Cooperative interfacial preconditioning in an S-scheme heterojunction for CO2 photoreduction

doi:10.1016/S1872-2067(26)65186-8

Abstract

Abstract:

Efficient S-scheme photocatalysis requires not only favorable band alignment but also sufficiently strong interfacial driving forces to direct photogenerated carrier migration across the junction. Local donor-acceptor (D-A) coordination and global Fermi-level equilibration are shown to cooperate in the dark to precondition interfacial energetics and thereby promote subsequent S-scheme charge transfer. A molecularly coupled heterojunction is constructed by integrating a triazine-imine covalent organic framework (TPT-COF) with ZnO quantum dots through interfacial Zn-N coordination. Spectroscopic analyses reveal that D-A-induced local electron redistribution and Fermi-level-equilibration-driven compensating charge redistribution coexist in the dark, cooperatively enlarging the effective interfacial energy offset and reinforcing the internal electric field prior to illumination. Ultrafast spectroscopy further shows that this preconditioned interface accelerates S-scheme charge transfer under light irradiation, enabling efficient spatial charge separation while preserving strong redox potentials. As a result, the optimized COF/ZnO heterojunction achieves selective CO₂ photoreduction to CH₄ without external photosensitizers or sacrificial agents. These findings identify a cooperative mechanism by which local coordination chemistry and interfacial electrostatics jointly regulate S-scheme energetics, offering a molecular strategy for designing adaptive photocatalytic interfaces for solar fuel production.

Key words: Donor-acceptor coordination, Fermi-level equilibration, Interfacial energetics, S-scheme heterojunction, CO₂ photoreduction

Xiaoqian Wang, Feifan Zhao, Wantian Mei, Jianjun Zhang, Chuanbiao Bie, Jiaguo Yu, Hermenegildo Garcia, Feiyan Xu. Cooperative interfacial preconditioning in an S-scheme heterojunction for CO₂ photoreduction[J]. Chinese Journal of Catalysis, 2026, 90: 169-183.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65186-8

https://www.cjcatal.com/EN/Y2026/V90/I11/169

Figures/Tables 6

Scheme 1. Cooperative dark-state interfacial preconditioning by local donor-acceptor coordination and Fermi-level equilibration in an S-scheme heterojunction.

Fig. 1. Synthesis, structural characterization, and interfacial D-A coordination in the COF/ZnO heterojunction. (a) Schematic illustration of the synthesis. (b) XRD pattern of TPT-COF. (c) TEM image and corresponding size distribution (inset) of ZnO QDs. (d) TEM and HRTEM images of CZ2 with the corresponding EDX spectrum (inset). (e) HAADF image and elemental mapping of C, N, Zn, and O elements in CZ2. (f) FTIR spectra of pristine COF, ZnO, and the CZ2 composite. (g) Schematic of the interfacial D-A coordination, with electron donation from the imine-N sites of the COF to the Zn sites in ZnO.

Fig. 2. Fermi-level shift and surface-potential evolution in the COF/ZnO heterojunction. UPS spectra of (a) pristine COF and (b) pure ZnO. (c) Schematic energy-level alignment of pristine COF and ZnO derived from UPS measurements. UPS spectra of COF-based composites containing 5 wt% (d) and 10 wt% (e) ZnO, respectively. (f) KPFM surface potential profiles of COF and COF/ZnO composites, showing progressively more negative potentials with increasing ZnO loading. UPS spectra of ZnO-based composites containing 5 (g) and 10 (h) wt% COF. (i) KPFM surface potential profiles of ZnO and COF/ZnO composites, revealing an upward shift of the surface potential upon COF incorporation. Schematic energy-level diagrams illustrating the enlarged ΔEF in the COF/ZnO heterojunction, arising from the downward shift of the COF Fermi level (j) and the upward shift of the ZnO Fermi level (k) upon D-A coupling.

Fig. 3. Dark-state interfacial preconditioning and subsequent S-scheme charge transfer in the COF/ZnO heterojunction. High-resolution XPS spectra of N 1s (a), Zn 2p (b), and O 1s (c). (d,e) Zn K-edge XANES spectra of ZnO and CZ2 under different atmospheres with and without light irradiation , together with Zn foil as the reference standard. (f) Fourier-transformed EXAFS spectra of ZnO and CZ2 under different atmospheres with and without light irradiation. (g) Schematic illustration of the preconditioned S-scheme charge-transfer pathway in the COF/ZnO heterojunction.

Fig. 4. Ultrafast charge-transfer dynamics and carrier relaxation in pristine COF, ZnO, and the COF/ZnO heterojunction. Pseudocolor plots and transient absorption spectra recorded at indicated delay times under 340 nm excitation of pure COF (a,b), pristine ZnO (c,d), CZ2 under Ar (e,f), and CZ2 under CO2 (g,h). (i) Kinetic decay profiles at 420 nm within 200 ps for COF under Ar and CZ2 under Ar and CO2. (j) Schematic illustration of charge-carrier relaxation pathways in pristine COF and the preconditioned S-scheme charge-transfer process in the COF/ZnO heterojunction under Ar and CO2 atmospheres. (k) Kinetic decay profiles at 360 nm within 200 ps for ZnO under Ar and CZ2 under Ar and CO2. (l) Schematic illustration of charge-carrier relaxation pathways in pristine ZnO and the preconditioned S-scheme charge-transfer mechanism in the COF/ZnO heterojunction under Ar and CO2 conditions.

Fig. 5. CO2 photoreduction performance and reaction mechanism in the COF/ZnO system. (a) CO2-TPD profiles of COF, ZnO, and CZ2. Time-dependent production rates of CO (b) and CH4 (c) during photocatalytic CO2 reduction under UV-visible light irradiation. (d) Total production yields and CH4 selectivity of CO2 photoreduction over COF, ZnO, and CZx composites. Error bars in panels b-d represent the standard deviations from three independent experiments. (e) Total ion chromatogram, and (f,g) corresponding mass spectra of 13CO and 13CH4 detected from the photocatalytic reduction of 13CO2 over CZ2. (h) Wavelength-dependent AQE and UV-vis absorption spectrum of CZ2. (i) In-situ DRIFT spectra for photocatalytic CO2 reduction over the COF/ZnO heterojunction in the dark and under light irradiation.

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Cooperative interfacial preconditioning in an S-scheme heterojunction for CO₂ photoreduction

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