Photo‐Promoted Thermocatalysis: Low‐Temperature Methanol Steam Reforming Toward Hydrogen Production

ABSTRACT Methanol steam reforming (MSR) is an important route for on‐site H 2 production, yet practical application is generally constrained by high operation temperature and substantial energy consumption. Photothermal catalysis, in which hot electrons participate in catalytic reaction, offers a promising pathway for low‐temperature MSR. Herein, a Cu/CeZrO x photothermal catalyst (denoted as CuCZ) was prepared through a coprecipitation–calcination–reduction strategy. The optimized CuCZ achieves a hydrogen production rate of 180.9 µmol g −1 s −1 under full‐spectrum irradiation at 199°C, which is 26.2 times larger than that obtained with thermocatalytic mode, while maintaining a CO selectivity below 0.2%. A comprehensive structural characterization reveals the formation of Cu δ + −O v –CeZrO x interfacial sites with pronounced light‐induced interfacial reconstruction. In situ spectroscopic studies, kinetic analyses, and density functional theory calculations substantiate a photo‐assisted thermocatalytic mechanism, in which photoexcitation drives hot electron injection and interfacial electron transfer, triggering a dynamic evolution of the Cu 0 /Cu + –[O*⇋O v ]–Ce 3+ /Ce 4+ interfacial structure. This dynamic interface enables the synergistic coupling of methanol dissociation, H 2 O activation, and lattice oxygen regeneration, which boosts the kinetically relevant step (HCOO* conversion) by five times and delivers a 21.8% reduction in the kinetic isotope effect. This photo‐assisted thermocatalysis overcomes the inherent kinetic limitations of low‐temperature MSR, accounting for significantly promoted reaction efficiency.