Cobalt single atom-phosphate functionalized reduced graphene oxide/perylenetetracarboxylic acid nanosheet heterojunctions for efficiently photocatalytic H2O2 production

doi:10.1016/S1872-2067(25)64744-9

Abstract

Abstract:

The production of hydrogen peroxide (H₂O₂) via artificial photosynthesis using single-atom semiconductor photocatalysts represents a promising green and sustainable technology. However, its efficiency is still limited by sluggish water oxidation kinetics, poor photogenerated charge separation, and insufficient O₂ adsorption and activation capabilities. Herein, uniformly dispersed single-atom catalysts (SACs) with a Co-N₄ coordination structure have been synthesized by thermally transforming cobalt phthalocyanine (CoPc) assemblies pre-anchored on phosphate functionalized reduced graphene oxide (Co@rGO-P), and then used to construct heterojunctions with perylenetetracarboxylic acid (PTA) nanosheets for photocatalytic H₂O₂ production by an in-situ growth method. The optimized Co@rGO-P/PTA achieved an H₂O₂ production rate of 1.4 mmol g^-1 h^-1 in pure water, with a 12.9-fold enhancement compared to pristine PTA nanosheets exhibiting competitive photoactivity among reported perylene-based materials. Femtosecond transient absorption spectra, in-situ diffuse reflectance infrared Fourier transform spectra and theoretical calculations reveal that the exceptional performance is attributed to the enhanced electron transfer from PTA to rGO via the phosphate bridge and then to the Co-N₄, and to the promoted O₂ adsorption and activation at Co-N₄ active sites. This work provides a feasible and effective strategy for designing highly efficient single-atom semiconductor heterojunction photocatalysts for H₂O₂ production.

Key words: Single-atom photocatalyst, Perylenetetracarboxylic acid nanosheetPhosphate-functionalized reduced, graphene oxide, Charge separation, H2O2 production

Wang Qihang, Meng Li, Li Zhuo, Yang Zhuoran, Tang Yinan, Yu Lang, Li Zhijun, Sun Jianhui, Jing Liqiang. Cobalt single atom-phosphate functionalized reduced graphene oxide/perylenetetracarboxylic acid nanosheet heterojunctions for efficiently photocatalytic H₂O₂ production[J]. Chinese Journal of Catalysis, 2025, 75: 192-203.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64744-9

https://www.cjcatal.com/EN/Y2025/V75/I8/192

Figures/Tables 6

Scheme 1. Schematic illustration of the synthesis process for Co@rGO-P/PTA.

Fig. 1. (a,b) TEM images of Co@rGO-P. (c) HAADF-STEM image. (d) TEM-EDX elemental mapping profiles of Co@rGO-P. (e) TEM image of Co@rGO-P/PTA. (f) AFM image and the corresponding height profile, and (g) theoretical model diagram of Co@rGO-P/PTA.

Fig. 2. (a) Co K-edge XANES profiles and (b) k3 weighted Co K-edge FT-EXAFS spectra at R space of Co foil, CoO, Co3O4, Co@rGO-P. (c) First-shell (Co-N) fitting of Fourier trans-formations of EXAFS spectra for Co@rGO-P. (d-f) Wavelet transform EXAFS spectra of Co@rGO-P, Co-foil, and Co3O4, respectively. (g,h) Optimized structural models, charge density difference plot and the binding energy of Co in Co@rGO and Co@rGO-P. (i) Charge density difference plot and the binding energy of PTA between Co@rGO and Co@rGO-P. The yellow and blue colors indicate charge depletion and accumulation, respectively; the isosurface value is 0.005 e ?-3.

Fig. 3. (a) Photocatalytic performance toward H2O2 production (pure water under visible-light irradiation, pH = 7.0) for PTA, rGO/PTA, rGO-P/PTA, Co@rGO/PTA and Co@rGO-P/PTA. (b) Five consecutive runs of H2O2 production by Co@rGO-P/PTA with pure water under visible-light irradiation. (c) The formation rate constant (Kf) and decomposition rate constant (Kd) of H2O2 for PTA, rGO/PTA, rGO-P/PTA, Co@rGO/PTA and Co@rGO-P/PTA. (d) Photoelectrochemical I-t curves of PTA, rGO/PTA, rGO-P/PTA, Co@rGO/PTA and Co@rGO-P/PTA. (e) TR-PL spectra of PTA, rGO/PTA, rGO-P/PTA, Co@rGO/PTA and Co@rGO-P/PTA. (f) DMPO spin-trapping EPR spectra recorded for ?O2- under light irradiation for PTA, rGO/PTA, rGO-P/PTA, Co@rGO/PTA and Co@rGO-P/PTA.

Fig. 4. (a) 2D mapping TAS spectra of PTA. (b) Time slices of the TAS spectra for PTA. (c) Femtosecond time-resolved transient absorption decay kinetics of PTA. (d) 2D mapping TAS spectra of Co@rGO-P/PTA. (e) Time slices of the TAS spectra for PTA. (f) Femtosecond time-resolved transient absorption decay kinetics of Co@rGO-P/PTA. (g) Frontier molecular orbital distribution within one stacked unit.

Fig. 5. The O2-TPD curves (a) and the photocatalytic H2O2 generation rates (b) of various samples under different reaction gases or sacrificial agents. (c) Top and side views of the structure with different charge densities for O2 adsorption on Co@rGO/PTA and Co@rGO-P/PTA. (d) Photodegradation of NBT by ?O2- radicals generated over different photocatalysts. (e,f) In-situ DRIFT spectra of Co@rGO-P/PTA recorded during photocatalytic H2O2 evolution. (g) Free energy diagrams for 2e- ORR processes on Co@rGO/PTA and Co@rGO-P/PTA with optimized configurations for each step, where the asterisk (*) denotes the active site of the catalyst. (h) Schematic of the charge transfer and redox reactions involved in Co@rGO-P/PTA.

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Cobalt single atom-phosphate functionalized reduced graphene oxide/perylenetetracarboxylic acid nanosheet heterojunctions for efficiently photocatalytic H₂O₂ production

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