Interface engineering of covalent β-ketoenamine-bridged S-scheme heterojunction for synergistic solar-powered CO2-to-CO conversion paired with selective alcohol oxidation

doi:10.1016/S1872-2067(25)64883-2

Abstract

Abstract:

To address persistent challenge of charge recombination in semiconductor photocatalysis, we engineered an S-scheme heterojunction via covalent β-ketoenamine bridges between zirconium-based MOFs and triazine-COFs (Zr-BTB-COF). This dual-functional system pioneered a "one-photon, two-value" strategy for simultaneous CO₂-to-CO reduction and 4-methoxybenzyl alcohol-to-anisaldehyde oxidation, enabling solar-driven carbon refineries. Synergistic in-situ XPS analysis and density functional theory calculations unambiguously validated the S-scheme charge transfer mechanism. The covalent interface overcame lattice mismatch constraints while Fermi-level alignment generated an enhanced built-in electric field (9.8 times stronger than pristine Zr-BTB-NH₂), achieving ultrafast charge separation. Low-energy carrier recombination through the β-ketoenamine bridge preserved high-potential carriers (-1.61 V for CO₂ reduction; +2.22 V for alcohol oxidation). Critically, this architecture reduced the activation energy barrier for the rate-limiting *COOH → *CO step to ΔG = 0.65 eV, a 42% reduction versus isolated Zr-BTB-NH₂. Through concerted thermodynamic and kinetic optimization, the covalent Zr-BTB-COF achieved high CO and anisaldehyde yields (71.9 and 44.7 μmol·g^-1·h^-1) with internal quantum efficiency of 3.75% (365 nm). This bond-resolved interface engineering paradigm establishes a new design framework for synchronizing carbon-neutral cycles with high-value chemical synthesis.

Key words: S-scheme heterojunction, Covalent β-ketoenamine bridge, Photocatalytic CO₂ reduction

Haopeng Jiang, Jinhe Li, Xiaohui Yu, Huilong Dong, Weikang Wang, Qinqin Liu. Interface engineering of covalent β-ketoenamine-bridged S-scheme heterojunction for synergistic solar-powered CO₂-to-CO conversion paired with selective alcohol oxidation[J]. Chinese Journal of Catalysis, 2026, 80: 113-122.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64883-2

https://www.cjcatal.com/EN/Y2026/V80/I1/113

Figures/Tables 10

Scheme 1. Design of Zr-BTB-COF S-scheme heterojunction with covalent bonds as an electron transport bridge.

Fig. 1. (a) Synthesis of the Zr-BTB-COF-3 composite. TEM images of Zr-BTB-NH2 (b) and Zr-BTB-COF-3 (c). (d,e) HAADF-STEM images of Zr-BTB-COF-3. XRD patterns (f), FT-IR spectra (g), UV-vis spectra (h) of TpTt-COF, Zr-BTB-NH2 and Zr-BTB-COF composites.

Fig. 2. The bandgaps of Zr-BTB-NH2 (a) and TpTt-COF (b). M-S plots of Zr-BTB-NH2 (c) and TpTt-COF (d). (e) Band structure of Zr-BTB-NH2 and TpTt-COF. (f) XPS full spectra of TpTt-COF, Zr-BTB-NH2 and Zr-BTB-COF-3.

Fig. 3. The XPS spectra of Zr 3d (a), N 1s (b) and C 1s (c) spectra of the prepared sample. (d) DFT calculation of electron transfer in Zr-BTB-COF-3 composite. (e,f) The mechanism diagram of BEF formation.

Fig. 4. (a,b) The CO and anisaldehyde production of TpTt-COF, Zr-BTB-NH2 and Zr-BTB-COF-3. (c,d) The CO and anisaldehyde yields of the prepared sample tested in the cycle. Photocatalytic reduction of CO2 under different conditions (e) and the result of 13C experiments (f).

Fig. 5. (a,b) In-situ XPS spectra of Zr-BTB-COF-3 under light and dark. (c,d) Possible S-scheme mechanism of the Zr-BTB-COF under light.

Fig. 6. The surface charge density (a), TS-SPV measurement (b) and BEF strength (c) of the pure Zr-BTB-NH2 and Zr-BTB-COF-3. PL (d), time-resolved PL spectra (e), charge extraction efficiencies (f), maximum charge extraction times (g), photocurrent density (h) and EIS (i) results of the prepared samples.

Fig. 7. In situ DRIFTS (a) and infrared contour map (b) for Zr-BTB-COF-3.

Fig. 8. (a) CO2 adsorption state over Zr-BTB-NH2, TpTt-COF, and Zr-BTB-COF (grey, red, green and silver spheres stand for C, O, Zr and N atoms, respectively). Intermediate configurations for Zr-BTB-COF along photoreduction CO2 reaction (b) and free energy diagram (c) of CO2 photoreduction to CO over Zr-BTB-NH2 and Zr-BTB-COF.

Fig. 9. A possible reaction mechanism of Zr-BTB-COF for solar-driven coupled redox systems.

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Interface engineering of covalent β-ketoenamine-bridged S-scheme heterojunction for synergistic solar-powered CO₂-to-CO conversion paired with selective alcohol oxidation

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