Confined dual-interface HRGO/Cu2O@CuMOF heterojunction for enhanced photothermal methanol/water reforming to hydrogen

Abstract

Photothermal-driven methanol/water reforming offers as a sustainable route for low-temperature, on-site hydrogen (H₂) production by coupling solar energy with liquid fuel compatibility. Herein, a HRGO/Cu₂O@CuMOF core-shell heterojunction catalyst was in situ constructed via a homologous coordination etching strategy. This design introduces dual-interface synergy and confined spatial architecture: HRGO-Cu⁺ interface enhances water adsorption and activation, accelerating OH· radical generation for C–H bond cleavage in methanol; Cu₂O-CuMOF junction facilitates charge separation and stepwise dehydrogenation through spatially confined intermediate transformation. Benefiting from this cooperative architecture, the catalyst achieves a high H₂ production rate of 77.2 mmol g_cat⁻¹ h⁻¹ at 210°C, nearly 8 times of thermal reforming, with activation energy significantly reduced by 29.6%. Notably, the catalyst can initiate H₂ generation as low as 100°C, and maintains excellent activity and integrity over 72 h. This work offers a scalable strategy for constructing MOF-based heterojunctions with confined interface synergy, advancing sustainable photothermal H₂ production.