Donor-engineered D-A nanophotocatalyst with dual surfactants-directed assembly for efficient photocatalytic hydrogen evolution

doi:10.1016/S1872-2067(26)65169-8

Abstract

Abstract:

Organic semiconductors hold promise for photocatalytic hydrogen production, yet their performance is often limited by excitonic effects that hinder charge separation and transport. To overcome these challenges, we present a synergistic strategy combining donor-acceptor (D-A) molecular engineering with dual-surfactant-directed nanoassembly. A series of structurally analogous D-A molecules based on 4-([1,1′-biphenyl]-4-yl)-2,6-bis(4-cyanophenyl) pyridine-3,5-dicarbonitrile (CNP) were synthesized with systematic variation of donor-unit substituents. Among them, the methoxy-containing CNP, namely CNP501, exhibited a 26-fold higher hydrogen evolution rate than pristine CNP. Leveraging this, a dual-surfactant-induced self-assembly approach yielded the CNP501/DDBAB/SDBS nanophotocatalyst, which achieved an additional 12-fold enhancement in photoactivity, delivering a hydrogen production rate of 1093 mmol g^-1 h^-1 and an apparent quantum yield of 77.2% at 365 nm. The exceptional performance arises from two synergistic effects: (1) donor engineering, which modulates intrinsic molecular electric fields to promote exciton dissociation, and (2) surfactant-mediated morphological control, which optimizes hydrophilicity, minimizes interfacial charge-transfer resistance, and suppresses carrier recombination. Notably, dual-surfactant regulation uniquely enables multiple light scattering with tunable efficiency, a feature absent in single-surfactant systems.

Key words: Donor-acceptor molecular, nanophotocatalyst, Donor engineering, Surfactant-directed assembly, Photocatalytic hydrogen evolution, Dual surfactants

Jiahui Xie, Luyao Ge, Pilang Zheng, Yuanzhen Ke, Qihua Yang, Xiaobo Li. Donor-engineered D-A nanophotocatalyst with dual surfactants-directed assembly for efficient photocatalytic hydrogen evolution[J]. Chinese Journal of Catalysis, 2026, 89: 269-278.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65169-8

https://www.cjcatal.com/EN/Y2026/V89/I10/269

Figures/Tables 4

Fig. 1. (a) Chemical structures of donor-acceptor molecules CNP14, CNP147, CNP505, CNP506, and CNP501. (b) Calculated electrostatic potential (ESP) surfaces and molecular dipole moments for CNP505, CNP14, CNP501. Color code: N = blue, C = gray, Cl = green, O = red, H = light gray. (c) Electron-hole distribution analysis for: CNP505, CNP14, CNP501. Color code: N = blue, C = gray, Cl = green, O = red, H = light gray. Blue regions: hole density; Green regions: electron density. (d) Fluorescence emission spectra of CNPs in THF (10 μmol L-1); λexc = 365 nm. (e) Fluorescence emission spectra of quasi-homogeneous photocatalysts prepared by UNP (0.125 mg CNP in 5 mL H2O); λexc = 365 nm. (f) HERs of UNP-prepared quasi-homogeneous photocatalysts. Conditions: 0.125 mg CNP in 5 mL H2O, 5 mmol L-1 AA, 3 wt% Pt; light source = AM 1.5G (58.5 mW cm-2). Error bars: mean ± SD (n = 3).

Fig. 2. (a) HERs of CNP501 synthesized by UNP under varied chemical environments, with molecular structures of DDBAB and SDBS surfactants. (b) HERs of CNP501 photocatalysts synthesized in aqueous solutions with different mass fractions of DDBAB. (c) HERs of CNP501 photocatalysts fabricated with varying DDBAB/SDBS mixing ratios. (d) HERs of CNP501/DDBAB/SDBS nanophotocatalysts with varying Pt co-catalyst loading. (e) HERs of CNP501/DDBAB/SDBS nanophotocatalysts at different ascorbic acid concentrations. (f) AQYs of CNP501/DDBAB/SDBS nanophotocatalysts measured at 365, 400, 420, and 450 nm, overlaid with the UV-vis absorption spectrum of the nanophotocatalyst. Conditions: 0.125 mg CNP501 in 15 ml aqueous solution containing 0.4 wt% surfactant (except b), 0.2 mol L-1 AA (except e, f), 6 wt% Pt (except d); light source: AM 1.5G (58.5 mW cm-2).

Fig. 3. Structural and interfacial characterization of nanophotocatalysts. SEM images of nanophotocatalysts prepared in pure water (a) and DDBAB/SDBS surfactant solution (b). (c) Cryo-TEM image of CNP501/DDBAB/SDBS. (d) Photographs of post-heated DDBAB/SDBS dual surfactants systems at varied mass ratios and their laser-irradiated counterparts. Surface properties of CNP501 nanophotocatalysts prepared in DDBAB/SDBS versus pure water: water contact angles on drop-cast films (e) and Zeta potential values (f).

Fig. 4. Charge transfer dynamics of CNP501 nanophotocatalysts modulated by surfactant assembly. (a) Transient photocurrent responses of CNP501/Water versus CNP501/DDBAB/SDBS nanophotocatalysts. (b) EIS of CNP501-based nanophotocatalysts synthesized in different media. Measurement conditions: Three-electrode system with Ag/AgCl reference electrode and Pt counter electrode. (c) PL spectra of CNP501/DDBAB/SDBS under four conditions: no additives, with Pt only, with AA only, with both Pt and AA; λexc = 295 nm. Pseudocolor 2D fs-TAS maps for CNP501/DDBAB/SDBS (d), CNP501/DDBAB/SDBS+Pt (e), and CNP501/DDBAB/SDBS+Pt+AA (f) samples. (g-i) Corresponding transient absorption spectra of the samples. (j-l) Transient absorption decay kinetics at 860 nm and biexponential fitting, from which the lifetimes of the slow (τ1) and fast (τ2) components are extracted. The Pt loading is 6 wt% relative to the catalyst mass, and the concentration of AA is 0.1 mol L?1; the group without additives only contains the catalyst solution with the same concentration.

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