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Metal-organic framework stabilizes Cu7S4-wrapped Cu2O heterostructure for photothermal-promoted methanol/water reforming into hydrogen

AICHE JOURNAL(2023)

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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 Cu2O/Cu7S4 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 Cu2O/ Cu7S4@MIL-101(Cr) with unprecedented activity at low temperature subside to 100 similar to C and accelerated the activation of water and methanol with distinctly decreased activation energy from 103.9 to 66.6 kJ similar to mol similar to 1. Meanwhile, the enhanced catalyst stability and facilitated charge separation between Cu2O/Cu7S4 and MIL101(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 Cu2O/Cu7S4.
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Key words
aqueous phase reforming of methanol, Cu-based catalyst, hierarchical heterojunction, metal-organic framework, photothermal synergism
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