Defect-coordinated Au nanoparticles in carbon nitride for efficient piezo-photocatalytic hydrogen peroxide production

doi:10.1016/S1872-2067(25)64901-1

Abstract

Abstract:

Hydrogen peroxide (H₂O₂), a versatile green oxidant and energy carrier, faces production challenges due to the energy-intensive anthraquinone process. Photocatalytic H₂O₂ synthesis via the two-electron oxygen reduction reaction (2e^- ORR) offers a sustainable alternative, but its efficiency is limited by sluggish charge transfer and insufficient active sites. Here, we design a dual-modulation strategy that combines defect-induced electronic tuning with piezoelectric polarization to enhance surface catalytic processes. Specifically, anchoring Au nanoparticles on N-deficient graphitic carbon nitride (CNNv-Au) allows N vacancies to modulate the electronic structure of the Au nanoparticles, increasing the proportion of electron-deficient Au^δ⁺ sites and enhancing Au-O₂ interactions, while the piezoelectric field simultaneously facilitates charge separation and directs electrons toward the adsorbed O₂ molecules. In-situ X-ray photoelectron spectroscopy (XPS) under simulated catalytic conditions revealed a 0.5 eV Au 4f shift toward higher binding energy, confirming enhanced electron transfer from Au^δ⁺ sites to adsorbed O₂ under light irradiation. Synergistic effects of these modifications elevate the H₂O₂ production rate from 247.0 to 1788.5 μmol g^-1 h^-1, a 7.2-fold enhancement. Combined XPS, electron paramagnetic resonance, density functional theory, and in-situ diffuse reflectance infrared Fourier transformed spectroscopy analyses confirm that N vacancies induce local polarization of Au sites, optimizing O₂ activation and intermediate stabilization. This work demonstrates a dual modulation strategy, defect-induced electronic tuning and piezoelectric polarization, to enhance surface catalytic processes, providing a blueprint for efficient photocatalytic H₂O₂ generation.

Key words: H₂O₂ production, Carbon nitride, N vacancy, Au nanoparticles, Piezo-photocatalysis

Na Tian, Chaofan Yuan, Tong Zhou, Wenying Yu, Yinghui Wang, Na Zhang, Yihe Zhang, Hongwei Huang. Defect-coordinated Au nanoparticles in carbon nitride for efficient piezo-photocatalytic hydrogen peroxide production[J]. Chinese Journal of Catalysis, 2026, 81: 272-283.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64901-1

https://www.cjcatal.com/EN/Y2026/V81/I2/272

Figures/Tables 7

Fig. 1. (a) Schematic illustration of the synthesis process of BCN-Au and CNNv-Au, and the electron deficient Auδ+ formation to reinforce Au-O2 interaction. High-resolution Au 4f XPS spectra of BCN-Au (b) and CNNv-Au (c). (d) EPR spectra of BCN, CNNv, BCN-Au and CNNv-Au.

Fig. 2. SEM images of CNNv (a) and CNNv-Au (b). (c) TEM and HRTEM images of CNNv-Au. TEM images of BCN-Au (d,e) and CNNv-Au (f,g). (h) EDX elemental mapping images of C, N, and Au elements of CNNv-Au.

Fig. 3. XRD (a), and FTIR (b) spectra of BCN, CNNv, BCN-Au and CNNv-Au. High-resolution N 1s (c) and C 1s (d) XPS spectra of BCN, CNNv, BCN-Au and CNNv-Au. The local piezoelectric butterfly curve and phase hysteresis loop of BCN (e) and CNNv-Au (f). (g) UV-vis DRS spectra of BCN, CNNv, BCN-Au and CNNv-Au.

Fig. 4. The photocatalytic, piezocatalytic and piezo-photocatalytic H2O2 production of BCN, CNNv, BCN-Au and CNNv-Au under visible light (a), ultrasonic (b), and simultaneous light and ultrasonic excitation (c). (d) The catalytic H2O2 production rate of catalyst in different conditions. (e) The comparison of H2O2 production rates for CNNv-Au compared with representative recently reported work.

Fig. 5. (a) The H2O2 production of CNNv-Au with trapping agent in the piezo-photocatalytic process. EPR signals of DMPO for ∙O2? trapping over all samples in piezo-photocatalytic process (b), and CNNv-Au (c) in different catalytic process. (d) The electron transfer numbers (insert: H2O2 selectivity) at different potentials of catalysts.

Fig. 6. (a) Transient current response synergistically excited by light and ultrasound. (b) Transient current response of CNNv-Au in different conditions. (c) EIS Nyquist of the four samples. 3D surface potential distribution and corresponding line-scanning surface potential profile of BCN (d), BCN-Au (e), CNNv (f), and CNNv-Au (g) in darkness, and CNNv-Au under irradiation (h), and the comparison of their surface potential (i).

Fig. 7. (a) In-situ XPS of Au 4f for the simulated O2 reduction process over CNNv-Au. In-situ DRIFT of BCN (b), BCN-Au (c) and CNNv-Au (d). (e) The O2-TPD spectra of prepared catalysts. (f) Schematic illustration of band bending and the H2O2 generation mechanism of CNNv-Au under different conditions. (g) The charge density difference of the catalyst and adsorbed O2.

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