Light-switchable product selectivity in CO2 photoreduction over hollow plasmonic TiO2/AuCu@COF core-shell architectures

doi:10.1016/S1872-2067(26)65075-9

Abstract

Abstract:

The development of photo-switchable CO₂ reduction catalysts capable of selectively generating two distinct target products under different light irradiation holds significant potential for achieving multifunctional catalysis and enhancing economic viability in industrial applications, yet remains a formidable challenge. Herein, we demonstrate a hollow core-shell plasmonic TiO₂/AuCu@TB-COF (TACT) photocatalyst that achieves 343.9 μmol g_cat^-1 h^-1 activity and 98.7% selectivity toward CH₄ under ultraviolet (UV) light, but switches to 132.7 μmol g_cat^-1 h^-1 activity with 86.6% selectivity for CO under visible light in pure water without altering any other reaction conditions. Comprehensive mechanistic studies reveal that UV and visible light selectively excite different components, inducing distinct interfacial charge transfer routes. This not only endows TACT with higher charge separation efficiency under UV light versus visible light, but also directs photocarriers to different active sites for redox reactions depending on the irradiation wavelength. Specifically, H₂O oxidation occurring on the TiO₂ core under UV light more favorably promotes O₂ evolution and proton liberation compared to oxidation on the TB-COF shell under visible light. For CO₂ reduction, UV light drives consecutive hydrogenation of *CO intermediates on the AuCu sites, whereas visible light preferentially induces *CO desorption from the TB-COF surface. The contrasting electron and proton supply, combined with the divergent fates of *CO intermediates, collectively govern the wavelength-dependent CO₂ reduction pathways.

Key words: Photo-switchable catalyst, CO₂ reduction, H₂O oxidation, Differential electron and proton supply, Divergent *CO intermediate fate

Xin Yuan, Linyi Wu, Fengying Cao, Lechu Xu, Peng Wang, Hulin Shi, Shuxian Zhong, Lian Liu, Weihao Mo, Leihong Zhao, Song Bai. Light-switchable product selectivity in CO₂ photoreduction over hollow plasmonic TiO₂/AuCu@COF core-shell architectures[J]. Chinese Journal of Catalysis, 2026, 87: 87-99.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65075-9

https://www.cjcatal.com/EN/Y2026/V87/I8/87

Figures/Tables 6

Fig. 1. Synthesis and electronic microscopy characterizations of TACT. (a) Schematic illustrating the synthesis of TACT. TEM (b,c) and HRTEM (d) images of TAC. TEM (e,f), HRTEM (g), and STEM-EDS mapping (h) images of TACT.

Fig. 2. Spectroscopic characterizations of TACT and reference samples. (a) XRD patterns. (b) UV-vis DRS. (c) N2 sorption isotherms. (d) CO2 adsorption isotherms. High-resolution XPS spectra of Ti 2p (e), Au 4f (f), Cu 2p (g), and N 1s (h).

Fig. 3. Photocatalytic performance of TACT and reference samples. CO and CH4 evolution rates and selectivities under UV (a) and visible light (b) irradiation. (c) CO and CH4 yields of TACT under alternating UV and visible light illumination. (d) O2 evolution rates under UV and visible light irradiation. (e) Mass spectra of generated 13CH4 (top) and 13CO (bottom). (f) Recycling tests over TACT under UV and visible light irradiation, respectively.

Fig. 4. Light-dependent charge kinetics and mechanisms in TACT. Steady-state (a) and time-resolved (b) PL spectra of TACT and reference samples. (c) Photocurrent responses under UV and visible light irradiation. (d) Schematic illustrating the heterojunction formation and charge transfer mechanisms in TACT under UV and visible light irradiation. Charge density differences of TiO2/AuCu (e), AuCu/TB-COF (f), and TiO2/TB-COF (g) heterointerfaces (electron accumulation and depletion are represented by the yellow and blue regions, respectively; the isosurface is 0.002 electron per Å3).

Fig. 5. Light-dependent surface reactivities of TACT. EPR spectra of TEMPO-e- signals (a), TEMPO-h+ signals (b), DMPO-CO2•- signals (c), and DMPO-H signals (d) under UV and visible light irradiation. (e) In-situ DRIFTS spectra of TACT in CO2 photoreduction under UV (top) and visible (bottom) light irradiation.

Fig. 6. DFT calculations and light-dependent photocatalytic mechanisms in TACT. (a) CO2 adsorption energies on AuCu and TB-COF as well as H2O adsorption energies on TiO2 and TB-COF. (b) Gibbs free energy diagrams for H2O-to-O2 oxidation on TiO2 and TB-COF surfaces. (c) Gibbs free energy diagrams for CO2 reduction to CO and CH4 on AuCu and TB-COF surfaces. (d) Schematic illustrating the photocatalytic reaction mechanisms in TACT under UV and visible light irradiation.

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Light-switchable product selectivity in CO₂ photoreduction over hollow plasmonic TiO₂/AuCu@COF core-shell architectures

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