Covalently Locked Donor–Acceptor Block Copolymer Nanoparticles Enable Efficient, Stable and Reproducible Photocatalytic Hydrogen Evolution
Journal article, 2026
Organic photocatalysts with tailored properties and unique processability offer a sustainable route to solar hydrogen. To maximize light harvesting and charge generation, donor and acceptor materials are usually physically mixed to form D:A heterojunction nanoparticles (NPs). However, weakly constrained interactions can promote phase segregation, morphological evolution, and limited reproducibility. Here, we introduce an all-conjugated donor–acceptor block copolymer, PBDB-T-b-PYT, in which covalent linkage between PBDB-T and PYT segments constrains nanoscale donor–acceptor organization and promotes intramolecular charge transfer. Compared with nanoparticles prepared from a physical PBDB-T:PYT blend, PBDB-T-b-PYT nanoparticles exhibit stronger photoluminescence quenching, more persistent charge-associated transient absorption features, and improved photoelectrochemical charge extraction. As a result, hydrogen evolution reaction (HER) rates exceeding 120 mmol cm−2 g−1 h−1 (>450 µmol h−1) are achieved with low Pt loading (<3 wt.%). PBDB-T-b-PYT NPs retained 95% of the initial HER rate after 96 h of photocatalysis. Conversely, NPs prepared from physically mixed PBDB-T and PYT show lower activity and faster deactivation, consistent with morphology-driven losses. PBDB-T-b-PYT also maintains high performance across polymer batches, improving reproducibility. These results establish all-conjugated donor–acceptor block copolymers as a promising design strategy for combining high activity, operational stability, and reproducibility in organic nanoparticle photocatalysis.
chemistry
organic chemistry
hydrogen production rate
hemoglobin
nanoparticle
photocatalysis
organic semiconductor
Author
Alexandre Holmes
Chalmers, Chemistry and Chemical Engineering, Applied Chemistry
Qiaonan Chen
Chalmers, Chemistry and Chemical Engineering, Applied Chemistry
Rafael B. Ribeiro
University of Sao Paulo (USP)
Leandro Rezende Franco
Chalmers, Chemistry and Chemical Engineering, Applied Chemistry
Soumi Roy
Chalmers, Chemistry and Chemical Engineering, Chemistry and Biochemistry
Linnea Lind
Chalmers, Chemistry and Chemical Engineering, Chemistry and Biochemistry
Xiaoman Bi
Zhengzhou University
Chalmers, Chemistry and Chemical Engineering, Applied Chemistry
Mateus Bergami
Karlstad University
Mathis Mortensen Brette
Chalmers, Chemistry and Chemical Engineering, Applied Chemistry
Lunjie Zeng
Chalmers, Physics, Nano and Biophysics
Eva Olsson
Chalmers, Physics, Nano and Biophysics
Bo Albinsson
Chalmers, Chemistry and Chemical Engineering, Chemistry and Biochemistry
Márcio T.do N. Varella
University of Sao Paulo (USP)
C. Moyses Araujo
Karlstad University
Uppsala University
Ergang Wang
Chalmers, Chemistry and Chemical Engineering
Zhengzhou University
Advanced Energy Materials
1614-6832 (ISSN) 1614-6840 (eISSN)
Vol. In PressSubject Categories (SSIF 2025)
Materials Chemistry
Physical Chemistry
DOI
10.1002/aenm.71708