D-Band Width Rationally Broadened by Configuring Nearest Coordination of Metal Site for Enhanced Active Site-Intermediate Interaction

Metal-based site, as an important type of active site, plays the benchmarking role in the redox and charge transfer processes in the heterogeneous catalysis. Modulating the valence state of metal site as a promising and simple strategy theoretically enables control over the adsorption strength of reaction intermediates. However, this strategy is intrinsically limited by the local atomic configuration, often leading to unpredictable catalytic failures. Here, it is reported that the intermediate adsorption strength of platinum active site with different valence states exhibits a linear relationship with the d-band width of Pt (W_d-Pt). Adjusting the nearest-neighbor coordination environment of Pt sites by changing the transition metals bonded to Pt effectively modulates the W_d-Pt, which offers a high activity (η₁₀ = 14 mV) in the hydrogen evolution reaction (HER). W_d-Pt broadening elevates the Pt─H anti-bonding states across the Fermi level, strengthening active site-absorbate interactions and thereby tuning HER catalytic activity. In addition, this d-band width engineering strategy can be expanded to other catalysts with the metal active site. The present study transcends limitations in valence state modulation and sheds light on deeper understanding of d-band structure of metal sites and a methodology to boost the activity of metal sites in heterogeneous catalysis.