Confinement of Cu2O by in-situ derived NH2-MIL-125@TiO2 for synergetic photothermal-driven hydrogen evolution from aqueous-phase methanol reforming

Photothermal synergism can effectively activate methanol at low operating temperature and significantly reduce the activation energy of the reaction, achieving more efficiently H 2 release from methanol reforming. Here, a novel hierarchical heterojunction that integrating photo- and thermal-active Cu 2 O catalytic species with in-situ derived NH 2 -MIL-125@TiO 2 framework was specifically designed for photothermal-driven aqueous phase reforming of methanol into H 2 . The afforded Cu 2 O/NH 2 -MIL-125@TiO 2 realized an outstanding photothermal H 2 production activity (apparent quantum efficiency of 22.3 % at 365 nm), ca. 13-times higher than that of thermocatalytic condition. Interestingly, the photothermal effect did confer the Cu 2 O/NH 2 -MIL-125@TiO 2 with unexpected activity at low temperature subsided to 100 °C and accelerated the activation of MeOH/H 2 O with an obvious reduction of activation energy from 82.62 kJ·mol −1 to 52.40 kJ·mol −1 .   The improvement of catalyst stability and the promotion of charge separation also contributed to a long-term photothermal H 2 evolution activity with average rate of 1.49x10 6 μmolg Cu -1 h −1 and a total turnover number (TON) up to 5971 in 63 h, almost 125-fold promotion compared with Cu 2 O.