Modulating Alcohol Adsorption Modes for Boosting Electrooxidation-Assisted Hydrogen Production

Oxygen evolution reaction (OER) suffers from sluggish kinetics and results in the increasing cost of hydrogen production. The exploration of an appropriate anode organic reaction occurring at low potential represents a feasible strategy to accelerate the implementation of water splitting in practice. Herein, we develop a ligand-confining thermolysis strategy to fabricate a Ru single-atom catalyst (Ru-SA/NSC) on N,S-codoped carbon. The adsorption mode effects of substrate alcohols on the electrocatalytic oxidation of Ru-SA/NSC are unraveled through modulation of substituent groups. The horizontal adsorption through the O atom on Ru-SA/NSC significantly facilitates the benzyl alcohol oxidation, delivering ultralow potential of 0.97 V vs reversible hydrogen electrode (RHE) at 10 mA cm–2 with high yield (∼96%), selectivity (∼99%), and Faraday efficiency (∼100%) to produce aldehydes. The vertical adsorption through the N atom in pyridine methanol over Ru-SA/NSC has no response to the reaction. Furthermore, in the coupling device of alcohol oxidation and hydrogen evolution reaction, hydrogen production with a low potential of 1.21 V at 10 mA cm–2 is achieved, surpassing that of benchmark Pt/C||IrO2 (1.56 V) and the state-of-the-art reports. This study provides insights into the design of nanocatalysts toward the rational conversion of organic molecules to value-added chemicals and concurrently produces clean energy carriers.