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Polymer photocatalysts have shown potential for light-driven hydrogen evolution from water. Here we studied the relative importance of the linker type in two series of conjugated polymers based on dibenzo[b,d]thiophene sulfone and dimethyl-9H-fluorene. The alkenyl-linked polymers were found to be more active photocatalysts than their alkyl and alkyne-linked counterparts. The co-polymer of dibenzo[b,d]thiophene sulfone and 1,2-diphenylethene has a hydrogen evolution rate of 3334 μmol g−1 h−1 and an external quantum efficiency of 5.6% at 420 nm.

Rational design of covalent organic frameworks has been performed for efficient photocatalytic H2O2 production without using any sacrificial agent.

Conjugated polymers have received significant attention as photocatalysts. However, photocatalytic oxygen evolution has only been reported for a few polymers so far. Here, we present a bipyridine based covalent triazine-based framework containing metal coordination sites (Bpy-CTF). The material is highly active for sacrificial photocatalytic oxygen evolution with a rate of 322 μmol g−1 h−1 under visible light illumination (≥420 nm) after post-synthetic cobalt coordination. An analogous photocatalyst containing biphenyl was found to be less active as it is not able to coordinate cobalt. Transient absorption spectroscopy studies showed that the cobalt coordinated in the bipyridine units of Bpy-CTF promotes charge separation and transfer, thus increasing water oxidation activity. The study demonstrates the growing potential of polymer photocatalysts for oxygen evolution by structural engineering and post-synthetic metalation.

In recent years, many of the highest performing polymer photocatalysts for hydrogen evolution from water have contained dibenzo[b,d]thiophene sulfone units in their polymer backbones. However, the reasons behind the dominance of this building block are not well understood. We use a new set of processable materials, in which the sulfone content is systematically controlled, to understand how the sulfone unit affects the three key processes involved in photocatalytic hydrogen generation in this system: light absorption; transfer of the photogenerated hole to the hole scavenger triethylamine (TEA); and transfer of the photogenerated electron to the palladium metal co-catalyst that remains in the polymer from synthesis. Using transient absorption spectroscopy and electrochemical measurements, and combined with molecular dynamics and density functional theory simulations, we find that the sulfone unit has two primary effects. On the picosecond timescale, it dictates the thermodynamics of hole transfer out of the polymer. The sulfone unit attracts water molecules such that the average permittivity experienced by the solvated polymer is increased, and we demonstrate here that TEA oxidation is only thermodynamically favourable above a certain permittivity threshold. On the microsecond timescale, we present experimental evidence that the sulfone unit acts as the electron transfer site out of the polymer, with the kinetics of electron extraction to palladium dictated by the ratio of photogenerated electrons to the number of sulfone units. For the highest performing, sulfone-rich material, hydrogen evolution appears to be limited by the photogeneration rate of electrons rather than their extraction from the polymer.

Polymer photocatalysts have received growing attention in recent years for photocatalytic hydrogen production from water. Most studies report hydrogen production with sacrificial electron donors, which is unsuitable for large‐scale hydrogen energy production. Here we show that the palladium/iridium oxide‐loaded homopolymer of dibenzo[b, d]thiophene sulfone (P10) facilitates overall water splitting to produce stoichiometric amounts of H2 and O2 for an extended period (>60 hours) after the system stabilized. These results demonstrate that conjugated polymers can act as single component photocatalytic systems for overall water splitting when loaded with suitable co‐catalysts, albeit currently with low activities. Transient spectroscopy shows that the IrO2 co‐catalyst plays an important role in the generation of the charge separated state required for water splitting, with evidence for fast hole transfer to the co‐catalyst.

Abstract: Conjugated materials have emerged as a new class of photocatalysts for solar fuel generation, thus allowing for the Sun’s energy to be converted into a storable fuel that can be used without further emissions at the point of use. Many different building blocks have been used to make conjugated materials that act as photocatalysts allowing for efficient light absorption and tuing of photophysical properties. The porphyrin moiety is a very interesting building block for photocatalysts as the large π-conjugated system allows efficient light absorption. Metalation of porphyrins allows for further tuning of the materials’ properties, thus further expanding the property space that these materials can cover. This allows to design and better control over the properties of the materials, which is discussed in this review together with the state-of-the-art in porphyrin photocatalysts and hybrid systems.

Photocatalytic hydrogen production from water has the potential to fulfil future energy needs by producing a clean and storable fuel. In recent years polymer photocatalysts have attracted significant interest in an attempt to address these challenges. One reason organic photocatalysts have been considered an attractive target is their synthetic modularity, therefore, the ability to tune their opto-electronic properties by incorporating different building blocks. A wide range of factors has been investigated and in particular nano-sized particles have found to be highly efficient due to the size effect resulting from the ability of these to increase the number of charges reaching catalytic sites.

A range of linear conjugated polymers is reported that promote photocatalytic CO2 reduction in water with a sacrificial hole-scavenger. Two photocatalysts containing dibenzo[b,d]thiophene sulfone were found to be the most active materials. A dibenzo[b,d]thiophene sulfone co-polymer with phenylene (P7) had the highest rate for producing CO, but also for the co-evolution of H2. The homopolymer of dibenzo[b,d]thiophene sulfone was found to be less active for CO production, but had a higher H2 production rate, which is explained by changes in the driving-force favouring proton reduction. The co-evolution of hydrogen is facilitated by residual palladium from the material synthesis. By varying the amount of palladium in the photocatalyst, syngas can be obtained with varying ratios of H2 to CO.

Wet-chemical bottom-up synthesis methods for two-dimensional (2D) layered materials are less explored than the top-down exfoliation of bulk materials. Here, we set out to synthesize a graphyne-type material by a wet-chemical synthesis method using Sonogashira–Hagihara cross-coupling polycondensation of a multifunctional monomer, 2, bearing alkyne and vinyl bromide functionalities. Spectroscopic and chemical analysis revealed that upon C–C bond formation, an unanticipated Bergman cyclization occurred to give an aromatic 2D porous carbon material (2D-PCM). 2D-PCM is a black material with graphene-like layers and a bulk structure that is similar to irregular graphite. It is porous with a hierarchical pore structure and an apparent Brunauer–Emmett–Teller surface area of 575 m2 g−1. The material has excellent electrochemical performance as an electrode in supercapacitors with a specific capacitance of 378 F g−1 at the current density of 0.1 A g−1, which surpasses state-of-the-art carbon materials, suggesting that wet-chemical methods might give functional benefits over top-down processing routes.

The first examples of linear conjugated organic polymer photocatalysts that produce oxygen from water after loading with cobalt and in the presence of an electron scavenger are reported. The oxygen evolution rates, which are higher than for related organic materials, can be rationalized by a combination of the thermodynamic driving force for water oxidation, the light absorption of the polymer, and the aqueous dispersibility of the relatively hydrophilic polymer particles. We also used transient absorption spectroscopy to study the best performing system and we found that fast oxidative quenching of the exciton occurs (picoseconds) in the presence of an electron scavenger, minimizing recombination.

Covalent organic frameworks (COFs) are distinguished from other organic polymers by their crystallinity1–3, but it remains challenging to obtain robust, highly crystalline COFs because the framework-forming reactions are poorly reversible4,5. More reversible chemistry can improve crystallinity6–9, but this typically yields COFs with poor physicochemical stability and limited application scope5. Here we report a general and scalable protocol to prepare robust, highly crystalline imine COFs, based on an unexpected framework reconstruction. In contrast to standard approaches in which monomers are initially randomly aligned, our method involves the pre-organization of monomers using a reversible and removable covalent tether, followed by confined polymerization. This reconstruction route produces reconstructed COFs with greatly enhanced crystallinity and much higher porosity by means of a simple vacuum-free synthetic procedure. The increased crystallinity in the reconstructed COFs improves charge carrier transport, leading to sacrificial photocatalytic hydrogen evolution rates of up to 27.98 mmol h−1 g−1. This nanoconfinement-assisted reconstruction strategy is a step towards programming function in organic materials through atomistic structural control.

We perform a high-throughput computational screening of a set of 3240 conjugated alternating binary co-polymers and homo-polymers, in which we predict their ability to drive sacrificial hydrogen evolution and overall water splitting when illuminated with visible light. We use the outcome of this screening to analyse how common the ability to drive either reaction is for conjugated polymers loaded with suitable co-catalysts, and to suggest promising (co-)monomers for polymeric overall water splitting catalysts.

The production of hydrogen from water via solar water splitting is a potential method to overcome the intermittency of the Sun’s energy by storing it as a chemical fuel. Inorganic semiconductors have been studied extensively as photocatalysts for overall water splitting, but polymer photocatalysts are also receiving growing attention. So far, most studies involving organic polymers report hydrogen production with sacrificial electron donors, which is unsuitable for large-scale hydrogen energy production. Here we show that a linear conjugated polymer photocatalyst can be used for overall water splitting to produce stoichiometric amounts of H2 and O2. We studied a range of different metal co-catalysts in conjunction with the linear polymer photocatalyst, the homopolymer of dibenzo[b,d]thiophene sulfone (P10). Photocatalytic activity was observed for palladium/iridium oxide-loaded P10, while other co-catalysts resulted in materials that showed no activity for overall water splitting. The reaction conditions were further optimized and the overall water splitting using the IrO2-loaded P10 was found to proceed steadily for an extended period (>60 hours) after the system stabilized. These results demonstrate that conjugated polymers can act as single component photocatalytic systems for overall water splitting when loaded with suitable co-catalysts, albeit currently with low activities. Significantly, though, organic polymers can be designed to absorb a large fraction of the visible spectrum, which can be challenging with inorganic catalysts. Transient spectroscopy shows that the IrO2 co-catalyst plays an important role in the generation of the charge separated state required for water splitting, with evidence for fast hole transfer to the co-catalyst. This solid-state approach should be transferable to other polymer photocatalysts, allowing this field to move away from sacrificial hydrogen production towards overall water splitting.

Polymer photocatalysts are a synthetically diverse class of materials that can be used for the production of solar fuels such as H2, but the underlying mechanisms by which they operate are poorly understood. Time-resolved vibrational spectroscopy provides a powerful structure-specific probe of photogenerated species. Here we report the use of time-resolved resonance Raman (TR3) spectroscopy to study the formation of polaron pairs and electron polarons in one of the most active linear polymer photocatalysts for H2 production, poly(dibenzo[b,d]thiophene sulfone), P10. We identify that polaron-pair formation prior to thermalization of the initially generated excited states is an important pathway for the generation of long-lived photoelectrons.

Covalent organic frameworks (COFs) are promising electrode materials for Li-ion batteries. However, the utilization of redox-active sites embedded within COFs is often limited by the low intrinsic conductivities of bulk-grown material, resulting in poor electrochemical performance. Here, a general strategy is developed to improve the energy storage capability of COF-based electrodes by integrating COFs with carbon nanotubes (CNT). These COF composites feature an abundance of redox-active 2,7-diamino-9,10-phenanthrenequinone (DAPQ) based motifs, robust β‑ketoenamine linkages, and well-defined mesopores. The composite materials (DAPQ-COFX—where X = wt% of CNT) are prepared by in situ polycondensation and have tube-type core-shell structures with intimately grown COF layers on the CNT surface. This synergistic structural design enables superior electrochemical performance: DAPQ-COF50 shows 95% utilization of redox-active sites, long cycling stability (76% retention after 3000 cycles at 2000 mA g−1), and ultra-high rate capability, with 58% capacity retention at 50 A g−1. This rate translates to charging times of ≈11 s (320 C), implying that DAPQ-COF50 holds excellent promise for high-power cells. Furthermore, the rate capability outperformed all previous reports for carbonyl-containing organic electrodes by an order of magnitude; indeed, this power density and the rapid (dis)charge time are competitive with electrochemical capacitors.

Linear conjugated polymers have potential as photocatalysts for hydrogen production from water but so far, most studies have involved non-scalable sacrificial reagents. Z-schemes comprising more than one semiconductor are a potential solution, but it is challenging to design these systems because multiple components must work together synergistically. Here, we show that a conjugated polymer photocatalyst for proton reduction can be coupled in a Z-scheme with an inorganic water oxidation photocatalyst to promote overall water splitting without any sacrificial reagents. First, a promising combination of an organic catalyst, an inorganic catalyst, and a redox mediator was identified by using high-throughput screening of a library of components. A Z-scheme system composed of P10 (homopolymer of dibenzo[b,d]thiophene sulfone)–Fe2+/Fe3+–BiVO4 was then constructed for overall water splitting under visible light irradiation. Transient absorption spectroscopy was used to assign timescales to the various steps in the photocatalytic process. While the overall solar-to-hydrogen efficiency of this first example is low, it provides proof of concept for other hybrid organic–inorganic Z-scheme architectures in the future.

Conjugated polymers are an emerging class of photocata-lysts for hydrogen production where the large breadth of potential synthetic diversity presents both an opportunity and a challenge. Here, we integrate robotic experimentation with high-throughput computation to navigate the available structure-property space. A total of 6354 co-polymers was considered computationally, followed by the synthesis and photocatalytic characterization of a sub-library of more than 170 co-polymers. This led to the discovery of new pol-ymers with sacrificial hydrogen evolution rates (HERs) of more than 6 mmol g-1 h-1. The variation in HER across the library does not correlate strongly with any single physical property but a machine learning model involving four sepa-rate properties can successfully describe up to 68% of the variation in the HER data between the different polymers. The four variables use in the model were the predicted elec-tron affinity, the predicted ionization potential, the optical gap, and the dispersibility of the polymer particles in solu-tion, as measured by optical transmittance.

Conjugated organic polymers have shown potential as photocatalysts for hydrogen production by water splitting. Taking advantage of a high throughput screening workflow, two series of acetylene-linked co-polymers were prepared and studied for their potential as photocatalysts for sacrificial hydrogen production from water. It was found that a triethynylbenzene-based polymer with a dibenzo[b,d]thiophene sulfone linker (TE11) had the highest performance in terms of hydrogen evolution rate under visible illumination in the presence of a sacrificial hole-scavenger. Synthetically elaborating the triethynylbenzene linker in TE11 by changing the core and by introducing nitrogen, the resulting hydrogen evolution rate was further increased by a factor of nearly two.

Solar water splitting offers a potential avenue for the production of clean and storable energy in the form of hydrogen. Semiconductors can be used as photocatalysts that enable the simultaneous production of hydrogen and oxygen from water via water splitting and in recent years inorganic semiconductor photocatalysts have been significantly improved in terms of their performance with organic semiconductors emerging as a potential alternative, though mostly studied for sacrificial half-reactions. Herein, we present recent developments in using organic semiconductors as photocatalysts highlighting their potential due to their synthetic tunability. We will particularly focus on their application in overall water splitting without using sacrificial reagents and suggest future directions in using these materials in large scale applications before concluding with suggestions for a wider community to focus research efforts on particular challenges in the field and opportunities that organic materials offer.

The most common strategy for introducing porosity into organic polymer photocatalysts has been the synthesis of cross-linked conjugated networks or frameworks. Here, we study the photocatalytic performance of a series of linear conjugated polymers of intrinsic microporosity (PIMs) as photocatalysts for hydrogen production from water in the presence of a hole scavenger. The best performing materials are porous and wettable, which allows for the penetration of water into the material. One of these polymers of intrinsic microporosity, P38, showed the highest sacrificial hydrogen evolution rate of 5226 μmol h−1 g−1 under visible irradiation (λ > 420 nm), with an external quantum efficiency of 18.1% at 420 nm, placing it among the highest performing polymer photocatalysts reported to date for this reaction.

The processability and optoelectronic properties of organic semiconductors can be tuned and manipulated via chemical design. The substitution of the popular alkyl side chains by oligoethers has recently been successful for applications such as bioelectronic sensors and photocatalytic hydrogen evolution. Beyond the differences in polarity, the carbon–oxygen bond in oligoethers is likely to render the system softer and more prone to dynamical disorder that can be detrimental to charge transport for example. In this context, we use neutron spectroscopy as a master method of probe, in addition to characterisation techniques such as X-ray diffraction, differential scanning calorimetry and polarized optical microscopy to study the effect of the substitution of n-hexyl (Hex) chains by triethylene glycol (TEG) chains on the structural dynamics of two organic semiconducting materials: a phenylene–bithiophene–phenylene (PTTP) small molecule and a fluorene-co-dibenzothiophene (FS) polymer. Counterintuitively, inelastic neutron scattering (INS) reveals a general softening of the modes of PTTP and FS materials with Hex chains, pointing towards an increased dynamical disorder in the Hex-based systems. However, temperature-dependent X-ray and neutron diffraction as well as INS and differential scanning calorimetry evidence an extra reversible transition close to room temperature for PTTP with TEG chains. The observed extra structural transition, which is not accompanied by a change in birefringence, can also be observed by quasi-elastic neutron scattering (QENS). A fastening of the TEG chains dynamics is observed in the case of PTTP and not FS. We therefore assign this transition to the melt of the TEG chains. Overall the TEG chains are promoting dynamical order at room temperature, but if crystallising, may introduce an extra reversible structural transition above room temperature leading to thermal instabilities. Ultimately, a deeper understanding of chain polarity and structural dynamics can help guide new materials design and navigate the intricate balance between electronic charge transport and aqueous swelling that is being sought for a number of emerging organic electronic and bioelectronic applications.

Nanostructured materials have interesting optical and electronic properties that are often drastically different from those of their bulk counterparts. While bulk organic/inorganic semiconductor composites have attracted much attention in the past decade, the preparation of organic/inorganic semiconductor nanocomposites (OISNs) still remains challenging. This work presents an assembly method for the co-encapsulation of titanium dioxide dots (TDs) with a cyano-substituted soluble conjugated polymer (CSCP) into a particular nanoparticle. The as-prepared CSCP/TD semiconductor nanocomposites (CSCP/TD NCs) exhibit different particle surfaces and morphologies depending on the mass ratio of the CSCP to TDs. We then tested them as photocatalysts for sacrificial hydrogen production from water. We found that nanocomposites outperformed nanoparticles of the individual components and physical mixtures thereof. The most active CSCP/TD NC had a catalytic H2 production rate that was 4.25 times higher than that of pure polymer nanoparticles prepared under the same conditions. We ascribe this to energy transfer between the semiconductors, where direct phase contact is essential, highlighting a potential avenue for using soluble, visible light-absorbing conjugated organic polymers to build Z-schemes for overall water splitting in the future.

Synthesis of zinc oxide (ZnO) nanowires (NWs) grown via vapor-liquid-solid (VLS) process using Gold (Au) as a catalyst metal on aluminum-doped zinc oxide (AZO) seed layer is reported in the present work. During the growth procedure, the nucleation process helps us to obtain ZnO nanowires with Au on the tip, confirming the VLS growth mechanism. Different morphologies were obtained after the variation in the growth parameters in the VLS process, and further, their role in the photocatalytic performance was studied. Changes in the structural properties of nanowires allowed us to modify the aspect ratio and surface area of the nanostructures. X-ray diffraction (XRD) showed that the principal orientation of the nanowires was (002) in the present case. Scanning electron microscopy (SEM) showed the structural properties of 1-D nanostructures (nanowires), and statistical analysis revealed that the average diameter in the present case was found to be varied from 57 to 85 nm. Scanning transmission electron microscopy (STEM) technique revealed the different elements present on the surface of ZnO NWs. Further, the compositional profile of nanostructures was cross-verified using Energy dispersive Spectroscopy (EDS). Photoluminescence (PL) and UV Visible studies were employed to study the optical properties of nanowires. UV–Vis measurements showed the role of different structural properties of nanowires on the absorption spectra, especially in the visible region. The ZnO nanowires were tested as photocatalysts for hydrogen production from water splitting reaction, and it was found in particular nanowires with random orientation with optimal diameter distribution show the stable and highest photocatalytic performance.

Covalent organic framework nanosheets (CONs), fabricated from twodimensional covalent organic frameworks (COFs), present a promising strategy for incorporating atomically distributed catalytic metal centers into well-defined pore structures with desirable chemical environments. Here, a series of CONs was synthesized by embedding single cobalt sites that were then evaluated for photocatalytic carbon dioxide reduction. A partially fluorinated, cobalt-loaded CON produced 10.1 μmol carbon monoxide with a selectivity of 76%, over 6 hours irradiation under visible light (TON = 28.1), and a high external quantum efficiency (EQE) of 6.6% under 420 nm irradiation in the presence of an iridium dye. The CONs appear to act as a semiconducting support, facilitating charge carrier transfer between the dye and the cobalt centers, and this results in a performance comparable with that of the state-of-the-art heterogeneous catalysts in the literature under similar conditions. The ultrathin CONs outperformed their bulk counterparts in all cases, suggesting a general strategy to enhance the photocatalytic activities of COF materials.

Compartmentalization is a ubiquitous building principle in cells, which permits segregation of biological elements and reactions. The carboxysome is a specialized bacterial organelle that encapsulates enzymes into a virus-like protein shell and plays essential roles in photosynthetic carbon fixation. The naturally designed architecture, semi-permeability, and catalytic improvement of carboxysomes have inspired rational design and engineering of new nanomaterials to incorporate desired enzymes into the protein shell for enhanced catalytic performance. Here, we build large, intact carboxysome shells (over 90 nm in diameter) in the industrial microorganism Escherichia coli by expressing a set of carboxysome protein-encoding genes. We develop strategies for enzyme activation, shell self-assembly, and cargo encapsulation to construct a robust nanoreactor that incorporates catalytically active [FeFe]-hydrogenases and functional partners within the empty shell for the production of hydrogen. We show that shell encapsulation and the internal microenvironment of the new catalyst facilitate hydrogen production of the encapsulated oxygen-sensitive hydrogenases. The study provides insights into the assembly and formation of carboxysomes and paves the way for engineering carboxysome shell-based nanoreactors to recruit specific enzymes for diverse catalytic reactions., The extreme oxygen sensitive character of hydrogenases is a longstanding issue for hydrogen production in bacteria. Here, the authors build carboxysome shells in E. coli and incorporate catalytically active hydrogenases and functional partners within the empty shell for the production of hydrogen.

Conjugated polymers with electrochemically active redox groups are a promising class of positive electrode material for lithium‐ion batteries. However, most polymers, such as polyimides, possess low intrinsic conductivity, which results in low utilization of redox‐active sites during charge cycling and, consequently, poor electrochemical performance. Here, it was shown that this limitation can be overcome by synthesizing polyimide composites (PIX) with reduced graphene oxide (rGO) using an in situ polycondensation reaction. The polyimide composites showed increased charge‐transfer performance and much larger specific capacities, with PI50, which contains 50 wt % of rGO, showing the largest specific capacity of 172 mAh g−1 at 500 mA g−1. This corresponds to a high utilization of the redox active sites in the active polyimide (86 %), and this composite retained 80 % of its initial capacity (125 mAh g−1) after 9000 cycles at 2000 mA g−1., Live long and prosper: Composites of reduced graphene oxide and a three‐dimensional polyimide with electrochemical redox active groups are synthesized and used as positive electrodes in lithium‐ion batteries. The composites show higher specific capacity (125 mAh g−1, 2000 mA g−1) and longer cycling life (80 % retention after 9000 cycles) than the polyimide on its own.

Most organic semiconductor photocatalysts for solar fuels production are linear polymers or polymeric networks with a broad distribution of molecular weights. Here, we study a series of molecular dibenzo[b,d]thiophene sulfone and fluorene oligomers as well-defined model systems to probe the relationship between photocatalytic activity and structural features such as chain length and planarity. The hydrogen evolution rate was found to vary significantly with bridge head atom, chain length, and backbone twisting. A trimer (S3) of only three repeat units has excellent activity for proton reduction with an EQE of 8.8% at 420 nm, approaching the activity of its polymer analogue and demonstrating that high molar masses are not a prerequisite for good activity. The dynamics of long-lived electrons generated under illumination in the S3 oligomer are very similar to the corresponding polymer, both under transient and quasi-continuous irradiation conditions.

Hydrogen fuel can contribute as a masterpiece in conceiving a robust carbon-free economic puzzle if cleaner methods to produce hydrogen become technically efficient and economically viable. Organic photocatalytic materials such as conjugated microporous materials (CMPs) are potential attractive candidates for water splitting as their energy levels and optical band gap as well as porosity are tunable through chemical synthesis. The performances of CMPs depend also on the mass transfer of reactants, intermediates, and products. Here, we study the mass transfer of water (H2O and D2O) and of triethylamine, which is used as a hole scavenger for hydrogen evolution, by means of neutron spectroscopy. We find that the stiffness of the nodes of the CMPs is correlated with an increase in trapped water, reflected by motions too slow to be quantified by quasi-elastic neutron scattering (QENS). Our study highlights that the addition of the polar sulfone group results in additional interactions between water and the CMP, as evidenced by inelastic neutron scattering (INS), leading to changes in the translational diffusion of water, as determined from the QENS measurements. No changes in triethylamine motions could be observed within the CMPs from the present investigations.

Technologies such as batteries, biomaterials and heterogeneous catalysts have functions that are defined by mixtures of molecular and mesoscale components. As yet, this multi-length-scale complexity cannot be fully captured by atomistic simulations, and the design of such materials from first principles is still rare1–5. Likewise, experimental complexity scales exponentially with the number of variables, restricting most searches to narrow areas of materials space. Robots can assist in experimental searches6–14 but their widespread adoption in materials research is challenging because of the diversity of sample types, operations, instruments and measurements required. Here we use a mobile robot to search for improved photocatalysts for hydrogen production from water15. The robot operated autonomously over eight days, performing 688 experiments within a ten-variable experimental space, driven by a batched Bayesian search algorithm16–18. This autonomous search identified photocatalyst mixtures that were six times more active than the initial formulations, selecting beneficial components and deselecting negative ones. Our strategy uses a dexterous19,20 free-roaming robot21–24, automating the researcher rather than the instruments. This modular approach could be deployed in conventional laboratories for a range of research problems beyond photocatalysis. A mobile robot autonomously operates analytical instruments in a wet chemistry laboratory, performing a photocatalyst optimization task much faster than a human would be able to.

A library of 237 organic binary/ternary nanohybrids consisting of conjugated polymers donors and both fullerene and non-fullerene molecular acceptors was prepared and screened for sacrificial photocatalytic hydrogen evolution. These donor-acceptor nanohybrids (DANHs) showed significantly enhanced hydrogen evolution rates compared with the parent donor or acceptor compounds. DANHs of a polycarbazole-based donor combined with a methanofullerene acceptor (PCDTBT/PC60BM) showed a high hydrogen evolution rate of 105.2 mmol g-1 h-1 under visible light (λ > 420 nm). This DANH photocatalyst produced 5.9 times more hydrogen than a sulfone-containing polymer (P10) under the same conditions, which is one of the most efficient organic photocatalysts reported so far. An apparent quantum yield of hydrogen evolution of 3.0 % at 595 nm was measured for this DANH. The photocatalytic activity of the DANHs, which in optimized cases reached 179.0 mmol g-1 h-1, is attributed to efficient charge transfer at the polymer donor/molecular acceptor interface. We also show that ternary donorA-donorB-acceptor nanohybrids can give higher activities than binary donor-acceptor hybrids in some cases.

The photocatalytic performance of fluorene-type polymer photocatalysts for hydrogen production from water in the presence of a sacrificial hole scavenger is significantly improved by the incorporation of heteroatoms into the bridge-head. This improvement can be explained by a combination of factors, including changes in thermodynamic driving-force, particle size, dispersibility under photocatalytic conditions, and light absorption, all of which vary as a function of the heteroatom incorporated.

The extremely large number of unique polymer compositions that can be achieved through copolymerisation makes it an attractive strategy for tuning their optoelectronic properties. However, this same attribute also makes it challenging to explore the resulting property space and understand the range of properties that can be realised. In an effort to enable the rapid exploration of this space in the case of binary copolymers, we train a neural network using a tiered data generation strategy to accurately predict the optical and electronic properties of 350 000 binary copolymers that are, in principle, synthesizable from their dihalogen monomers via Yamamoto, or Suzuki-Miyaura and Stille coupling after one-step functionalisation. By extracting general features of this property space that would otherwise be obscured in smaller datasets, we identify simple models that effectively relate the properties of these copolymers to the homopolymers of their constituent monomers, and challenge common ideas behind copolymer design. We find that binary copolymerisation does not appear to allow access to regions of the optoelectronic property space that are not already sampled by the homopolymers, although it conceptually allows for more fine-grained property control. Using the large volume of data available, we test the hypothesis that copolymerisation of 'donor' and 'acceptor' monomers can result in copolymers with a lower optical gap than their related homopolymers. Overall, despite the prevalence of this concept in the literature, we observe that this phenomenon is relatively rare, and propose conditions that greatly enhance the likelihood of its experimental realisation. Finally, through a 'topographical' analysis of the co-polymer property space, we show how this large volume of data can be used to identify dominant monomers in specific regions of property space that may be amenable to a variety of applications, such as organic photovoltaics, light emitting diodes, and thermoelectrics.

Plasma treatment was used as a new method to enhance the photocatalytic performance of a hydrophobic polymer photocatalyst. The sacrificial hydrogen evolution rate was enhanced by a factor of more than 8 after a plasma treatment time of 20 minutes. Contact angle measurements confirmed that the plasma treatment improved the wettability of the polymer film and XPS results indicated a surface chemical modification.

We show that a hydrogen-bonded framework, TBAP-α, with extended π-stacked pyrene columns has a sacrificial photocatalytic hydrogen production rate of up to 3108 μmol g -1 h -1. This is the highest activity reported for a molecular organic crystal. By comparison, a chemically-identical but amorphous sample of TBAP was 20-200 times less active, depending on the reaction conditions, showing unambiguously that crystal packing in molecular crystals can dictate photocatalytic activity. Crystal structure prediction (CSP) was used to predict the solid-state structure of TBAP and other functionalised, conformationally-flexible pyrene derivatives. Specifically, we show that energy-structure-function (ESF) maps can be used to identify molecules such as TBAP that are likely to form extended π-stacked columns in the solid state. This opens up a methodology for the a priori computational design of molecular organic photocatalysts and other energy-relevant materials, such as organic electronics.

Organic polymers have demonstrated promise as photocatalysts, but their photocatalytic efficiencies remain relatively low. Now, borrowing principles from organic photovoltaics, heterojunctions of polymer photocatalysts and small molecule acceptors have been shown to have excellent solar hydrogen production efficiencies. Organic polymers have demonstrated promise as photocatalysts, but their photocatalytic efficiencies remain relatively low. Now, borrowing principles from organic photovoltaics, heterojunctions of polymer photocatalysts and small molecule acceptors have been shown to have excellent solar hydrogen production efficiencies.

Nature uses organic molecules for light harvesting and photosynthesis, but most man-made water splitting catalysts are inorganic semiconductors. Organic photocatalysts, while attractive because of their synthetic tunability, tend to have low quantum efficiencies for water splitting. Here we present a crystalline covalent organic framework (COF) based on a benzo-bis(benzothiophene sulfone) moiety that shows a much higher activity for photochemical hydrogen evolution than its amorphous or semicrystalline counterparts. The COF is stable under long-term visible irradiation and shows steady photochemical hydrogen evolution with a sacrificial electron donor for at least 50 hours. We attribute the high quantum efficiency of fused-sulfone-COF to its crystallinity, its strong visible light absorption, and its wettable, hydrophilic 3.2 nm mesopores. These pores allow the framework to be dye-sensitized, leading to a further 61% enhancement in the hydrogen evolution rate up to 16.3 mmol g −1 h −1 . The COF also retained its photocatalytic activity when cast as a thin film onto a support.

Photocatalytic conversion of CO2 into fuels is an important challenge for clean energy research and has attracted considerable interest. Here we show that tethering molecular catalysts - a rhenium complex, [Re(bpy)(CO)3Cl] - together in the form of a crystalline covalent organic framework (COF) affords a heterogeneous photocatalyst with a strong visible light absorption, a high CO2 binding affinity, and ultimately an improved catalytic performance over its homogeneous Re counterpart. The COF incorporates bipyridine sites, allowing for ligation of the Re complex, into a fully π-conjugated backbone that is chemically robust and promotes light-harvesting. A maximum rate of 1040 μmol g-1 h-1 for CO production with 81% selectivity was measured. CO production rates were further increased up to 1400 μmol g-1 h-1, with an improved selectivity of 86%, when a photosensitizer was added. Addition of platinum resulted in production of syngas, hence, the co-formation of H2 and CO, the chemical composition of which could be adjusted by varying the ratio of COF to platinum. An amorphous analog of the COF showed significantly lower CO production rates, suggesting that crystallinity of the COF is beneficial to its photocatalytic performance in CO2 reduction.

The quest for efficient and economically accessible cleaner methods to develop sustainable carbon-free energy sources induced a keen interest in the production of hydrogen fuel. This can be achieved via the water-splitting process and by exploiting solar energy. However, the use of adequate photocatalysts is required to reach this goal. Covalent triazine-based frameworks (CTFs) are potential target photocatalysts for water splitting. Both electronic and structural characteristics of CTFs, particularly energy levels, optical band gaps, and porosities are directly relevant to water splitting and can be engineered through chemical design. Porosity can, in principle, be beneficial to water splitting by providing a larger surface area for the catalytic reactions to take place. However, porosity can also affect both charge transport within the photocatalyst and mass transfer of both reactants and products, thus impacting the overall kinetics of the reaction. Here, we focus on the link between chemical design and water (reactant) mass transfer, which plays a key role in the water uptake process and the subsequent hydrogen generation in practice. We use neutron spectroscopy to study the mass transfer of water in two porous CTFs, CTF-CN and CTF-2, that differ in the polarity of their struts. Quasi-elastic neutron scattering is used to quantify the amount of bound water and the translational diffusion of water. Inelastic neutron scattering measurements complement the quasi-elastic neutron scattering study and provide insights into the softness of the CTF structures and the changes in librational degrees of freedom of water in the porous CTFs. We show that two different types of interaction between water and CTFs take place in CTF-CN and CTF-2. CTF-CN exhibits a smaller surface area and lower water uptake due to its softer structure than CTF-2. However, the polar cyano group interacts locally with water leading to a large amount of bound water and a strong rearrangement of the water hydration monolayer, while water diffusion in CTF-2 is principally impacted by microporosity. The current study leads to new insights into the structure-dynamics-property relationship of CTF photocatalysts that pave the road for a better understanding of the guest-host interaction on the basis of water-splitting applications.

Reductive dehalogenation polycondensation of a series of penta- or hexacyclic, bisgeminal tetrachlorides with dicobalt octacarbonyl leads to the formation of homopolymers and copolymers with very different optical spectra. While the formation of tetrabenzoheptafulvalene connectors introduces efficient conjugation barriers due to their strongly folded structure, linking of 5-membered ring-based pentacyclic building blocks via bifluorenylidene connectors allows for an extended π-conjugation along the main chain. A comparison of homopolymer P57 and copolymer P55/77 indicates a quite different reactivity for dichloromethylene functions if incorporated into 5- or 7-membered rings. Interestingly, all investigated (co)polymers show an intrinsic microporosity in the solid-state (forming so-called Conjugated Polymers of Intrinsic Microporosity C-PIMs) and have SBET values of up to 760 m2 g−1 for homopolymer P77. This value is one of the highest reported values to date for C-PIMs.

A metal–organic conjugated micorporous polymer (CMP) containing a manganese carbonyl electrocatalyst for CO2 reduction has been synthesised and electrochemically characterised. Incorporation in a rigid framework changes the behavior of the catalyst, preventing reductive dimerization. These initial studies demonstrate the feasibility of CMP electrodes that can provide both high local CO2 concentrations and well defined electrocatalytic sites.

The use of hydrogen as a fuel, when generated from water using semiconductor photocatalysts and driven by sunlight, is a sustainable alternative to fossil fuels. Polymeric photocatalysts are based on Earth-abundant elements and have the advantage over their inorganic counterparts in that their electronic properties are easily tuneable through molecular engineering. Polymeric photocatalysts have developed rapidly over the past decade, resulting in the discovery of many active materials. However, our understanding of the key properties underlying their photoinitiated redox processes has not kept pace, and this impedes further progress to generate cost-competitive technologies. Here, we discuss state-of-the-art polymeric photocatalysts and our microscopic understanding of their activities. We conclude with a discussion of five outstanding challenges in this field: non-standardized reporting of activities, limited photochemical stability, insufficient knowledge of reaction mechanisms, balancing charge carrier lifetimes with catalysis timescales and the use of unsustainable sacrificial reagents. Solar-driven photocatalytic water splitting provides a clean pathway for production of hydrogen fuel. This Review examines both amorphous and crystalline polymeric materials for water splitting, exploring polymer design strategies, theoretical understanding and challenges for the field.

A structurally diverse family of 39 covalent triazine-based framework materials (CTFs) is synthesized by Suzuki-Miyaura polycondensation and tested as hydrogen evolution photocatalysts using a high-throughput workflow. The two best-performing CTFs are based on benzonitrile and dibenzo[b,d]thiophene sulfone linkers, respectively, with catalytic activities that are among the highest for this material class. The activities of the different CTFs are rationalized in terms of four variables: the predicted electron affinity, the predicted ionization potential, the optical gap, and the dispersibility of the CTFs particles in solution, as measured by optical transmittance. The electron affinity and dispersibility in solution are the best predictors of photocatalytic hydrogen evolution activity.

Post-polymerization ladderization is explored as a promising technique to boost the photo-catalytic activity of conjugated polymers., Conjugated ladder polymers (cLaPs) are introduced as organic semiconductors for photocatalytic hydrogen evolution from water under sacrificial conditions. Starting from a linear conjugated polymer (cLiP1), two ladder polymers are synthesized via post-polymerization annulation and oxidation techniques to generate rigidified, planarized materials bearing dibenzo[b,d]thiophene (cLaP1) and dibenzo[b,d]thiophene sulfone subunits (cLaP2). The high photocatalytic activity of cLaP1 (1307 μmol h–1 g–1) in comparison to that of cLaP2 (18 μmol h–1 g–1) under broadband illumination (λ > 295 nm) in the presence of a hole-scavenger is attributed to a higher yield of long-lived charges (μs to ms timescale), as evidenced by transient absorption spectroscopy. Additionally, cLaP1 has a larger overpotential for proton reduction and thus an increased driving force for the evolution of hydrogen under sacrificial conditions.

The photophysical properties of conjugated microporous polymers (CMPs) are tuned using an acceptor doping strategy. This allows the fluorescence of a native polyphenylene network to be controlled by introducing low loadings (0.1-5 mol %) of an acceptor comonomer, such as benzothiadiazole (BT), bisthiophenebenzothiadiazole (TBT) and perylenediimide (PDI). Fluorescence quantum yields are around 10 times higher than analogous nonporous polymers because of avoidance of chain aggregation in the porous network. White emitting CMPs with high quantum yields are prepared using this approach. Different domain structures can be prepared by changing the addition sequence of the monomers, and this has a strong effect on the fluorescent properties. These doped porous polymers can also be used as fluorescence sensors for volatile organic compounds (VOCs).

Tracking charge transfer to residual metal clusters in conjugated polymers for photocatalytic hydrogen evolution (Journal of the American Chemical Society (2020) 142:34 (14574-14587) DOI: 10.1021/jacs.0c06104) Page 14585. Appreciation for Dr. Yan-Gu Lin was inadvertently left out of the Acknowledgments. The scientific part of the paper remains unchanged. The complete correct Acknowledgments paragraph is as follows: ¦ ACKNOWLEDGMENTS M.S. is grateful to Imperial College for a President’s Ph.D. Scholarship and to the EPSRC for a Doctoral Prize Fellowship. J.R.D. and I.M. acknowledge support from KAUST (project numbers OSR-2015-CRG4-2572 and OSR-2018-CRG7- 3749.2). C.M.A., A.I.C., and R.S.S. acknowledge the Engineering and Physical Sciences Research Council (EPSRC, EP/ N004884/1). L.F. thanks the EU for a Marie Curie fellowship (658270). S.C. thanks Imperial College London for a Schro¨dinger Scholarship. R.G. is grateful to the FRQNT for a postdoctoral award and NSERC Discovery Grant funding. C.-L.C. appreciates his supervisor, Dr. Yan-Gu Lin, for his efforts on the beamtime support of XAS beamline and corresponding equipment/technical setup. All plotted data have been deposited on the open-access repository Zenodo and can be accessed via dx.doi.org/10.5281/zenodo.3932340.