Iron Active Center Coordination Reconstruction in Iron Carbide Modified on Porous Carbon for Superior Overall Water Splitting

Abstract

In this work, a novel liquid nitrogen quenching strategy is engineered to fulfill iron active center coordination reconstruction within iron carbide (Fe3C) modified on biomass-derived nitrogen-doped porous carbon (NC) for initiating rapid hydrogen and oxygen evolution, where the chrysanthemum tea (elm seeds, corn leaves, and shaddock peel, etc.) is treated as biomass carbon source within Fe3C and NC. Moreover, the original thermodynamic stability is changed through the corresponding force generated by liquid nitrogen quenching and the phase transformation is induced with rich carbon vacancies with the increasing instantaneous temperature drop amplitude. Noteworthy, the optimizing intermediate absorption/desorption is achieved by new phases, Fe coordination, and carbon vacancies. The Fe3C/NC-550 (550 refers to quenching temperature) demonstrates outstanding overpotential for hydrogen evolution reaction (26.3 mV at −10 mA cm−2) and oxygen evolution reaction (281.4 mV at 10 mA cm−2), favorable overall water splitting activity (1.57 V at 10 mA cm−2). Density functional theory (DFT) calculations further confirm that liquid nitrogen quenching treatment can enhance the intrinsic electrocatalytic activity efficiently by optimizing the adsorption free energy of reaction intermediates. Overall, the above results authenticate that liquid nitrogen quenching strategy open up new possibilities for obtaining highly active electrocatalysts for the new generation of green energy conversion systems.