Atomically Isolated Rh Sites within Highly Branched Rh2Sb Nanostructures Enhance Bifunctional Hydrogen Electrocatalysis

Breaking the bottleneck of hydrogen oxidation/evolution reactions (HOR/HER) in alkaline media is of tremendous importance for the development of anion exchange membrane fuel cells/water electrolyzers. Atomically dispersed active sites are known to exhibit excellent activity and selectivity toward diverse catalytic reactions. Here, a class of unique Rh2 Sb nanocrystals with multiple nanobranches (denoted as Rh2 Sb NBs) and atomically dispersed Rh sites are reported as promising electrocatalysts for alkaline HOR/HER. Rh2 Sb NBs/C exhibits superior HER performance with a low overpotential and a small Tafel slope, outperforming both Rh NBs/C and commercial Pt/C. Significantly, Rh2 Sb NBs show outstanding HOR performance of which the HOR specific activity and mass activity are about 9.9 and 10.1 times to those of Rh NBs/C, and about 4.2 and 3.7 times to those of Pt/C, respectively. Strikingly, Rh2 Sb NBs can also exhibit excellent CO tolerance during HOR, whose activity can be largely maintained even at 100 ppm CO impurity. Density functional theory calculations reveal that the unsaturated Rh sites on Rh2 Sb NBs surface are crucial for the enhanced alkaline HER and HOR activities. This work provides a unique catalyst design for efficient hydrogen electrocatalysis, which is critical for the development of alkaline fuel cells and beyond.