Ru−FeNi Alloy Heterojunctions on Lignin‐derived Carbon as Bifunctional Electrocatalysts for Efficient Overall Water Splitting

Abstract Rational design of efficient, stable, and inexpensive bifunctional electrocatalysts for oxygen evolution reactions (OER) and hydrogen evolution reactions (HER) is a key challenge to realize green hydrogen production via electrolytic water splitting. Herein, Ru nanoparticles and FeNi alloy heterojunction catalyst (Ru−FeNi@NLC) encapsulated via lignin‐derived carbon was prepared by self‐assembly precipitation and in situ pyrolysis. The designed catalyst displays excellent performance at 10 mA cm −2 with low overpotentials of 36 mV for HER and 198 mV for OER, and only needs 1.48 V for overall water splitting. Results and DFT calculations show the unique N‐doped lignin‐derived carbon layer and Ru−FeNi heterojunction contribute to optimized electronic structure for enhancing electron transfer, balanced free energy of reactants and intermediates in the sorption/desorption process, and significantly reduced reaction energy barrier for the HER and OER rate‐determining steps, thus improved reaction kinetics. This work provides a new in situ pyrolysis doping strategy based on renewable biomass for the construction of highly active, stable and cost‐effective catalysts.