Currently, platinum-based electrocatalysts show the best performance for hydrogen evolution. All hydrogen evolution reaction catalysts should however obey Sabatier’s principle, that is, the adsorption energy of hydrogen to the catalyst surface should be neither too high nor too low to balance between hydrogen adsorption and desorption. To overcome the limitation of this principle, here we choose a composite (rhodium/silicon nanowire) catalyst, in which hydrogen adsorption occurs on rhodium with a large adsorption energy while hydrogen evolution occurs on silicon with a small adsorption energy. We show that the composite is stable with better hydrogen evolution activity than rhodium nanoparticles and even exceeding those of commercial platinum/carbon at high overpotentials. The results reveal that silicon plays a key role in the electrocatalysis. This work may thus open the door for the design and fabrication of electrocatalysts for high-efficiency electric energy to hydrogen energy conversion.

Direct methane conversion (DMC) to high value-added products is of significant importance for the effective utilization of CH₄ to combat the energy crisis. However, there are ongoing challenges in DMC associated with the selective C−H activation of CH₄. The quest for high-efficiency catalysts for this process is limited by the current drawbacks including poor activity and low selectivity. Here we show a cerium dioxide (CeO₂) nanowires supported rhodium (Rh) single-atom (SAs Rh-CeO₂ NWs) that can serve as a high-efficiency catalyst for DMC to oxygenates (i.e., CH₃OH and CH₃OOH) under mild conditions. Compared to Rh/CeO₂ nanowires (Rh clusters) prepared by a conventional wet-impregnation method, CeO₂ nanowires supported Rh single-atom exhibits 6.5 times higher of the oxygenates yield (1231.7 vs. 189.4 mmol g_Rh⁻¹ h⁻¹), which largely outperforms that of the reported catalysts in the same class. This work demonstrates a highly efficient DMC process and promotes the research on Rh single-atom catalysts in heterogeneous catalysis.