Covalent Networking of a Conjugated‐Polymer Photocatalyst to Promote Exciton Diffusion in the Aqueous Phase for Efficient Hydrogen Production

Abstract

A conjugated polymer particle in an aqueous phase is covalently networked in 3D by crosslinking with azide groups, leading to significantly enhanced activity—a high photocatalytic H2 evolution rate (11 024 µmol g−1 h−1 (λ > 420 nm)) and a high apparent quantum yield (up to 0.8%). The reaction between the photoactive azide and the alkyl chains of the conjugated polymer provides more intact intermolecular polymeric interactions in the colloidal state, thus preventing physical swelling and inhibiting the recombination of photoproduced carriers. The covalent network efficiently promotes exciton diffusion, which greatly facilitates charge separation and transfer. The azide photo‐crosslinking also leads to more compact and better‐packed nanoparticles in the aqueous phase and efficient transfer of excitons to the outer surface of the nanoparticles, where photocatalytic reactions occur. These results show that photo‐crosslinking can suppress the adverse effects of alkyl chains which inhibit photocatalytic performance. Therefore, covalent crosslinking is a promising strategy for the development of solar and hydrogen energy.

Molecular Regioisomerism of Benzobisthiazole‐Based Conjugated Polymers Promotes Photocatalytic Hydrogen Production

“…The photocatalytic H 2 production rate and AQE of LCP-BT-48 measured here are superior to most other LCP-based photocatalysts available so forth (Figure 3f; Table S2, Supporting Information). [50][51][52][53][54] In addition, LCP-BT-48 also exhibits impressive photostability, retaining its activity throughout 20 consecutive photocatalytic cycles and a total reaction time of 100 h (Figure 3g). The recycled LCP-BT-48 was subjected to SEM, TEM, FTIR, and UV-vis characterizations (Figure S16, Supporting Information).…”

Azide-functionalized ligand enabling organic–inorganic hybrid dielectric for high-performance solution-processed oxide transistors

“…2a. Bis-FPA was prepared via DCC coupling between ethylene glycol and 4-azido-2,3,5,6-tetrafluorobenzoic acid 32,33 . Bis-FPA and acac-FPA are soluble in methanol, ethanol, 2-methoxyethanol, and aprotic solvents, including acetonitrile, acetone, dichloromethane, chloroform, dimethylformamide (DMF), and DMSO; hence, such photocrosslinkers can be blended with various types of polymers in appropriate solvents.…”

Azide-functionalized Ligand Enabling Organic–Inorganic Hybrid Dielectric for High-Performance Solution-Processed Oxide Transistors

“…2a. Bis-FPA was prepared via DCC coupling between ethylene glycol and 4-azido-2,3,5,6-tetra uorobenzoic acid, as described in our previous report 30,31 . Bis-FPA and acac-FPA are soluble in methanol, ethanol, acetone, dichloromethane, chloroform, and aprotic solvents, including acetonitrile, 2-methoxyethanol, dimethylformamide (DMF), and DMSO; hence, such photocrosslinkers can be blended with various types of polymers in appropriate solvents.…”