Citric directional coordination for efficient photocatalytic synthesis of H2O2 with high value-added β-Ketoglutaric acid

doi:10.1016/S1872-2067(25)64885-6

Abstract

Abstract:

Photocatalytic hydrogen peroxide (H₂O₂) production offers a green alternative to the traditional anthraquinone process but remains limited by inefficient charge separation and underutilized photogenerated holes. Herein, we present a spatially resolved coordination strategy to couple efficient H₂O₂ generation with selective oxidation of biomass-derived hydroxy acids. Anisotropic Au-modified BiVO₄ photocatalysts were constructed, where Au nanoparticles on the (010) facet promoted H₂O₂ formation, while undercoordinated Bi atoms on the (110) facet selectively oxidized citric acid (CA). A five-membered chelate ring formed between β-hydroxyl and carboxyl groups of CA and surface Bi atoms, enabling directional coordination that enhanced hole extraction and guided a selective decarboxylation pathway to produce acetone dicarboxylic acid with 99% selectivity. This dual-functional design achieved a high H₂O₂ production rate (~0.6 mmol L^-1 h^-1) and exhibited broad applicability to other hydroxy acids. This work provides mechanistic insights into photocatalyst-substrate interactions and establishes a generalizable strategy for integrating H₂O₂ photosynthesis with value-added chemical production under solar irradiation.

Key words: Photocatalytic H₂O₂ production, Selective oxidation, Spatial charge separation, Directional coordination, High-value-added chemicals

Jing Zhang, Xidong Zhang, Kaiyan Wang, Xuefei Wang, Ping Wang, Feng Chen, Huogen Yu. Citric directional coordination for efficient photocatalytic synthesis of H₂O₂ with high value-added β-Ketoglutaric acid[J]. Chinese Journal of Catalysis, 2026, 82: 201-211.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64885-6

https://www.cjcatal.com/EN/Y2026/V82/I3/201

Figures/Tables 7

Fig. 1. Schematic illustration of Au/BiVO4 for H2O2 photosynthesis coupled with citric acid (CA) photo-oxidation via a directional coordination strategy.

Fig. 2. (a) Schematic drawing illustrating the controllable preparation of Au/BiVO4 single-crystal photocatalyst. Typical FESEM results of the BiVO4 (b) and Au/BiVO4 (c). XRD patterns (d) and UV-vis diffuse reflection spectra (e).

Fig. 3. (a,b) Photocatalytic performance of Au/BiVO4 for H2O2 production in different systems. (c) Optimizing CA concentration in photocatalytic H2O2 production of Au/BiVO4. (d) Recycles test of Au/BiVO4 for H2O2 production.

Fig. 4. The DFT calculation structure of BiVO4 (a), CA (b), and the DFT calculation optimal structure (c) of Bi sites and coordination of CA. (d) DFT calculated values for different coordination modes of CA and BiVO4. (e) FTIR spectra of Au/BiVO4 and CA modified Au/BiVO4. (f) The high-resolution XPS spectra of Bi 4f for Au/BiVO4 and CA modified Au/BiVO4. (g) Schematic diagram of the band structure of BiVO4. (h) High-resolution XPS spectra of O 1s for Au/BiVO4-CA. LSV curves obtained for glass electrodes modified with different sacrificial agents (i) and transient photocurrent response (j) obtained for glass electrodes modified with BiVO4 photocatalyst in 0.1 mol L-1 HClO4 with CA (1), CH3OH (2), and EtOH (3) at 0.05 V s-1.

Fig. 5. (a) The reaction mechanism of Au/BiVO4 forming OGA under the coordination of CA. LC-MS results of the CA reaction solution after Au/BiVO4 photocatalytic reaction for 0 h (b) and 2 h (c). In-situ DRIFTS result (d) and enlarged spectra (e-g) for Au/BiVO4 sample under light illumination for 0-90 min.

Fig. 6. (a) Evolutions of CA, H2O2, OGA, and CO2 with increasing illumination time. (b) Performance comparison of photocatalytic H2O2 evolution coupled with organic oxidation. (c) Photocatalytic redox reaction equation for OGA and H2O2. (d) The pathways for OGA and H2O2 formation on Au/BiVO4.

Fig. 7. DFT theoretical calculation models. (a) Malic acid (MA). (b) DFT calculated values for different coordination modes of MA and BiVO4. In-situ DRIFTS result (c) and enlarged spectra (d-f) for AuPd/BiVO4 sample under light illumination for 0-90 min. (g) LC-MS results of the MA reaction solution after AuPd/BiVO4 photocatalytic reaction for 2 h. (h) Evolutions of MA, H2O2, and PA with increasing illumination time.

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Citric directional coordination for efficient photocatalytic synthesis of H₂O₂ with high value-added β-Ketoglutaric acid

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