Boosting photocatalytic water oxidation via interfacial electric field-mediated charge separation in S-scheme photocatalyst

doi:10.1016/S1872-2067(25)64757-7

Abstract

Abstract:

The major challenge in photocatalytic water splitting lies in water oxidation reactions, which still suffer from poor charge separation. This study overcame inefficient charge separation by establishing a robust interfacial electric field through the electrostatic-driven assembly of Co₃O₄ nanoparticles with a perylene imide supramolecule (PDINH). The well-aligned band structures and intimate interfacial contact in the PDINH/Co₃O₄ heterostructure create an enhanced interfacial electric field that is 4.1- and 53.2-fold stronger than those of individual PDINH and Co₃O₄, thus promoting directional charge separation and transfer. Moreover, S-scheme charge transfer strongly preserves the oxidative holes in PDINH to drive efficient water oxidation reactions. Consequently, PDINH/Co₃O₄ composite achieves a photocatalytic oxygen evolution rate of 29.26 mmol g^-1 h^-1 under visible light irradiation, 8.2-fold improvement over pristine PDINH, with an apparent quantum yield of 6.66% at 420 nm. This study provides fundamental insights into interfacial electric field control for the development of high-performance organic photocatalysts for efficient water oxidation.

Key words: Photocatalysis, Oxygen evolution, Interfacial electric field, S-scheme heterojunction, Perylene imide

Xinyue Tan, Minghui Zhang, Yang Bai, Xiaoyu Liu, Jianfang Jing, Yiguo Su. Boosting photocatalytic water oxidation via interfacial electric field-mediated charge separation in S-scheme photocatalyst[J]. Chinese Journal of Catalysis, 2025, 77: 199-209.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64757-7

https://www.cjcatal.com/EN/Y2025/V77/I10/199

Figures/Tables 5

Fig. 1. TEM images of PDINH (a) and Co3O4 (inset is particle size distribution) (b). (c) HRTEM image of Co3O4. (d) TEM image of PDINH/Co3O4 (inset is HRTEM images of Co3O4). (e) XRD patterns of PDINH, Co3O4, and PDINH/Co3O4. (f) XPS high resolution spectra of Co 2p for Co3O4 and PDINH/Co3O4. (g) EDX elemental mapping of PDINH/Co3O4 high-resolution.

Fig. 2. (a) Contact potential differences (CPD) between the sample and Kelvin probe. (b) Schematics of the band structures of PDINH and Co3O4 before contact. (c) Energy band bending and interfacial electric field formation. In situ light irradiation XPS Co 2p (d) and N 1s (e) spectra of PDINH/Co3O4. (f) Differential charge density map of PDINH/Co3O4. Isosurface value is 0.02 a.u.; Charge accumulation and depletion are depicted in blue and green, respectively. (g) SPV spectra. (h) Surface charge density measured through the electrochemical method. (i) Relative interfacial electric field intensity of PDINH, Co3O4 and PDINH/Co3O4. CB: conduction band; VB: valence band; FL: Fermi energy level; VL: vacuum energy level.

Fig. 3. Fs-TAS of PDINH (a) and PDINH/Co3O4 (b) with a 430 nm pump excitation. Time profiles and the corresponding decay kinetics of normalized transient absorption for PDINH (c) and PDINH/Co3O4 (d). Inset tables are fitted with time constants of photogenerated holes and electrons.

Fig. 4. Surface potential mapping of Co3O4 (a), PDINH (b), and PDINH/Co3O4 (c). (d) Transient photovoltage spectra. Inset is the corresponding TPV kinetic fitting curves. (e) Normalized open-circuit potential decay profiles upon illumination termination. (f) Steady-state PL spectra. (g) EPR spectra of PDI anion radicals. (h) EPR spectra of ?OH radicals. (i) Electrochemical impedance spectra. Inset is the equivalent circuit impedance model.

Fig. 5. (a) Time-course plots of photocatalytic oxygen production. (b) Photocatalytic oxygen production rate of PDINH, Co3O4 and PDINH/Co3O4. (c) AQY and absorption spectrum of PDINH/Co3O4. (d) Comparison of photocatalytic oxygen evolution performances of PDINH/Co3O4 with other reported materials. (e) Cyclic experiment of PDINH/Co3O4. (f) Computational geometry models of PDINH and PDINH/Co3O4. (g) Gibbs free energy profiles of the O2 formation pathway. Insets are the corresponding intermediate adsorption models.

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