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

doi:10.1016/j.actphy.2026.100329

Abstract

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.

Key words: HOFs/MOFs, Built-in electric field, S-scheme heterojunctions, π-π stacking charge-transfer channels, Photocatalysis

Qinghong Cai, Xingyan Liu, Yuhan Li, Youzhou He, Xianyan Xu, Jia Zeng, Siping Wei. 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[J]. Acta Phys. -Chim. Sin. 2026, 42(11), 100329. doi: 10.1016/j.actphy.2026.100329

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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

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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

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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