Atomic-level lattice matching in hexagonal WO3/TiO2 S-scheme heterojunctions for high-efficiency selective photoelectrocatalytic glycerol-to-dihydroxyacetone conversion

doi:10.1016/S1872-2067(26)64955-8

Abstract

Abstract:

This study developed a lattice-matching engineering strategy to construct atomic-level coherent interfaces in hexagonal WO₃/TiO₂ S-scheme heterojunctions to boost photoelectrocatalytic glycerol (Gly) valorization. Through precise annealing control, hexagonal WO₃/TiO₂ achieved an ultra-low lattice mismatch (m) of 0.027%, significantly lower than the 2.30% mismatch of its monoclinic counterparts, thus inducing a strong built-in electric field (3.71 eV) and optimized S-scheme charge transfer. These features resulted in 90% suppressed carrier recombination, 2.64-fold extended carrier lifetime, and enhanced secondary hydroxyl adsorption affinity (1.854 eV), collectively steering Gly oxidation toward high-value dihydroxyacetone with 35% selectivity (1.9-fold higher than that of monoclinic systems). The heterojunction also delivered a 21% Gly conversion rate (40% higher than its monoclinic counterparts), while maintaining > 85% total C3-product selectivity and stability over 40 h. This study identified the atomic-scale interface coherence as a critical factor for synchronizing charge dynamics and surface reactions in biomass upgrading.

Key words: Hexagonal WO₃/TiO₂, Glycerol valorization, Photoelectrochemical, S-scheme heterojunction, Interface engineering

Wanggang Zhang, Haochen Xie, Hongliang Wang, Rufeng Tian, Lei Liu, Jian Wang, Yiming Liu. Atomic-level lattice matching in hexagonal WO₃/TiO₂ S-scheme heterojunctions for high-efficiency selective photoelectrocatalytic glycerol-to-dihydroxyacetone conversion[J]. Chinese Journal of Catalysis, 2026, 82: 161-173.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)64955-8

https://www.cjcatal.com/EN/Y2026/V82/I3/161

Figures/Tables 9

Fig. 1. HRTEM images of h-WT (a) and enlarged interface of Area 1 (b). The inset in (a) shows the FFT patterns of Area 1. (c) Geometric phase analysis (GPA) results of Area 1 along the ex vector direction. (d) Schematic diagrams used to calculate the m between TiO2 and h-WO3. HRTEM images of m-WT (e) and enlarged interface of Area 2 (f). The inset in (f) shows the FFT patterns of Area 2. (g) GPA results of Area 2 along the exvector direction. (h) Schematic diagrams used to calculate the m between TiO2 and m-WO3. Expanded AC-HAADF (i) and AC-BF (j) images recorded from the boxed region in Area 3. Expanded AC-HAADF (k) and AC-BF (l) images recorded from the boxed region in Area 4. (m) STEM-EDS mapping results of h-WT.

Fig. 2. Transient photocurrent density-time profiles (a), ABPE values (b), and IPCE spectra (c) of TiO2, m-WT, and h-WT at 1.23 V vs RHE in 0.1 mol L-1 Na2SO4 with 0.1 mol L-1 Gly under AM 1.5G illumination. (d) LSV curves of the TiO2, m-WT, and h-WT photoanodes. (c) Selectivity and FE of organic products over the TiO2, m-WT, and h-WT photoanodes at 1.23 V vs. RHE (measured over a 4-h period). (e) The organic products included DHA and glyceraldehyde (GLD). (f) Production rate of DHA and GLD on the TiO2, m-WT, and h-WT photoanodes at different potentials (measured over a 4-h period).

Fig. 3. Kinetic curves for the PEC GOR over h-WT (a) and m-WT (d) at 1.23 V vs. RHE. Selectivity of organic products over the h-WT (b) and m-WT (e) photoanodes at 1.23V vs. RHE (measured over a 10-h period). Stabilities of the h-WT (c) and m-WT (f) photoanodes for the PEC GOR. Error bars represent the standard deviation of the results from three parallel repeated experiments, which is within 10%; the corresponding data are the average values.

Fig. 4. (a) UV-vis DRS spectra of TiO2, m-WO3, and h-WO3. (b) Energy diagrams of h-WO3 and TiO2. (c) High-resolution Ti 2p XPS spectra of TiO2 and h-WT. (d) High-resolution W 4f XPS spectra of h-WO3 and h-WT. (e) Potential calculation for h-WT.

Fig. 5. (a,b) KPFM surface potential images of m-WT under dark and light (AM 1.5G, 100 mW cm-2) conditions, respectively. (c) Line profile (corresponding to curve 1 in panels a and b) of the surface potential across the m-WT interface under dark and light conditions. (d,e) KPFM surface potential images of h-WT under dark and light conditions, respectively. (f) Line profile (corresponding to curve 2 in panels (d) and (e)) of the surface potential across the h-WT interface under dark and light conditions. (g,h) High-resolution XPS spectra of the W 4f (g) and Ti 2p (h) regions for h-WT under dark and light conditions. (i) Schematic diagram illustrating the S-scheme charge transfer mechanism between h-WO3 and TiO2 under illumination.

Fig. 6. (a) Mott-Schottky plots measured under AM 1.5G illumination. (b) Time-resolved transient PL decay spectra up-on excitation at 280 nm. (c) EIS plots under light irradiation (inset shows the equivalent circuit of the Nyquist plots). (d) IMPS responses. (e) Plot of the potential-dependent rate constant for charge transfer. (f) Plot of the potential-dependent rate constant for charge recombination.

Fig. 7. EQCM plots (a) and FTIR spectra (b,c) for the TiO2, m-WT, and h-WT photoanodes after absorbing isopropanol and n-propanol. (d,e) DFT-calculated energies for Gly adsorption on the TiO2, m-WT, and h-WT surfaces via the primary or secondary hydroxyl group. (f,g) Adsorption energies of the GLD and DHA adsorbed on the TiO2, m-WT, and h-WT surfaces. (h) Current density-time profiles of the h-WT photoanode at 1.23 V vs. RHE in a 0.1 mol L-1 Na2SO4 electrolyte with 0.1 mol L-1 GLY, GLD, glyceric acid (GLA), or DHA under AM 1.5G illumination. (i) Proposed reaction pathway of the GOR.

Fig. 8. FTIR spectra of the dynamic isopropanol oxidation process on TiO2 (a) and h-WT (b) under AM 1.5G (100 mW cm?2) illumination for 60 min. (c) Room-temperature ESR spectra of h-WT in different electrolytes. (d) LC-MS spectra of the DHA product of the PEC GOR in an isotope-labeled electrolyte with 10% H218O. (e) Gibbs free energy profiles of the oxidation processes involving the primary and secondary hydroxyl groups on the h-WT surface.

Fig. 9. Schematic diagram illustrating the photocatalytic GOR enhancement mechanism of the interface-matched WO3-TiO2 S-heterojunction.

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Atomic-level lattice matching in hexagonal WO₃/TiO₂ S-scheme heterojunctions for high-efficiency selective photoelectrocatalytic glycerol-to-dihydroxyacetone conversion

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