RESUMEN
2-Styrylthiophene-based donor-acceptor linear conjugated polymers with tunable cyano substituents are atom-economically obtained via direct C-H arylation for platinum-free photocatalytic hydrogen production, affording a HER of up to 9.79 mmol h-1 g-1.
RESUMEN
[This corrects the article DOI: 10.1039/D1SC05784G.].
RESUMEN
3,4-Ethylene dioxythiophene (EDOT), as a monomer of commercial conductive poly(3,4-ethylene dioxythiophene) (PEDOT), has been facilely incorporated into a series of new π-conjugated polymer-based photocatalysts, i.e., BSO2-EDOT, DBT-EDOT, Py-EDOT and DFB-EDOT, through atom-economic C-H direct arylation polymerization (DArP). The photocatalytic hydrogen production (PHP) test shows that donor-acceptor (D-A)-type BSO2-EDOT renders the highest hydrogen evolution rate (HER) among the linear conjugated polymers (CPs) ever reported. A HER up to 0.95 mmol h-1/6 mg under visible light irradiation and an unprecedented apparent quantum yield of 13.6% at 550 nm are successfully achieved. Note that the photocatalytic activities of the C-H/C-Br coupling-derived EDOT-based CPs are superior to those of their counterparts derived from the classical C-Sn/C-Br Stille coupling, demonstrating that EDOT is a promising electron-rich building block which can be facilely integrated into CP-based photocatalysts. Systematic studies reveal that the enhanced water wettability by the integration of polar BSO2 with hydrophilic EDOT, the increased electron-donating ability by O-C p-π conjugation, the improved electron transfer by D-A architecture, broad light harvesting, and the nano-sized colloidal character in a H2O/NMP mixed solvent rendered BSO2-EDOT as one of the best CP photocatalysts toward PHP.
RESUMEN
Conjugated polymers (CPs) as photocatalysts have evoked substantial interest. Their geometries and physical (e.g., chemical and thermal stability and solubility), optical (e.g., light absorption range), and electronic properties (e.g., charge carrier mobility, redox potential, and exciton binding energy) can be easily tuned via structural design. In addition, they are of light weight (i.e., mainly composed of C, N, O, and S). To improve the photocatalytic performance of CPs and better understand the catalytic mechanisms, many strategies with respect to material design have been proposed. These include tuning the bandgap, enlarging the surface area, enabling more efficient separation of electron-hole pairs, and enhancing the charge carrier mobility. In particular, donor-acceptor (D-A) polymers were demonstrated as a promising platform to develop high-performance photocatalysts due to their easily tunable bandgaps, high charge carrier mobility, and efficient intramolecular charge transfer. In this minireview, recent advances of D-A polymers in photocatalytic hydrogen evolution are summarized with a particular focus on modulating the optical and electronic properties of CPs by varying the acceptor units. The challenges and prospects associated with D-A polymer-based photocatalysts are described as well.