal nodes of CoFe-MOF-74@MWCNT provided more active sites for the electrocatalytic reaction, and promoted the bond-breaking of critical intermediates in the oxidation process, significantly reducing the free energy of catalytic intermediates and accelerating reaction kinetics. This work provides a strategy for designing multifunctional electrocatalysts for OER and biomass small molecule oxidation and highlights the potential for significant energy savings in practical applications.