Interfacial Engineering of TiO ₂ ‐Ni Heterojunctions for Synergistic Light‐Promoted Electrocatalytic Methanol Oxidation

Developing efficient and durable nonprecious metal anode catalysts for visible‐light‐assisted methanol fuel cells remains challenging. This work innovatively constructs a Ni nanoparticle‐decorated anatase TiO ₂ heterojunction on Ti substrates (Ti/TiO ₂ ‐Ni) via a three‐step anodization‐calcination‐electrodeposition strategy. The optimized Ti/TiO ₂ ‐Ni exhibits exceptional photo‐electrocatalytic methanol oxidation performance, achieving a current density of 11.03 mA cm ⁻² and a photocurrent density of 0.62 mA cm ⁻² at 1.5 V (vs. NHE) under visible light. Crucially, it retains 85% activity after 12 h of continuous operation, demonstrating remarkable stability. Mechanistic studies reveal that the Ti/TiO ₂ ‐Ni heterojunction narrows the bandgap from 3.1 to 2.2 eV, extends visible‐light absorption, and suppresses charge recombination. Furthermore, interfacial oxygen vacancies promote •OH generation, while photogenerated holes (h ⁺ ) and •OH synergistically oxidize methanol and intermediates, mitigating surface passivation. This work provides a viable noble‐metal‐free heterojunction strategy for high‐performance photo‐assisted fuel cell catalysts.