Decoupled active centers on crystalline carbon nitride nanoarrays for synergistic photocatalytic hydrogen peroxide synthesis

doi:10.1016/S1872-2067(26)65229-1

Abstract

Abstract:

Photocatalytic hydrogen peroxide (H₂O₂) synthesis from water and oxygen represents a sustainable pathway for solar energy conversion. However, its efficiency is limited by rapid charge recombination, sluggish water oxidation kinetics, and insufficient proton supply. Herein, we report a photocatalyst featuring spatially separated redox centers, constructed by co-anchoring indium single atoms (In SAs) and cyano groups on highly crystalline carbon nitride nanoarrays. Structural and in situ spectroscopic analyses reveal that cyano groups act as efficient oxygen reduction reaction (ORR) sites. Concurrently, the In SAs act as water oxidation reaction (WOR) centers, which activate water molecules and supply protons for the ORR pathway. The optimized catalyst achieves a remarkable H₂O₂ production rate of 475 μmol g^-1 h^-1 under visible light, a 17-fold improvement over pristine carbon nitride. Theoretical calculations attribute this performance to an induced orbital distribution asymmetry, which facilitates directional carrier migration to respective active sites and concurrently lowers the energy barrier for the critical OOH* intermediate formation. This work establishes a dual-site design strategy to synergistically advance WOR and ORR, offering a promising route for efficient solar-driven H₂O₂ production.

Key words: Catalytic sites, Crystalline carbon nitride, Hydrogen peroxide, Photocatalysis, Single-atom catalyst

Jiaqi Li, Haojie Song, Yuxin Gao, Xinming Zhang, Jingnan Li, Siyu Wang, Huiquan Gu, Laiyu Luo, Baojiang Jiang. Decoupled active centers on crystalline carbon nitride nanoarrays for synergistic photocatalytic hydrogen peroxide synthesis[J]. Chinese Journal of Catalysis, 2027, 92: 157-169.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65229-1

https://www.cjcatal.com/EN/Y2027/V92/I1/157

Figures/Tables 7

Scheme 1. Mechanism and energy-level diagram of H2O2 photogeneration on a semiconductor.

Fig. 1. (a) Schematic diagram of the In-CCN synthesis process. (b) SEM image, (c,d) HR-TEM images, (e) AC-HAADF-STEM image and (f) EDX images with C (red), N (green), In (yellow), K (blue) distributions of In-CCN.

Fig. 2. (a) Solid-state13C NMR spectra of the BCN and In-CCN. (b) EPR patterns of BCN, In-BCN, CCN and In-CCN. (c) High-resolution XPS spectra of In 3d in the In-BCN and In-CCN. In K-edge XANES spectra (d) and the Fourier-transformed (FT) k2-weighted EXAFS spectra (e) of In-CCN, In(OH)3, and In foil. (f) In K-edge EXAFS (line) and fit curve (points) for In-CCN, shown in k2 weighted R-space. The inset is structure model of In-N4C2. g-i) WT-EXAFS plots of In-CCN, In and In(OH)3.

Fig. 3. In-situ high-resolution C 1s (a), N 1s (b), K 2p (c), and In 3d (d) XPS spectra of In-CCN under dark and light irradiation. Two‑dimensional pseudo-color fs-TAS of BCN (e), In-BCN (f), CCN (g) and In-CCN (h) at various probe delays. The fs-TAS kinetic plots and corresponding fitting curves at 500 nm for BCN (i), In-BCN (j), CCN (k) and In-CCN (l). (m) Schematic illustration of carrier transfer and the corresponding TA signals detected in In-CCN.

Fig. 4. (a) Photocatalytic H2O2 production performance of BCN, In-BCN, CCN and In-CCN. Reaction conditions: 10 mg catalyst in 50 mL of oxygen-saturated pure water under AM 1.5 illumination (pH = 7.0). (b) Time-dependent profiles of H2O2 photoproduction over BCN, In-BCN, CCN and In-CCN. (c) Photocatalytic O2 evolution performance of BCN, In-BCN, CCN, In-CCN. (d) AQE for H2O2 production of In-CCN at different wavelengths and its corresponding UV-Vis DRS. (e) Formation rate constant (Kf) and decomposition rate constant (Kd) of H2O2 for BCN, In-BCN, CCN and In-CCN. (f) Comparison of H2O2 generation performance between In-CCN and other recently reported g-C3N4 based photocatalysts in pure water.

Fig. 5. Surface potential mapping by light-assisted KPFM for BCN (a-c) and In-CCN (d-f). (g) RRDE polarization curves of BCN and In-CCN measured at 1600 rpm in O2 saturated 0.1 mol L-1 KOH solution with a ring current (upper part) and disk current (bottom part). (h) Calculated average number of transferred electrons of BCN and In-CCN. (i) Photocatalytic H2O2 generation rates of different samples under different reaction atmospheres or with different sacrificial agents. (j) DMPO spin-trapping EPR spectra recorded for radicals under light irradiation for BCN, In-BCN, CCN and In-CCN. (k) O2-TPD profiles of BCN, In-BCN, CCN, In-CCN. (l) GC-MS spectra of O2 produced by H218O+16O2.

Fig. 6. (a) In-situ DRIFTS of photocatalytic H2O2 synthesis under H2O, O2, dark or illumination of 30 min. (b) Infrared contour map for In-CCN in O2 and H2O atmospheres under illumination for 30 min. Calculated ESP distributions of BCN (c), In-BCN (d), CCN (f) and In-CCN (g). (e,h) PDOS of BCN and In-CCN. (i) Free energy diagrams for 2e- RR processes on BCN, In-BCN, CCN and In-CCN with optimized configurations for each step, where the asterisk (*) denotes the active site of the catalyst. (j) Schematic of redox reactions involved in In-CCN.

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