【摘要】 Imine-linked covalent organic frameworks（COFs） often face limitations in solar-driven hydrogen evolution owing to inefficient charge separation.To address this,we introduce atomically anchored Pt-N sites as bidirectional electron highways into theπ-conjugated TpTz-COF,which features an inherently heterogeneous electronic structure.Through robust Pt-N coordination anchoring,these atomic-scale clusters reconfigure the charge dynamics of the matrix by establishing bidirectional charge-transport pathways.This architecture simultaneously harvests photogenerated electrons from both donor and acceptor moieties while effectively suppressing charge carrier recombination.The resulting heterostructure achieves a remarkable apparent quantum efficiency（80.72%） under 420-nm irradiation.Such a high value results from the low work function（Φ=4.306 eV） of Pt driving directional electron migration,and the optimized Gibbs free energy of hydrogen absorption(ΔG_H*=-0.13 eV) accelerates the catalytic turnover.Crucially,covalent Pt-N interfacial bonds endow the material with exceptional operational stability across extreme pH conditions and during 22-d cycling tests,resolving long-standing durability issues in metal-organic hybrids.This innovative approach employs Pt clusters as active charge-directing centers rather than mere catalytic sites,establishing a paradigm-shifting principle for the design of next-generation photocatalysts that extends beyond the optimization of intrinsic material properties.更多还原

【Abstract】 Imine-linked covalent organic frameworks（COFs） often face limitations in solar-driven hydrogen evolution owing to inefficient charge separation.To address this,we introduce atomically anchored Pt-N sites as bidirectional electron highways into theπ-conjugated TpTz-COF,which features an inherently heterogeneous electronic structure.Through robust Pt-N coordination anchoring,these atomic-scale clusters reconfigure the charge dynamics of the matrix by establishing bidirectional charge-transport pathways.This architecture simultaneously harvests photogenerated electrons from both donor and acceptor moieties while effectively suppressing charge carrier recombination.The resulting heterostructure achieves a remarkable apparent quantum efficiency（80.72%） under 420-nm irradiation.Such a high value results from the low work function（Φ=4.306 eV） of Pt driving directional electron migration,and the optimized Gibbs free energy of hydrogen absorption(ΔG_H*=-0.13 eV) accelerates the catalytic turnover.Crucially,covalent Pt-N interfacial bonds endow the material with exceptional operational stability across extreme pH conditions and during 22-d cycling tests,resolving long-standing durability issues in metal-organic hybrids.This innovative approach employs Pt clusters as active charge-directing centers rather than mere catalytic sites,establishing a paradigm-shifting principle for the design of next-generation photocatalysts that extends beyond the optimization of intrinsic material properties.更多还原