Entropy-Mediated Gradient Oxygenophilic Architecture on High-Entropy Alloy for Dynamic Spillover and Bifunctional Hydrogen Electrocatalysis.
basic_science · Level V
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- Also identified by DOI 10.1002/adma.202517450.
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Abstract
Breaking scaling relations and overcoming kinetic limitations in multistep hydrogen electrocatalysis remains a fundamental challenge. In this work, we designed and synthesized a high-entropy alloy catalyst comprising Ir, Ru, Mo, W, and Cu supported on nitrogen-doped carbon spheres. This unique structure creates active sites with a quasi-continuous distribution of binding energies for H* and OH* intermediates. Density functional theory (DFT) calculations confirm that the random spatial arrangement of sites enables low-energy-barrier spillover pathways for H* and OH* (χ<sub>H*</sub> <sup>max</sup> = 0.27 eV; χ<sub>OH*</sub> <sup>max</sup> = 0.61 eV), while continuous d-orbital coupling facilitates efficient electron transfer. This design enables each elementary step of hydrogen oxidation and evolution reactions (HOR/HER) to be directed to a site with favorable energetics. As a result, it exhibits exceptional bifunctional performance with a HOR mass activity of 8.83 A mg<sup>-1</sup> and an HER overpotential of only 11 mV at 10 mA cm<sup>-2</sup>, significantly outperforming commercial Pt/C<sub>com</sub> and previously reported catalysts. Operando spectroscopy and DFT analyses reveal that the gradient energy landscape promotes dynamic intermediate spillover, preventing site blocking and enhancing reaction kinetics. This work establishes a universal design strategy develop high-performance electrocatalysts that transcend conventional Sabatier principle limitations.