Interface‐Triggered Spin‐Magnetic Effect in Rare Earth Intraparticle Heterostructured Nanoalloys for Boosting Hydrogen Evolution

Rare earth (RE) elements are attractive for spin‐magnetic modulation due to their unique 4 f electron configuration and strong orbital couplings. Alloying RE with conventional 3d transition‐metal (TM) is promising for the fabrication of advanced spin catalysts yet remains much difficulties in preparation, which leads to the mysteries of spin‐magnetic effect between RE and 3d TM on catalysis. Here we define a solid‐phase synthetic protocol for creating RE‐3d TM‐noble metal integrated intraparticle heterostructured nanoalloys (IHAs) with distinct Gd and Co interface within the entire Rh framework, denoted as RhCo−RhGd IHAs. They exhibit interface‐triggered antiferromagnetic interaction, which can induce electron redistribution and regulate spin polarization. Theoretical calculations further reveal that active sites around the heterointerface with weakened spin polarization optimize the adsorption and dissociation of H2O, thus promoting alkaline hydrogen evolution catalysis. The RhCo−RhGd IHAs show a small overpotential of 11.3 mV at 10 mA cm−2, as well as remarkable long‐term stability, far superior to previously reported Rh‐based catalysts. The antiferromagnetic couplings between rare earth and 3d transition‐metal were achieved by creating RhCo−RhGd intraparticle heterostructured nanoalloys (IHAs), which could regulate the spin polarization of active sites to optimize adsorption and dissociation of H2O, thus boosting hydrogen evolution reaction (HER). RhCo−RhGd IHAs demonstrated excellent alkaline HER catalytic activity, with a small overpotential of 11.3 mV at 10 mA cm−2 and robust stability over 100 h operation.