Processing polymer photocatalysts for photocatalytic hydrogen evolution.

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.

Conjugated Polymer/Recombinant Escherichia coli Biohybrid Systems for Photobiocatalytic Hydrogen Production.

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.

Making the connections: physical and electric interactions in biohybrid photosynthetic systems.

Biohybrid photosynthesis systems, which combine biological and non-biological materials, have attracted recent interest in solar-to-chemical energy conversion. However, the solar efficiencies of such systems remain low, despite advances in both artificial photosynthesis and synthetic biology. Here we discuss the potential of conjugated organic materials as photosensitisers for biological hybrid systems compared to traditional inorganic semiconductors. Organic materials offer the ability to tune both photophysical properties and the specific physicochemical interactions between the photosensitiser and biological cells, thus improving stability and charge transfer. We highlight the state-of-the-art and opportunities for new approaches in designing new biohybrid systems. This perspective also summarises the current understanding of the underlying electron transport process and highlights the research areas that need to be pursued to underpin the development of hybrid photosynthesis systems.

Impact of Interfaces, and Nanostructure on the Performance of Conjugated Polymer Photocatalysts for Hydrogen Production from Water.

The direct conversion of sunlight into hydrogen through water splitting, and by converting carbon dioxide into useful chemical building blocks and fuels, has been an active area of research since early reports in the 1970s. Most of the semiconductors that drive these photocatalytic processes have been inorganic semiconductors, but since the first report of carbon nitride organic semiconductors have also been considered. Conjugated materials have been relatively extensively studied as photocatalysts for solar fuels generation over the last 5 years due to the synthetic control over composition and properties. The understanding of materials' properties, its impact on performance and underlying factors is still in its infancy. Here, we focus on the impact of interfaces, and nanostructure on fundamental processes which significantly contribute to performance in these organic photocatalysts. In particular, we focus on presenting explicit examples in understanding the interface of polymer photocatalysts with water and how it affects performance. Wetting has been shown to be a clear factor and we present strategies for increased wettability in conjugated polymer photocatalysts through modifications of the material. Furthermore, the limited exciton diffusion length in organic polymers has also been identified to affect the performance of these materials. Addressing this, we also discuss how increased internal and external surface areas increase the activity of organic polymer photocatalysts for hydrogen production from water.

Why Do Sulfone-Containing Polymer Photocatalysts Work So Well for Sacrificial Hydrogen Evolution from Water?

Many of the highest-performing polymer photocatalysts for sacrificial 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 study films, dispersions, and solutions of a new set of solution-processable materials, where 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. Transient absorption spectroscopy and electrochemical measurements, combined with molecular dynamics and density functional theory simulations, show 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. We show that TEA oxidation is only thermodynamically favorable 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 seems to be limited by the photogeneration rate of electrons rather than their extraction from the polymer.

Linear conjugated polymer photocatalysts with various linker units for photocatalytic hydrogen evolution from water.

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.

Reconstructed covalent organic frameworks.

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.

Photocatalytic Overall Water Splitting Under Visible Light Enabled by a Particulate Conjugated Polymer Loaded with Palladium and Iridium.

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.

Time-Resolved Raman Spectroscopy of Polaron Formation in a Polymer Photocatalyst.

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.

Probing Dynamics of Water Mass Transfer in Organic Porous Photocatalyst Water-Splitting Materials by Neutron Spectroscopy.

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.

Effect of substituting non-polar chains with polar chains on the structural dynamics of small organic molecule and polymer semiconductors.

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.

Impact of Chemical Structure on the Dynamics of Mass Transfer of Water in Conjugated Microporous Polymers: A Neutron Spectroscopy Study.

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.

Conjugated nanomaterials for solar fuel production.

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.

Nano-assemblies of a soluble conjugated organic polymer and an inorganic semiconductor for sacrificial photocatalytic hydrogen production from water.

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.

Reprogramming bacterial protein organelles as a nanoreactor for hydrogen production.

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.

Tracking Charge Transfer to Residual Metal Clusters in Conjugated Polymers for Photocatalytic Hydrogen Evolution.

Semiconducting polymers are versatile materials for solar energy conversion and have gained popularity as photocatalysts for sunlight-driven hydrogen production. Organic polymers often contain residual metal impurities such as palladium (Pd) clusters that are formed during the polymerization reaction, and there is increasing evidence for a catalytic role of such metal clusters in polymer photocatalysts. Using transient and operando optical spectroscopy on nanoparticles of F8BT, P3HT, and the dibenzo[b,d]thiophene sulfone homopolymer P10, we demonstrate how differences in the time scale of electron transfer to Pd clusters translate into hydrogen evolution activity optima at different residual Pd concentrations. For F8BT nanoparticles with common Pd concentrations of >1000 ppm (>0.1 wt %), we find that residual Pd clusters quench photogenerated excitons via energy and electron transfer on the femto-nanosecond time scale, thus outcompeting reductive quenching. We spectroscopically identify reduced Pd clusters in our F8BT nanoparticles from the microsecond time scale onward and show that the predominant location of long-lived electrons gradually shifts to the F8BT polymer when the Pd content is lowered. While a low yield of long-lived electrons limits the hydrogen evolution activity of F8BT, P10 exhibits a substantially higher hydrogen evolution activity, which we demonstrate results from higher yields of long-lived electrons due to more efficient reductive quenching. Surprisingly, and despite the higher performance of P10, long-lived electrons reside on the P10 polymer rather than on the Pd clusters in P10 particles, even at very high Pd concentrations of 27000 ppm (2.7 wt %). In contrast, long-lived electrons in F8BT already reside on Pd clusters before the typical time scale of hydrogen evolution. This comparison shows that P10 exhibits efficient reductive quenching but slow electron transfer to residual Pd clusters, whereas the opposite is the case for F8BT. These findings suggest that the development of even more efficient polymer photocatalysts must target materials that combine both rapid reductive quenching and rapid charge transfer to a metal-based cocatalyst.

A mobile robotic chemist.

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.

Crosslinked Polyimide and Reduced Graphene Oxide Composites as Long Cycle Life Positive Electrode for Lithium-Ion Cells.

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 .

Water Oxidation with Cobalt-Loaded Linear Conjugated Polymer Photocatalysts.

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.