Self-reconstructing amorphous high-entropy oxides for CO2-free methanol electroreforming and hydrogen generation

Amorphous electrocatalysts, unconstrained by crystalline order, offer a versatile landscape of active sites that promote enhanced reactivity and structural adaptability. When fused with the compositional complexity of high-entropy materials, this disordered architecture yields enhanced electronic interactions and catalytic adaptability. In this work, we design a self-supporting amorphous high-entropy oxide (a-HEO) electrode by in-situ growth of FeCoNiMnMo-based nanosheets on nickel foam (a-FeCoNiMnMoO/NF). Electrochemical activation triggers a self-reconstruction process, yielding oxyhydroxide species embedded with oxygen vacancies that collectively enhance electron conductivity and catalytic performance for the alkaline methanol oxidation reaction (MOR). Machine learning potential-based simulations demonstrate that the amorphous oxyhydroxide layer offers a diverse array of catalytic sites, fine-tunes the electronic structure, and optimizes intermediates adsorption, thus enhancing the reaction dynamics of methanol oxidation. When employed in a hybrid acid/alkali flow electrolyzer, the system operates at just 0.54 V to reach 10 mA cm −2 , enabling over 300 h of continuous, CO 2 -free production of hydrogen and formate, demonstrating a durable and energy-saving strategy for sustainable fuel and chemical generation. This study highlights the compelling synergy between structural disorder and elemental complexity, charting a promising course toward low-energy, carbon-neutral methanol reforming and sustainable hydrogen production.