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Photocatalysts can use visible light to convert CO 2 into useful products. However, to date photocatalysts for CO 2 conversion are limited by insufficient long-term stability and low CO 2 conversion rates. Here we report hybrid photocatalysts consisting of conjugated polymers and a ruthenium(ii)-ruthenium(ii) supramolecular photocatalyst which overcome these challenges. The use of conjugated polymers allows for easy fine-tuning of structural and optoelectronic properties through the choice of monomers, and after loading with silver nanoparticles and the ruthenium-based binuclear metal complex, the resulting hybrid systems displayed remarkably enhanced activity for visible light-driven CO 2 conversion to formate. In particular, the hybrid photocatalyst system based on poly(dibenzo[ b , d ]thiophene sulfone) drove the very active, durable and selective photocatalytic CO 2 conversion to formate under visible light irradiation. The turnover number was found to be very high (TON = 349 000) with a similarly high turnover frequency (TOF) of 6.5 s -1 , exceeding the CO 2 fixation activity of ribulose-1,5-bisphosphate carboxylase/oxygenase in natural photosynthesis (TOF = 3.3 s -1 ), and an apparent quantum yield of 11.2% at 440 nm. Remarkably, quantitative conversion of CO 2 (737 μmol, 16.5 mL) to formate was achieved using only 8 mg of the hybrid photocatalyst containing 80 nmol of the supramolecular photocatalyst at standard temperature and pressure. The system sustained photocatalytic activity even after further replenishment of CO 2 , yielding a very high concentration of formate in the reaction solution up to 0.40 M without significant photocatalyst degradation within the timeframe studied. A range of experiments together with density functional theory calculations allowed us to understand the activity in more detail., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Photoelectrochemical (PEC) devices hold huge potential to convert solar energy into chemical energy. However, the high cost of raw materials and film processing has hindered its practical use. In this study, we attempt to tackle this issue by fabricating straightforward semiconducting polymer films. These films function as photoanodes for various oxidation reactions, including water oxidation and oxidative organosynthesis. The structures of the polymer were assessed by incorporating electron-rich and electron-deficient co-monomers into dibenzo[ b , d ]thiophene sulfone materials. Furthermore, to gain comprehensive insight into the performance, we conducted both steady-state and in operando investigations, revealing that the active site on the polymer surface determines the rate of the conversion process. This study marks a significant stride towards leveraging economically viable semiconductors in PEC systems for efficient solar-to-chemical conversions. It addresses the challenges of high material costs and complex film processing, paving the way for the scaled-up application of this burgeoning technology., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Photocatalyst systems combining donor polymers with acceptor molecules have shown the highest evolution rates for sacrificial hydrogen production from water for organic systems to date. Here, new donor molecules have been designed and synthesised taking inspiration from the structure-performance relationships which have been established in the development of non-fullerene acceptors. While a conventional bulk heterojunction (BHJ) pairing consists of a donor polymer and acceptor small molecule, here we have successfully reversed this approach by using new p-type small molecules in combination with a n-type conjugated polymer to produce non-conventional BHJ (ncBHJ) nanoparticles. We have applied these ncBHJs as photocatalysts in the sacrificial hydrogen evolution from water, and the best performing heterojunction displayed high activity for sacrificial hydrogen production from water with a hydrogen evolution rate of 22 321 μmol h -1 g -1 which compares well with the state-of-the-art for conventional BHJ photocatalyst systems., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Conjugated materials have emerged as competitive photocatalysts for the production of sustainable hydrogen from water over the last decade. Interest in these polymer photocatalysts stems from the relative ease to tune their electronic properties through molecular engineering, and their potentially low cost. However, most polymer photocatalysts have only been utilised in rudimentary suspension-based photocatalytic reactors, which are not scalable as these systems can suffer from significant optical losses and often require constant agitation to maintain the suspension. Here, we will explore research performed to utilise polymeric photocatalysts in more sophisticated systems, such as films or as nanoparticulate suspensions, which can enhance photocatalytic performance or act as a demonstration of how the polymer can be scaled for real-world applications. We will also discuss how the systems were prepared and consider both the benefits and drawbacks of each system before concluding with an outlook on the field of processable polymer photocatalysts.

Biohybrid photocatalysts are composite materials that combine the efficient light-absorbing properties of synthetic materials with the highly evolved metabolic pathways and self-repair mechanisms of biological systems. Here, we show the potential of conjugated polymers as photosensitizers in biohybrid systems by combining a series of polymer nanoparticles with engineered Escherichia coli cells. Under simulated solar light irradiation, the biohybrid system consisting of fluorene/dibenzo [ b,d ]thiophene sulfone copolymer (LP41) and recombinant E. coli (i.e., a LP41/HydA BL21 biohybrid) shows a sacrificial hydrogen evolution rate of 3.442 mmol g -1 h -1 (normalized to polymer amount). It is over 30 times higher than the polymer photocatalyst alone (0.105 mmol g -1 h -1 ), while no detectable hydrogen was generated from the E. coli cells alone, demonstrating the strong synergy between the polymer nanoparticles and bacterial cells. The differences in the physical interactions between synthetic materials and microorganisms, as well as redox energy level alignment, elucidate the trends in photochemical activity. Our results suggest that organic semiconductors may offer advantages, such as solution processability, low toxicity, and more tunable surface interactions with the biological components over inorganic materials.