Proceedings of MATSUS Fall 2026 Conference (MATSUSFall26)
Publication date: 22nd July 2026
While inorganic photocatalysts for solar hydrogen evolution (HER) often require complex structures to achieve high efficiency, organic semiconductor nanoparticles (NPs) offer a promising, easily processable alternative. [1] Here, we evaluate the impact of a novel surfactant, sodium 4-((2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy)butane-1-sulfonate (S-EDOT), against conventional sodium dodecyl sulfate (SDS) on the photocatalytic HER activity of P3HT:PCBM NPs. The NPs were synthesized via miniemulsion-evaporation assisted by ultrasonication [2] and decorated with 18 wt% Pt co-catalyst via photodeposition [3] . Our cryo-TEM investigations reveal a strong tendency to form core-shell structures (PCBM-rich core, P3HT-rich shell) in SDS-capped NPs. In contrast, S-EDOT partially frustrates such tendency, yielding a more intermixed shell with surface-exposed PCBM, as confirmed by HAADF-STEM-EDS. As a consequence of the enhanced NP morphology, S-EDOT-capped NPs achieve a stable H₂ evolution rate of ~11 mmol h⁻¹ g⁻¹, more than double the ~5.4 mmol h⁻¹ g⁻¹ achieved by SDS-capped NPs, despite their larger size distribution (30–110 nm vs. 35–50 nm for SDS). Interestingly, time-resolved photoluminescence reveals a longer interfacial exciton lifetime for S-EDOT NPs upon P3HT excitation, which contrasts with their higher activity, but is explained by the larger P3HT shell thickness. Finally, we replaced chloroform with chlorobenzene to induce further morphological changes in S-EDOT NPs and achieve a more intermixed nanostructure, further elevating the H2 evolution rate to 24 mmol h-1 g-1. Our results demonstrate that surfactant-driven surface engineering can override traditional particle size constraints. S-EDOT enhances photocatalytic performance of P3HT:PCBM NPs by tailoring their morphology to expose reduction-active PCBM domains at the surface.
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