Optimally Miscible Polymer Bulk-Heterojunction-Particles for Nonsurfactant Photocatalytic Hydrogen Evolution

Mini-emulsion and nanoprecipitation techniques relied on large amounts of surfactants, and unresolved miscibility issues of heterojunction materials limited their efficiency and applicability in the past. Through our molecular design and developed surfactant-free precipitation method, we successfully fabricated the best miscible bulk-heterojunction-particles (BHJP) ever achieved, using donor (PS) and acceptor (PSOS) polymers. The structural similarity ensures optimal miscibility, as supported by the interaction parameter of the PS/PSOS blend is positioned very close to the binodal curve. Experimental studies and molecular dynamics simulations further revealed that surfactants hinder electron output sites and reduce the concentration of sacrificial agents at the interface, slowing polaron formation. Multiscale experiments verified that these BHJP, approximately 12 nm in diameter, further form cross-linked fractal networks of several hundred nanometers. Transient absorption spectroscopy showed that BHJP facilitates polaron formation and electron transfer. Our BHJP demonstrated a superior hydrogen evolution rate (HER) compared to traditional methods. The most active BHJP achieved an HER of 251.2 mmol h^-1 g^-1 and an apparent quantum yield of 26.2% at 500 nm. This work not only introduces a practical method for preparing BHJP but also offers a new direction for the development of heterojunction materials.