Highly efficient hydroxyethyl radicals-mediated photocatalytic benzimidazole synthesis and hydrogen evolution over defect-engineered Pt/Nb2O5

doi:10.1016/S1872-2067(26)64999-6

Abstract

Abstract:

The hydroxyethyl radical (•CH(CH₃)OH)-mediated pathway, by avoiding the formation of aldehyde intermediates, constitutes a promising approach for the highly selective photocatalytic synthesis of benzimidazoles from ethanol and o-phenylenediamine. However, inefficient reactant adsorption and activation, as well as severe recombination of photogenerated charge carriers of traditional photocatalysts, impose a fundamental challenge for this reaction pathway. Herein, we construct an oxygen vacancy (V_O)-rich Nb₂O₅ decorated with Pt nanoparticles (NPs), which exhibits the highest photocatalytic activity to date, with production rates of 4.0 mmol g^-1 h^-1 for 2-methylbenzimidazole and 10.2 mmol g^-1 h^-1 for H₂, respectively. The synergistic interaction between V_O and Pt NPs markedly promotes the migration and separation of photogenerated charge carriers. The electron-accumulating Pt NPs drive efficient H₂ evolution through proton reduction, while the engineered V_O sites enhance ethanol adsorption and selectively activate α-C-H bond cleavage to generate •CH(CH₃)OH radicals, suppressing the accumulation of N-ethyl-2-methylbenzimidazole by-products inherent to conventional aldehyde-mediated reaction pathways, significantly facilitating the co-production of benzimidazoles and H₂. This work achieves directional pathway regulation via rational design of semiconductor defects and metal co-catalysts, establishing a radical-mediated strategy for efficient and selective green synthesis of N-heterocyclic compounds.

Key words: Hydroxyethyl radical, Pt nanoparticles, Oxygen vacancy, Nb₂O₅, Benzimidazoles synthesis

Yao-Yao Xie, Chang-Long Tan, Liang Mao, Zi-Rong Tang, Yi-Jun Xu. Highly efficient hydroxyethyl radicals-mediated photocatalytic benzimidazole synthesis and hydrogen evolution over defect-engineered Pt/Nb₂O₅[J]. Chinese Journal of Catalysis, 2026, 83: 132-142.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)64999-6

https://www.cjcatal.com/EN/Y2026/V83/I4/132

Figures/Tables 6

Fig. 1. (a) Schematic illustration for the synthesis of Pt/Nb2O5-VO. TEM images (b,c) and HRTEM image (d) of Pt/Nb2O5-VO. (e) Elemental mapping results of Pt/Nb2O5-VO.

Fig. 2. (a,b) XPS spectra of Nb 3d, O 1s of Nb2O5, Nb2O5-VO, and Pt/Nb2O5-VO. (c) XPS spectra of Pt 4f of Pt/Nb2O5-VO. (d) Calculation of the work function of Nb2O5-VO. (e) Calculation of the work function of Pt (110). (f) Simulated differential charge density distribution at the interface between Nb2O5-VO and Pt in the Pt/Nb2O5-VO composite (the yellow and blue areas represent electron accumulation and depletion, respectively). (g) EPR spectra of Nb2O5, Nb2O5-VO, and Pt/Nb2O5-VO. XRD patterns (h) and DRS spectra (i) of Nb2O5, Nb2O5-VO, and Pt/Nb2O5-VO.

Fig. 3. (a) Diagram illustrating the cross-coupling of OPD with ethanol. (b) Photocatalytic activity of Nb2O5-VO with varying Pt decorations after 4.5 h of illumination. (c) Photocatalytic activity of Nb2O5, Pt/Nb2O5, Nb2O5-VO, and Pt/Nb2O5-VO after 4.5 h of illumination. (d) Recycle tests of 0.4%Pt/Nb2O5-VO. (e) Time-dependent analysis of 0.4%Pt/Nb2O5-VO. (Reaction conditions: 5.0 mg catalysts, 0.1 mmol OPD, 10 mL ethanol, 300 W Xe lamp, illumination for 4.5 h.) (f) Photocatalytic activity of Nb2O5-VO with various metal co-catalysts after 4.5 h of illumination. (g) DRS spectrum of 0.4%Pt/Nb2O5-VO and AQYs of 2MBZ under different monochromatic lights. (h) Comparisons of H2 and 2MBZ yield rates with those reported in recent literature. Catalyst: 1Pd/TiO2-VO [8], 15Pd/ZnO [9], Au/MIL-101 [11], Pt@MIL-101 [44], Pt/TiO2 [10], c-TiO2 [45].

Fig. 4. EIS Nyquist plots (a), CV curves (b), LSV curves (c), Transient photocurrent spectra (d), PL emission spectra (e), and TRPL decay spectra (f) of Nb2O5, Nb2O5-VO, and Pt/Nb2O5-VO.

Fig. 5. (a) The DRIFTS measurements upon Nb2O5, Nb2O5-VO, and Pt/Nb2O5-VO adsorbed with ethanol. (b) The photocatalytic activity of control experiments on Pt/Nb2O5-VO within 4.5 h of irradiation. (c) The quantitative analysis result of the EPR spectrum of DMPO spin adducts derived from the reaction of OPD, ethanol and Pt/Nb2O5-VO in Ar-saturated ethanol solution. (d) In-situ DRIFTS spectra of photocatalytic synthesis of 2MBZ on Pt/Nb2O5-VO.

Fig. 6. (a) Calculated potential energy diagrams for cross-coupling of OPD and ethanol to 2MBZ catalyzed by Nb2O5, Nb2O5-VO, and Pt/Nb2O5-VO. (b) Proposed reaction mechanism for photocatalytic synthesis of 2MBZ and H2 evolution on Pt/Nb2O5-VO.

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Highly efficient hydroxyethyl radicals-mediated photocatalytic benzimidazole synthesis and hydrogen evolution over defect-engineered Pt/Nb₂O₅

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