Surface Electron Localization in Cu-MOF-Bonded Double-Heterojunction Cu2O Induces Highly Efficient Photocatalytic CO2 Reduction

Truncated octahedron Cu2O (TOC) has attracted more attention for its suitable band gap and high carrier separation efficiency due to introduction of the facet heterojunction, but its practical drawback is still the instability caused by the irreversible disproportionation reaction (Cu2O → Cu + CuO). Here, we design and fabricate the TOC/Cu-MOF (MOF: metal-organic framework) double-heterojunction structures with different Cu-MOF loadings. The introduced heterojunction between TOC and Cu-MOF not only produces a stable interface Cux+ bonding structure with the electronic states localized within the average collisional diameter of electrons 1.72 nm for TOC/2.1 wt %Cu-MOF as the active sites, but also promotes the surface energy level difference between the (100) and (111) facet heterojunctions. Meanwhile, the bonded Cu-MOF with a narrow bandgap effectively consumes holes by recombination with the photoexcited electrons from Cu-MOF itself. In our experiments, the TOC/Cu-MOF double heterostructure with a loading amount of 2.1 wt % Cu-MOF shows an optimal photocatalytic CO2 reduction performance. The CO evolution rate reaches 23.01 μmol g-1 h-1, which is about 2.01 and 4.47 times larger than those of octahedral and hexahedral Cu2O/Cu-MOF, respectively, and an excellent photostability is shown for four cycles with each cycle lasting for 4 h. Such a double heterostructure provides insight into highly efficient electron transfer and photostability in Cu2O-related composite materials.