Highly Active Si Sites Enabled by Negative Valent Ru for Electrocatalytic Hydrogen Evolution in LaRuSi

The discovery and identification of novel active sites are paramount for deepening the understanding of the catalytic mechanism and driving the development of remarkable electrocatalysts. Here, we reveal that the genuine active sites for the hydrogen evolution reaction (HER) in LaRuSi are Si sites, not the usually assumed Ru sites. Ru in LaRuSi has a peculiar negative valence state, which leads to strong hydrogen binding to Ru sites. Surprisingly, the Si sites have a Gibbs free energy of hydrogen adsorption that is near zero (0.063 eV). The moderate adsorption of hydrogen on Si sites during the HER process is also validated by in situ Raman analysis. Based on it, LaRuSi exhibits an overpotential of 72 mV at 10 mA cm−2 in alkaline media, which is close to the benchmark of Pt/C. This work sheds light on the recognition of real active sites and the exploration of innovative silicide HER electrocatalysts. Unlike other Ru‐containing compounds whose active sites are Ru sites, the Si sites in LaRuSi function as real active sites. The unusual negative valence Ru in this compound has excessively tight adsorption for hydrogen, according to both theoretical calculations and in situ Raman observations, but the Si sites have excellent hydrogen adsorption properties.