Nitrided Rhodium Nanoclusters with Optimized Water Bonding and Splitting Effects for pH-Universal H₂-Production

The nitridation of noble metals-based catalysts to further enhance their hydrogen evolution reaction (HER) kinetics in neutral and alkaline conditions would be an effective strategy for developing high-performance wide pH HER catalysts. Herein, a facile molten urea method is employed to construct the nitrided Rh nanoclusters (Rh_xN) supported on N-doped carbon (Rh_xN-NC). The uniformly distributed Rh_xN clusters exhibited optimized water bonding and splitting effects, therefore resulting in excellent pH-universal HER performance. The optimized Rh_xN-NC catalyst only requires 8, 12, and 109 mV overpotentials to reach the current density of 10 mA cm⁻² in 0.5 M H₂SO₄, 1.0 M KOH, and 1.0 M PBS electrolytes, respectively. The spectroscopic characterizations and theoretical calculation further confirm the vital role of Rh-N moieties in Rh_xN clusters in improving the transfer of electrons and facilitating the generation of H₂. This work not only provides a suitable nitridation method for noble metal species in mild conditions but also makes a breakthrough in synthesizing noble metal nitrides-based electrocatalysts to achieve an exceptional wide-pH HER performance and other catalysis. © 2023 Wiley-VCH GmbH.