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 dual- functions remain 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.