Electronegativity regulation and graphitization: Synergistic enhancement of wood-derived carbon-based high-entropy alloy electrocatalysts for efficient hydrogen evolution

Abstract

Developing efficient and durable hydrogen evolution reaction (HER) electrocatalysts based on wood-supported high-entropy alloy (HEA) nanoparticles (NPs) remains challenging due to the difficulty in achieving uniform dispersion of HEA, strong interfacial anchoring between HEA and carbonized wood (CW), and rational modulation of interfacial electronic configurations simultaneously. In this work, HEA NPs anchored on CW via graphitized carbon layer, denoted as FeCoCuRuM@CW (M = Mn, Cr, Ni), were successfully synthesized by a carbothermal shock strategy. Before carbothermal shock, the negatively charged CW enabled efficient adsorption of metal ions, thereby increasing the metal loading. Metals (Fe, Co, Cu, Ru, Mn, Cr, and Ni) with distinct electronegativities induced the formation of high-activity HEA NPs during the carbothermal shock process. Meanwhile, the graphitized carbon layer formed on the surface of HEA reinforced the interfacial anchoring between HEA NPs and CW, which in turn enhanced the stability. Compared with FeCoCuRuCr@CW and FeCoCuRuNi@CW, FeCoCuRuMn@CW exhibited the best HER performance, requiring only 28 mV to achieve 10 mA/cm² in 1.0 mol/L KOH along with excellent durability. Electronic modulation via Mn incorporation is the key, as the element with the lowest electronegativity, Mn donated electrons to Ru and the carbon matrix. This process optimized the d-band center and strengthened interfacial water polarization. This electronic redistribution lowered the water dissociation barrier to 0.759 eV and yielded a near-thermoneutral hydrogen adsorption free energy (Δ G^*_H of −0.381 eV for FeCoCuRuMn@CW, which is significantly more favorable than those of FeCoCuRuCr@CW (Δ G^*_H = −1.861 eV) and FeCoCuRuNi@CW (Δ G^*_H = −2.087 eV). This study highlighted an electronegativity-driven electronic modulation mechanism, coupled with the synergistic enhancement effect derived from carbon graphitization degree, thereby offering a novel strategy for the rational design of high-performance HEA-based electrocatalysts with reinforced carbon-HEA interfacial anchoring.

Keywords

Hydrogen evolution reaction / High-entropy alloy / Carbonized wood / Electronegativity modulation / Graphitization

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