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

• Published in: Chemical engineering journal (Lausanne, Switzerland : 1996) Vol. 465; p. 142904
• Main Authors: Zhang, Baofang, Zengcai, Ziyu, Lin, Wenting, Zhang, Meijin, Pi, Yunhong, Wang, Tiejun
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 01.06.2023
• Subjects: Controllable in-situ derived TiO2; Cu-based catalysts; Hydrogen production from methanol aqueous-phase reforming; Metal-organic framework; Photothermal catalysis; Hydrogen production from methanol aqueous-phase reforming; Metal-organic framework; Photothermal catalysis; Controllable in-situ derived TiO2; Cu-based catalysts
• ISSN: 1385-8947; 1873-3212
• DOI: 10.1016/j.cej.2023.142904

A novel hierarchical heterojunction that integrating photo- and thermal-active Cu2O catalytic species with in-situ derived NH2-MIL-125@TiO2 framework specifically facilitates photothermal aqueous phase reforming of methanol into H2. [Display omitted] •Cu2O and in-situ derived TiO2 layer were hierarchically integrated in NH2-MIL-125(Ti) framework.•Cu2O/NH2-MIL-125@TiO2 afforded 13-fold photothermally-promoted H2 yield from reforming of MeOH/H2O than thermocatalytic process.•The synergistic effect between TiO2 and Cu2O catalysts in MOF enhanced stability and mobility of charge carriers.•Photothermal effect effectively activated methanol at 100 °C and reduced reaction activation energy by 36.5%.•The reaction pathway for photothermal H2 yield was fully discussed. Photothermal synergism can effectively activate methanol at low operating temperature and significantly reduce the activation energy of the reaction, achieving more efficiently H2 release from methanol reforming. Here, a novel hierarchical heterojunction that integrating photo- and thermal-active Cu2O catalytic species with in-situ derived NH2-MIL-125@TiO2 framework was specifically designed for photothermal-driven aqueous phase reforming of methanol into H2. The afforded Cu2O/NH2-MIL-125@TiO2 realized an outstanding photothermal H2 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 Cu2O/NH2-MIL-125@TiO2 with unexpected activity at low temperature subsided to 100 °C and accelerated the activation of MeOH/H2O 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 H2 evolution activity with average rate of 1.49x106 μmolgCu-1h−1 and a total turnover number (TON) up to 5971 in 63 h, almost 125-fold promotion compared with Cu2O.