物理化学学报2026，Vol.42Issue(11)：66-80,15.DOI:10.1016/j.actphy.2026.100329
由HOFs/MOFs S型异质结中π-π堆叠电荷转移通道促进的强内置电场用于提升光催化产氢或过氧化氢
Strong built-in electric field promoted by π-π stacking charge-transfer channels in HOFs/MOFs S-scheme heterojunction for boosting photocatalytic H2 or H2O2 production
摘要
Abstract
Despite hydrogen-bonded organic frameworks(HOFs)and metal-organic framework(MOFs)exhibit distinct advantages in photocatalysis,the fabrication of HOFs/MOFs heterojunction remains scarcely explored.In particular,the deep-seated charge transfer dynamics in such heterojunctions remain unclear.Herein,in situ coupling HOFs(SA-TCPP)and MOFs(ZnTCPP)through π-π interaction to fabricate the porphyrin-based HOFs/MOFs(SA-TCPP/ZnTCPP)S-scheme heterojunction with strong built-in electric field(IEF),in which the optimal IEF intensity for SA-TCPP/ZnTCPP was increased by 11.5 and 4.9 times compared to individual SA-TCPP and ZnTCPP,respectively.Within the SA-TCPP/ZnTCPP S-scheme heterojunction system,the contact interface serves as the charge carriers regulation centers to promote IEF pumps strength via π-π stacking HOMO-LOMO charge-transfer channels,which adjusts the precise direction of spatial separation for photogenerated charge carriers and triggers a sophisticated cascade reactions via"photoexcitation-migration channel-pump acceleration"strategy.Compared with the individual SA-TCPP and ZnTCPP,the photocatalytic rate of H2(2307 μmol g-1 h-1)and H2O2(295.2 μmol g-1 h-1)for SA-TCPP/ZnTCPP increased 7.02 times,5.6 times and 3.09 times,2.85 times,respectively.The significant improvement can be ascribed to the efficient separation efficiency of charge carriers,which has been elucidated by femtosecond transient absorption spectroscopy(fs-TAS),kelvin probe force microscopy(KPFM),in situ X-ray photoelectron spectroscopy(in situ XPS)and density functional theory(DFT).This work achieves the cross-functional integration of frameworks,providing a novel design strategy for developing excellent and multifunctional artificial photosynthesis systems.关键词
HOFs/MOFs/内置电场/S型异质结/π-π堆叠电荷传输通道/光催化Key words
HOFs/MOFs/Built-in electric field/S-scheme heterojunctions/π-π stacking charge-transfer channels/Photocatalysis分类
化学化工引用本文复制引用
蔡清红,刘兴燕,李宇涵,贺有周,徐先燕,曾嘉,韦思平..由HOFs/MOFs S型异质结中π-π堆叠电荷转移通道促进的强内置电场用于提升光催化产氢或过氧化氢[J].物理化学学报,2026,42(11):66-80,15.基金项目
国家自然科学基金(22001026,52370109和22171233) （22001026,52370109和22171233）
重庆市自然科学基金(CSTB2025YITP-QCRCX0064,CSTB2025NSCQ-GPX0827,CSTB2024NSCQ-LZX0073,CSTB2025NSCQ-GPX0816) （CSTB2025YITP-QCRCX0064,CSTB2025NSCQ-GPX0827,CSTB2024NSCQ-LZX0073,CSTB2025NSCQ-GPX0816）
重庆市教委科学技术研究计划(KJZD-M202400802和KJZD-K202300806)资助. （KJZD-M202400802和KJZD-K202300806）
