Visible light-driven photoreforming of polystyrene segmented glycopolymer architectures for enhanced hydrogen generation

In this report, a series of polystyrene segmented new glycopolymer architectures are synthesized, which are utilized in the photoreforming process to achieve a remarkable rate of hydrogen production. The primary building blocks of mono-, bi-, and tetra-functional photo-iniferter were employed in the RAFT polymerization process to design a series of block copolymer architectures using styrene and acetylated glucose methacrylate monomers. Acetylated polymer architectures exhibited higher thermal stability compared to deacetylated polymers. Deacetylated polymers showed lower T values than the acetylated polymers. In addition, a wide range of T values (55–96 °C) and variations in the T values of the acetylated polymers indicate the dependence on the nature of the pendant unit and macromolecular architecture. The deacetylated macromolecule, 1A-PS--PGM diblock copolymer exhibits a hydrogen generation rate of ∼753 μmol/g/h with an AQY of ∼1.84% compared to that of the polystyrene segment alone (53 μmol/g/h, AQY of ∼0.02%). Within the range of possible synthesized glycopolymer architectures, linear and glucose-based triblock glycopolymers show promising activity. The kinetics of the water-splitting reaction are influenced by adjustments to both the solution's pH and the hydrophilicity of the glycomacromolecular chains.