20.500.12556/DKUM-100388 Microenvironmental tuning in isostructural conjugated metal–organic frameworks for superior photocatalytic ▫$H_2O_2$▫ generation Photocatalytic hydrogen peroxide (H2O2) generation via sunlight-driven water and oxygen reduction reactions presents a sustainable alternative to the energy-intensive anthraquinone process. Although metal–organic frameworks (MOFs) offer tunable platforms for photocatalysis, the influence of metal–ligand microenvironment modulation within isostructural systems remains largely unexplored. In this work, we report two chemically robust conjugated 3D MOFs, Mn-Tp and Fe-Tp, synthesized via a scalable, solvent-free mechanochemical route and their exploration as photocatalysts. Despite sharing identical topologies and morphologies, Mn-Tp exhibits markedly superior photocatalytic performance, achieving a remarkable H2O2 yield of 10,487 µmol g−1 h−1, an apparent quantum yield of 9.94% at 467 nm, and a solar-to-chemical conversion efficiency of 0.45%. Mechanistic investigations, supported by theoretical calculations, reveal that subtle differences in the metal-node microenvironment modulate the electronic structure, promote dual-channel H2O2 generation via oxygen reduction and water oxidation, and suppress decomposition pathways. This study highlights the crucial role of local redox tuning in enhancing photocatalytic functionality, providing a strategic blueprint for designing next-generation MOF-based catalysts for the sustainable production of oxidants. 3D-structures density functional theory hydrogen peroxide isostructural materials metal-organic framework photocatalysis 3D strukture teorija funkcionalne gostote fotokataliza true false false Wiley Angleški jezik Slovenski jezik https://onlinelibrary.wiley.com/journal/15213773 Članek v reviji 2026-09-16 09:33:58 2026-09-16 09:33:58 2026-09-17 03:10:57 0000-00-00 00:00:00 2026 0 0 14 str. [article no.] e6760851 2026 0000-00-00 Zaloznikova Objavljeno NiDoloceno 0000-00-00 2026-07-14 2026-08-13 54 288990979 10.1002/anie.6760851 1521-3773 https://onlinelibrary.wiley.com/doi/epdf/10.1002/anie.6760851 1 fb906254-b1a0-11f1-b05b-00155d0001be https://dk.um.si/Dokument.php?lang=slv&id=212562 Angew_Chem_Int_Ed_-_2026_-_Ranjeesh_-_Microenvironmental_Tuning_in_Isostructural_Conjugated_Metal_Organic_Frameworks_for.pdf Angew_Chem_Int_Ed_-_2026_-_Ranjeesh_-_Microenvironmental_Tuning_in_Isostructural_Conjugated_Metal_Organic_Frameworks_for.pdf 1 41B1F282E1AE99521715D8ED1AC7D90A 3111c2cd7a9b1bcca5a6dbb1c021d596cccfba04a461360f035383bf3b0de023 de84646c-b1a5-11f1-b05b-00155d0001be https://dk.um.si/Dokument.php?lang=slv&id=212563 Fakulteta za kemijo in kemijsko tehnologijo 0 0 0