Designing 1-nm-Thick MOF Nanosheets with Donor-Acceptor Complexes for Photosynthesis of H₂O₂ Using Water and Dioxygen Only.

Abstract

Artificial photosynthesis of hydrogen peroxide (H₂O₂) presents a promising environmentally friendly alternative to the industrial anthraquinone process. This work designed ultrathin metal-organic framework (MOF) nanosheets on which porphyrin ligand as an electron donor (D) and anthraquinone (AQ) as an electron acceptor (A) are integrated as the D-A complexes. The porphyrin component allows the MOF nanosheets to absorb full-spectrum solar light while the acceptor AQ motif promotes central aluminum ion coordination, hindering layer stacking to achieve a thickness of 1.0 nm. The ultrathin D-A design facilitates the separation of electrons from the MOF skeleton to the AQ motif, which induces the direct two-electron oxygen reduction reaction (ORR) mediated by the reversible redox couple of AQ-AQH₂ and multielectron water oxidation reaction (WOR) driven by holes remaining on the porphyrin part. In O₂-saturated water, the ultrathin MOF nanosheets outperformed the AQ-free bulk and multilayered counterparts by 2.9 and 2.6 times in H₂O₂ production, respectively, achieving the apparent quantum yield of 4.8% at 420 nm. It also surpasses other benchmark photocatalysts, including the typical MOF photocatalyst, MIL-125-NH₂, and organic polymeric photocatalysts. The ultrathin D-A MOF photocatalyst generated H₂O₂ via both two-electron ORR as a major path and two-electron WOR as a minor path. This approach presents a promising strategy for the rational design of efficient nanostructured photocatalysts for solar fuels and chemicals.