Multi-intermolecular forces strengthen interfacial carrier mobility in poly (barbituric acid) all-organic heterojunction systems for efficient solar-to-hydrogen conversion

doi:10.1016/S1872-2067(25)64845-5

Abstract

Abstract:

The development of high-performance all-organic heterojunction photocatalytic systems and the elucidation of their charge carrier excitation and interface migration dynamics have attracted significant research interest. Herein, poly (barbituric acid)/g-C₃N₄ (PBA/UCN) all-organic heterojunctions were prepared by exploiting multiple intermolecular interactions to induce fast interface charge-carrier transfer with a lifetime of approximately 5.05 ps, as was directly verified by in-situ Kelvin probe force microscopy and in-situ irradiation X-ray photoelectron spectroscopy. Moreover, the dynamics and lifetimes of charge carriers were studied by fitting the decay curves of excited-state absorption signals at 600 nm and ground-state bleaching signals at 495 nm obtained by femtosecond transient absorption spectroscopy to further reveal the diffusion, relaxation, and transfer processes of PBA/UCN. The as-prepared PBA/UCN all-organic molecular heterojunction with optimal redox ability exhibits an excellent H₂ evolution rate of 12.55 mmol h^-1 g^-1 and an apparent quantum efficiency of 17.12% at 420 ± 15 nm. In particular, we demonstrate that PBA, which is a promising oxidizing organic semiconductor, can be coupled with various reducing organic photocatalytic materials such as poly(triazine imide), poly(heptazine imide), perylene-3,4,9,10- tetracarboxylic acid, and covalent triazine-based frameworks to obtain a series of efficient all-organic heterojunction photocatalysts.

Key words: Photocatalysis, Heterojunction, Poly (barbituric acid), Intermolecular force, H₂ production

Zhe Zhang, Guixu Pan, Wei Zhu, Keyu Zhang, Guijie Liang, Shihan Wang, Ning Wang, Yan Xing, Yunfeng Li. Multi-intermolecular forces strengthen interfacial carrier mobility in poly (barbituric acid) all-organic heterojunction systems for efficient solar-to-hydrogen conversion[J]. Chinese Journal of Catalysis, 2026, 81: 284-298.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64845-5

https://www.cjcatal.com/EN/Y2026/V81/I2/284

Figures/Tables 7

Fig. 1. (A) Schematic diagram for formation process of PBA/UCN S-scheme heterojunctions. SEM image of PBA (B) and UCN (C) samples. (D) HAADF-STEM image of PBA/UCN1:3 heterojunction. TEM image of PBA/UCN1:3 (E) and the corresponding elemental mapping images of C (F) and N (G) elements. (H) HRTEM images of PBA/UCN1:3. (I) AFM image of PBA/UCN1:3 heterojunction. FT-IR spectra (J), in-situ temperature dependent FT-IR spectra (K), and solid-state 1H NMR spectra (L) of the as-prepared samples.

Fig. 2. UV-vis DRS (A) and corresponding Kubelka-Munk plots (B) of the as-prepared samples. (C) Mott-Schottky plots of PAB and UCN samples. Steady state PL spectra (D), TSPV tests (E), transient photocurrent responses (F), EIS tests (G), and time-resolved PL spectra (H) of PAB, UCN, and PBA/UCN1:3 samples.

Fig. 3. UPS tests of PBA (A) and UCN (B) samples. High-resolution XPS of C 1s (C) and N 1s (D) for PAB, UCN and PBA/UCN1:3 samples. High-resolution in-situ XPS of O 1s (E), C 1s (F) and N 1s (G) of PAB, UCN and PBA/UCN1:3 samples. Calculated band structure (H), density of states (I), calculated work function and differential charge density map (inset of J) (J) for PBA/UCN heterojunctions.

Fig. 4. AFM image (A), KPFM image (B), and corresponding line-scanning CPD from A to B (C) of PBA/UCN heterojunction in dark. AFM image (D), KPFM image (E), and corresponding line-scanning CPD from A to B (F) of PBA/UCN heterojunction under light illumination. (G) Illustration of in-situ light-assisted KPFM measurement (i) and formation of interface potential (ii and iii).

Fig. 5. Time-resolved diffuse reflectance spectra of PBA (A,E), UCN (C,G) and PBA/UCN1:3 (B, F, D, H) samples. Time profiles of normalized transient absorption for PBA (I), UCN (K), and PBA/UCN1:3 (J, L) samples after 320 nm laser pulse irradiation.

Fig. 6. SPV tests (A), EPR spectra of DMPO-·O2- (B) and DMPO-·OH (C) for PBA, UCN and PBA/UCN1:3 samples. In-situ EPR spectra of DMPO-·O2- (D) and DMPO-·OH (E) for PBA/UCN1:3 heterojunction under light irradiation of 0, 5, 10 min, respectively. (F) Formation process and charge carriers transfer pathway of all-organic S-scheme photocatalytic system.

Fig. 7. Photocatalytic H2 production (A) and hydrogen evolution rate (B) of the as-prepared samples. (C) Apparent quantum efficiency of PBA//UCN1:3 heterojunction. (D) Comparison with various g-C3N4-based photocatalysts reported previously (corresponding Refs. [49-75]). (E) Stability test of PBA/UCN1:3 heterojunction for H2 generation. (F) Calculated Gibbs free-energy diagram of H2 production reaction. (G) Band structure of PBA and various reducing organic photocatalytic materials. (H) Photocatalytic hydrogen evolution rate of the as-prepared various all-organic heterojunctions.

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