Metal‐organic framework stabilizes Cu ₇ S ₄ ‐wrapped Cu ₂ O heterostructure for photothermal‐promoted methanol/water reforming into hydrogen

Abstract To realize highly efficient in situ release of hydrogen energy from methanol reforming at lower operation temperature, the introduction of solar energy can effectively activate the methanol and significantly reduce activation energy of reaction. Herein, the hierarchical integration of photoactive Cu 2 O/Cu 7 S 4 core‐shell nanospheres stabilized by MIL‐101(Cr) support for H 2 evolution from photothermal‐driven aqueous phase reforming of methanol afforded nearly sixfold enhanced performance compared with thermocatalytic process. Impressively, the photothermal effect conferred the Cu 2 O/Cu 7 S 4 @MIL‐101(Cr) with unprecedented activity at low temperature subside to 100°C and accelerated the activation of water and methanol with distinctly decreased activation energy from 103.9 to 66.6 kJ·mol −1 . Meanwhile, the enhanced catalyst stability and facilitated charge separation between Cu 2 O/Cu 7 S 4 and MIL‐101(Cr) also contribute to the extraordinary photothermal‐enhanced H 2 evolution with an overall turnover number of up to 14,266 in 60 h (apparent quantum efficiency of 25.08% at 365 nm), almost 10,000 times higher than that of Cu 2 O/Cu 7 S 4 .