Regulation of hydrogen binding energy via oxygen vacancy enables an efficient trifunctional Rh-Rh2O3 electrocatalyst for fuel cells and water splitting.

[Display omitted] Developing multi-functional electrocatalysts is of great practical significance for fuel cells and water splitting. Herein, Rh-Rh 2 O 3 nanoclusters are prepared and the surface oxygen vacancy content is regulated elaborately by post-treatment. The optimized Rh-Rh 2 O 3 /C-400 exhibits superior trifunctional catalytic activity for hydrogen oxidation reaction (HOR), hydrogen evolution reaction (HER) and hydrazine oxidation reaction (HzOR), i.e., the mass activity for HOR is 2.29 mA μg Rh -1, and the overpotential for HER and HzOR at 10 mA cm−2 is as low as 12 mV and 31 mV, respectively, superior to the benchmark Pt/C. Rh-Rh 2 O 3 /C-400 also displays promising performance in practical devices, with the H 2 -O 2 anion-exchange-membrane fuel cell delivering a peak power density of 0.66 W cm−2, and the hydrazine-assisted water splitting electrolyzer requiring a low electrolysis voltage of 0.161 V at 0.1 A cm−2. The experimental and theoretical investigations discover that the hydrogen binding energy (HBE) is linearly depended on surface oxygen vacancy contents, and the HBE directly determines the catalytic activity for HOR, HER and HzOR. This work not only innovates an efficient Rh-based nanocluster tri-functional electrocatalyst, but also eludicates the intrinsic relationship of surface structure-intermediate adsorption-catalytic activity. [ABSTRACT FROM AUTHOR]