Intrareticular Energy Transfer in Dual-Photosensitized Metal–Organic Frameworks to Enhance Photoelectrochemical Performance

Metal-organic frameworks (MOFs) have garnered significant interest in photoelectrochemistry (PEC). To overcome the intrinsic drawbacks of narrow-wavelength absorption and limited photon utilization, this study used two photosensitizers as hybrid ligands to realize intrareticular energy transfer (IRET) and multiple wavelength light absorption for enhancing photoelectrochemical performance. The dual-photosensitized MOF (dpMOF) contained a [Cd₂(COO)₄] paddlewheel unit as the metal node along with meso-tetra(4-carboxyphenyl)porphine and pyridine-functionalized boron dipyrromethene ligands serving as the energy acceptor and donor units, respectively. Both experimental data and theoretical calculations confirmed the energy transfer. The IRET process possessed an energy transfer efficiency of up to 88.3%, significantly promoting photon utilization and charge separation. Compared with single photosensitized MOFs with similar topologies, IRET in dpMOF resulted in 2.6-6.5 times enhanced photocurrent under multiple wavelength irradiation. Therefore, an advanced PEC biosensing strategy was proposed to demonstrate the PEC application of dpMOF. This work offers new insights into the design of enhanced MOFs and photoconversion applications.