Incorporating electron-deficient Cu nanoparticles in photoactive Zr-MOFs for highly efficient amine oxidative coupling with H2O2 photosynthesis

Abstract

Developing multifunctional photocatalytic systems that synergistically drive the selective syntheses of organic fine chemicals and photocatalytic H₂O₂ production offers a dual-benefit paradigm, achieving enhanced solar energy utilization efficiency while generating valuable organic chemicals. Despite the inherent potential, research on photocatalysts capable of performing dual functions remains scarce. In this study, an electron donor–acceptor (D–A) interface with superior charge separation and migration between electron-rich Zr-TPBD and electron-poor Cu nanoparticles is successfully constructed for boosting photocatalytic oxidative evolution. Integrating D–A interfacial engineering, Zr-TPBD–Cu demonstrates unprecedented efficiency in H₂O₂ synthesis, attaining a production rate of 73.5 mmol g⁻¹ h⁻¹ and an apparent quantum yield of 13.1%, which surpasses previously reported MOF-based and even most non-MOF-based photocatalysts. Additionally, under optimized oxidative coupling conditions, benzylamine underwent highly selective dimerization to form N-benzylidenebenzylamine, attaining a remarkable conversion efficiency exceeding 99.5%. This study pioneers the rational design of MOF-based materials with precisely engineered D–A interfaces, achieving unprecedented activity in dual-photocatalytic systems for solar energy conversion and organic chemical synthesis.