The Emergence of High-Performance Conjugated Polymer/Inorganic Semiconductor Hybrid Photoelectrodes for Solar-Driven Photoelectrochemical Water Splitting.

Solar-driven photoelectrochemical (PEC) energy conversion holds great potential in converting solar energy into storable and transportable chemicals or fuels, providing a viable route toward a carbon-neutral society. Conjugated polymers are rapidly emerging as a new class of materials for PEC water splitting. They exhibit many intriguing properties including tunable electronic structures through molecular engineering, excellent light harvesting capability with high absorption coefficients, and facile fabrication of large-area thin films via solution processing. Recent advances have indicated that integrating rationally designed conjugated polymers with inorganic semiconductors is a promising strategy for fabricating efficient and stable hybrid photoelectrodes for high-efficiency PEC water splitting. This review introduces the history of developing conjugated polymers for PEC water splitting. Notable examples of utilizing conjugated polymers to broaden the light absorption range, improve stability, and enhance the charge separation efficiency of hybrid photoelectrodes are highlighted. Furthermore, key challenges and future research opportunities for further improvements are also presented. This review provides an up-to-date overview of fabricating stable and high-efficiency PEC devices by integrating conjugated polymers with state-of-the-art semiconductors and would have significant implications for the broad solar-to-chemical energy conversion research.

Fully Conjugated 2D sp2 Carbon-Linked Covalent Organic Frameworks for Photocatalytic Overall Water Splitting.

Covalent organic frameworks (COFs) hold great promise for solar-driven hydrogen production. However, metal-free COFs for photocatalytic overall water splitting remain elusive, primarily due to challenges in simultaneously regulating their band structures and catalytic sites to enable concurrent half-reactions. Herein, two types of π-conjugated COFs containing the same donor-acceptor structure are constructed via Knoevenagel condensation and Schiff base reaction to afford cyanovinylene- and imine-bridged COFs, respectively. The difference in the linkage leads to a remarkable difference in their photocatalytic activity toward water splitting. The 2D sp2 carbon-linked COF exhibits notable activity for photocatalytic overall water splitting, which can reach an apparent quantum efficiency of 2.53% at 420 nm. In contrast, the 2D imine-linked COF cannot catalyze the overall water-splitting reaction. Mechanistic investigations reveal that the cyanovinylene linkage is essential in modulating the band structure and promoting charge separation in COFs, thereby enabling overall water splitting. Moreover, it is further shown that crystallinity substantially impacts the photocatalytic performance of COFs. This study represents the first successful example of developing metal-free COFs with high crystallinity for photocatalytic overall water splitting.

Covalent Organic Frameworks Containing Dual O2 Reduction Centers for Overall Photosynthetic Hydrogen Peroxide Production.

Covalent organic frameworks (COFs) are highly desirable for achieving high-efficiency overall photosynthesis of hydrogen peroxide (H2 O2 ) via molecular design. However, precise construction of COFs toward overall photosynthetic H2 O2 remains a great challenge. Herein, we report the crystalline s-heptazine-based COFs (HEP-TAPT-COF and HEP-TAPB-COF) with separated redox centers for efficient H2 O2 production from O2 and pure water. The spatially and orderly separated active sites in HEP-COFs can efficiently promote charge separation and enhance photocatalytic H2 O2 production. Compared with HEP-TAPB-COF, HEP-TAPT-COF exhibits higher H2 O2 production efficiency for integrating dual O2 reduction active centers of s-heptazine and triazine moieties. Accordingly, HEP-TAPT-COF bearing dual O2 reduction centers exhibits a remarkable solar-to-chemical energy efficiency of 0.65 % with a high apparent quantum efficiency of 15.35 % at 420 nm, surpassing previously reported COF-based photocatalysts.

Printable and Highly Stretchable Viscoelastic Conductors with Kinematically Reconstructed Conductive Pathways.

Printable and stretchable conductors based on metallic-filler-reinforced polymer composites that can maintain high electrical conductivity at large strains are essential for emerging applications in wearable electronics, soft robotics, and bio-integrated devices. Regulating microstructures of conductive fillers during mechanical deformations is the key to reconstructing the conductive pathway and retaining high electrical conductivity, which has proven to be challenging. Here, it is reported that Ag flakes can spontaneously reorganize inside a viscoelastic, liquid-like polymer matrix by cyclic mechanical stretching, resulting in reconstructed microstructures and forming highly efficient and stable conductive pathways. Consequently, the electrical conductivities of the resultant composites can be dramatically enhanced by ≈4-8 orders of magnitude and reach ≈104 S cm-1 . The stretch-induced kinematic movements of Ag flakes inside the polymer matrix, together with the reorganization and stabilization mechanisms, are unraveled and validated by the dissipative particle dynamics simulations. This unique phenomenon enables high-performance stretchable conductors to be fabricated with significantly reduced conductive fillers. The printable and stretchable composites presented here hold great promise for use in soft and stretchable electronics, as demonstrated in stretchable light-emitting diode arrays and wearable electronics.

A Transparent, High-Performance, and Stable Sb2 S3 Photoanode Enabled by Heterojunction Engineering with Conjugated Polycarbazole Frameworks for Unbiased Photoelectrochemical Overall Water Splitting Devices.

Developing low-cost, high-performance, and durable photoanodes is essential in solar-driven photoelectrochemical (PEC) energy conversion. Sb2 S3 is a low-bandgap (≈1.7 eV) n-type semiconductor with a maximum theoretical solar conversion efficiency of ≈28% for PEC water splitting. However, bulk Sb2 S3 exhibits opaque characteristics and suffers from severe photocorrosion, and thus the use of Sb2 S3 as a photoanode material remains underexploited. This study describes the design and fabrication of a transparent Sb2 S3 -based photoanode by conformably depositing a thin layer of conjugated polycarbazole frameworks (CPF-TCzB) onto the Sb2 S3 film. This structural design creates a type-II heterojunction between the CPF-TCzB and the Sb2 S3 with a suitable band-edge energy offset, thereby, greatly enhancing the charge separation efficiency. The CPF-TCzB/Sb2 S3 hybrid photoanode exhibits a remarkable photocurrent density of 10.1 mA cm-2 at 1.23 V vs reversible hydrogen electrode. Moreover, the thin CPF-TCzB overlayer effectively inhibits photocorrosion of the Sb2 S3 and enables long-term operation for at least 100 h with ≈10% loss in photocurrent density. Furthermore, a standalone unbiased PEC tandem device comprising a CPF-TCzB/Sb2 S3 photoanode and a back-illuminated Si photocathode can achieve a record solar-to-hydrogen conversion efficiency of 5.21%, representing the most efficient PEC water splitting device of its kind.

Polarization Engineering of Covalent Triazine Frameworks for Highly Efficient Photosynthesis of Hydrogen Peroxide from Molecular Oxygen and Water.

Two-electron oxygen photoreduction to hydrogen peroxide (H2 O2 ) is seriously inhibited by its sluggish charge kinetics. Herein, a polarization engineering strategy is demonstrated by grafting (thio)urea functional groups onto covalent triazine frameworks (CTFs), giving rise to significantly promoted charge separation/transport and obviously enhanced proton transfer. The thiourea-functionalized CTF (Bpt-CTF) presents a substantial improvement in the photocatalytic H2 O2 production rate to 3268.1 µmol h-1 g-1 with no sacrificial agents or cocatalysts that is over an order of magnitude higher than unfunctionalized CTF (Dc-CTF), and a remarkable quantum efficiency of 8.6% at 400 nm. Mechanistic studies reveal the photocatalytic performance is attributed to the prominently enhanced two-electron oxygen reduction reaction by forming endoperoxide at the triazine unit and highly concentrated holes at the thiourea site. The generated O2 from water oxidation is subsequently consumed by the oxygen reduction reaction (ORR), thereby boosting overall reaction kinetics. The findings suggest a powerful functional-groups-mediated polarization engineering method for the development of highly efficient metal-free polymer-based photocatalysts.

Molecular Design of Two-Dimensional Covalent Heptazine Frameworks for Photocatalytic Overall Water Splitting under Visible Light.

Photocatalytic water splitting sustainably offers clean hydrogen energy, but it is challenging to produce low-cost photocatalysts that split water stoichiometrically into H2 and O2 without sacrificial agents under visible light. Here, we designed 17 two-dimensional (2D) covalent heptazine frameworks (CHFs) by topologically assembling heptazine and benzene-containing molecular units that provide active sites for hydrogen and oxygen evolution reactions, respectively. Among them, 12 CHFs have band gap values of <3.0 eV with band margins straddling the chemical reaction potential of H2/H+ and O2/H2O. In particular, a 2D H@DBTD CHF based on heptazine and 4,7-diphenyl-2,1,3-benzothiadiazole is a potential photocatalyst with a band gap of 2.47 eV for overall water splitting, which was confirmed with the calculated Gibbs free energy, non-adiabatic molecular dynamics, and preliminary experiment. This study presents an experimentally feasible molecular design of 2D CHFs as metal-free photocatalysts for overall water splitting under visible light.

Rational Design of Covalent Heptazine Frameworks with Spatially Separated Redox Centers for High-Efficiency Photocatalytic Hydrogen Peroxide Production.

The redox reaction centers in natural organisms conducting oxygenic photosynthesis are well arranged in a physically separated manner to convert sunlight into chemical energy efficiently. Mimicking natural photosynthesis via precisely constructing oxidative and reductive reaction centers within photocatalysts is ideal for enhancing catalytic performances in artificial photosynthesis. In this study, new covalent heptazine frameworks (CHFs) with spatially separated redox centers are rationally designed for photocatalytic production of H2 O2 from water and oxygen without using any sacrificial agents. Both experimental and computational investigations indicate that the two-electron oxygen reduction reaction occurs on the heptazine moiety, whereas the two-electron water oxidation reaction occurs on the acetylene or diacetylene bond in the CHFs. This unique spatial separation feature is critical for enhancing charge separation and achieving efficient H2 O2 production. Meanwhile, the measured exciton binding energy of the diacetylene-containing polymer is merely 24 meV. Under simulated solar irradiation, the rationally designed CHFs can achieve a solar-to-chemical conversion efficiency of 0.78%, surpassing previously reported photocatalytic materials. This study establishes a molecular engineering approach to construct periodically arranged and spatially separated redox centers in single-component polymer photocatalysts, representing a hallmark to create more exciting polymer structures for photocatalysis moving forward.

PEG-stabilized coaxial stacking of two-dimensional covalent organic frameworks for enhanced photocatalytic hydrogen evolution.

Two-dimensional covalent organic frameworks (2D COFs) featuring periodic frameworks, extended π-conjugation and layered stacking structures, have emerged as a promising class of materials for photocatalytic hydrogen evolution. Nevertheless, the layer-by-layer assembly in 2D COFs is not stable during the photocatalytic cycling in water, causing disordered stacking and declined activity. Here, we report an innovative strategy to stabilize the ordered arrangement of layered structures in 2D COFs for hydrogen evolution. Polyethylene glycol is filled up in the mesopore channels of a ß-ketoenamine-linked COF containing benzothiadiazole moiety. This unique feature suppresses the dislocation of neighbouring layers and retains the columnar π-orbital arrays to facilitate free charge transport. The hydrogen evolution rate is therefore remarkably promoted under visible irradiation compared with that of the pristine COF. This study provides a general post-functionalization strategy for 2D COFs to enhance photocatalytic performances.

Stable Unbiased Photo-Electrochemical Overall Water Splitting Exceeding 3% Efficiency via Covalent Triazine Framework/Metal Oxide Hybrid Photoelectrodes.

Photo-electrochemical (PEC) water splitting systems using oxide-based photoelectrodes are highly attractive for solar-to-chemical energy conversion. However, despite decades-long efforts, it is still challenging to develop efficient and stable photoelectrodes for practical applications. Here, thin layers of covalent triazine frameworks (CTF-BTh) containing a bithiophene moiety are conformably deposited onto the surfaces of a Cu2 O photocathode and a Mo-doped BiVO4 photoanode via electropolymerization to construct new hybrid photoelectrodes, successfully addressing the efficiency and stability issues. The CTF-BTh possesses a suitable band structure to form favorable band edge alignment with each metal oxide, creating a p-n junction and a staggered type-II heterojunction with Cu2 O and Mo-doped BiVO4 , respectively. Thus, the as-fabricated hybrid photoelectrodes exhibit substantially increased PEC performances. Meanwhile, the CTF-BTh film also serves as an effective corrosion-resistant overlayer for both photoelectrodes to inhibit photocorrosion and enable long-term operation for 150 h with only ≈10% loss in photocurrent densities. Furthermore, a stand-alone unbiased PEC tandem device comprising CTF-BTh-coated photoelectrodes exhibits 3.70% solar-to-hydrogen conversion efficiency. Even after continuous operation for 120 h, the efficiency can still retain at 3.24%.

Forming electron traps deactivates self-assembled crystalline organic nanosheets toward photocatalytic overall water splitting.

Most biological photoredox reactions occur in sophisticated molecular assemblies consisting of highly organized light-harvesting moieties and catalytic centers. Mimicking these prototypes by creating supramolecular assemblies could be a potentially viable approach toward artificial photosynthesis. Although self-assembled organic materials are known to carry out water splitting reactions, developing self-assembled organic materials for photocatalytic overall water splitting still remains a critical challenge. Herein, we first demonstrate that crystalline organic nanosheets assembled from linear oligo(phenylene butadiynylene) (OPB) are able to catalyze overall water splitting under visible light irradiation. Further investigations reveal that the photocatalytic activity of self-assembled organic structures is closely related to the crystalline structure along with the corresponding electronic structure. Structural disorders in OPB nanosheets and extrinsic factors such as adsorbed water molecules will induce the formation of electron traps which can make the OPB nanosheets thermodynamically unfavorable for photocatalytic overall water splitting. The deactivation mechanism unveiled in this study provides crucial insights into the assembling of artificial organic materials for future solar-to-chemical energy conversion.

Modulating Benzothiadiazole-Based Covalent Organic Frameworks via Halogenation for Enhanced Photocatalytic Water Splitting.

Two-dimensional covalent organic frameworks (2D COFs), an emerging class of crystalline porous polymers, have been recognized as a new platform for efficient solar-to-hydrogen energy conversion owing to their pre-designable structures and tailor-made functions. Herein, we demonstrate that slight modulation of the chemical structure of a typical photoactive 2D COF (Py-HTP-BT-COF) via chlorination (Py-ClTP-BT-COF) and fluorination (Py-FTP-BT-COF) can lead to dramatically enhanced photocatalytic H2 evolution rates (HER=177.50 µmol h-1 with a high apparent quantum efficiency (AQE) of 8.45 % for Py-ClTP-BT-COF). Halogen modulation at the photoactive benzothiadiazole moiety can efficiently suppress charge recombination and significantly reduce the energy barrier associated with the formation of H intermediate species (H*) on polymer surface. Our findings provide new prospects toward design and synthesis of highly active organic photocatalysts toward solar-to-chemical energy conversion.

A Simple Molecular Design Strategy for Two-Dimensional Covalent Organic Framework Capable of Visible-Light-Driven Water Splitting.

Two-dimensional (2D) covalent organic frameworks (COFs) are promising metal-free materials for photocatalytic water splitting because of their high surface area and predictability to assemble various molecules with tunable electronic properties. Unfortunately, 2D COFs capable of visible-light-driven photocatalytic overall water splitting are rare, partly due to rigorous requirements to their band alignments and coexistence of catalytic sites for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Herein, 12 2D nitrogen-linked COFs are designed based on first-principles calculations and topological assembly of molecular segments with catalytic activities toward either HER or OER, respectively. The electronic band structures calculated with HSE06 method indicate that 2D COFs are semiconductors with a widely tunable bandgap ranging from 1.92 to 3.23 eV. The positions of both conduction and valence band edges of nine 2D COFs match well with the chemical reaction potential of H2/H+ and O2/H2O, which are capable of photocatalytic overall water splitting. Of particular importance is that three of them based on 2,4,6-tris(4-methylphenyl)-1,3,5-triazine (TST) can split water into hydrogen and oxygen under visible light. Our results agree with respect to the literature, with three of them having been studied for photocatalytic HER or CO2 reduction. In addition, we further experimentally demonstrate that I-TST presents both HER and OER activity under visible light. Our findings present a route to design practical 2D COFs as metal-free and single-material photocatalysts for overall water splitting under visible light.

Regulating Heterogeneous Catalysis of Gold Nanoparticles with Polymer Mechanochemistry.

Polymer mechanochemistry has emerged as a unique approach to regulate homogeneous catalysis in chemical transformations. The utilization of polymer mechanochemistry to regulate heterogeneous catalysis, however, still remains to be investigated. In this study, using polymer-grafted gold nanoparticles as the model heterogeneous catalysts, we show that polymer chains can be mechanically ruptured from the surface of gold nanoparticles, and thus, the catalytic activity of gold nanoparticles can be accelerated under sonication. The mechanical activation of polymer-grafted gold nanoparticles only occurs when the grafted polymer chains exceed a threshold molecular weight. This mechanical behavior is similar to those mechanophore-linked polymers. More importantly, further characterizations reveal that the Au-Au bonds instead of the Au-S bonds are broken at the heterointerfaces of polymer chains and gold nanoparticles. Our study unveils an unprecedented characteristic of polymer-grafted metallic nanoparticles in response to external mechanical stress.

Acetylene and Diacetylene Functionalized Covalent Triazine Frameworks as Metal-Free Photocatalysts for Hydrogen Peroxide Production: A New Two-Electron Water Oxidation Pathway.

Metal-free polymer photocatalysts have shown great promise for photocatalytic H2 O2 production via two-electron reduction of molecular O2 . The other half-reaction, which is the two-electron oxidation of water, still remains elusive toward H2 O2 production. However, enabling this water oxidation pathway is critically important to improve the yield and maximize atom utilization efficiency. It is shown that introducing acetylene (CC) or diacetylene (CCCC) moieties into covalent triazine frameworks (CTFs) can remarkably promote photocatalytic H2 O2 production. This enhancement is inherent to the incorporated carbon-carbon triple bonds which are essential in modulating the electronic structures of CTFs and suppressing charge recombinations. Furthermore, the acetylene and diacetylene moieties can significantly reduce the energy associated with OH* formation and thus enable a new two-electron oxidation pathway toward H2 O2 production. The study unveils an important reaction pathway toward photocatalytic H2 O2 production, reflecting that precise control over the chemical structures of polymer photocatalysts is vital to achieve efficient solar-to-chemical energy conversion.

Stretchable Polymer Composite with a 3D Segregated Structure of PEDOT:PSS for Multifunctional Touchless Sensing.

Soft electronics with the capability of perceiving surrounding objects and acquiring information without direct touch have become increasingly important for applications in remote safety and healthcare monitoring, artificial prosthetics, and augmented reality. So far, materials that are inherently stretchable and can exhibit distinct touchless sensing capability are still scarce. Here, we report that constructing a three-dimensional (3D) segregated structure in the carboxylated styrene-butadiene latex film using poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) can lead to a highly stretchable polymer composite with high sensitivity toward various touchless stimuli. Consequently, the resultant composite can be directly used for touchless sensing. Control experiments reveal that the unique 3D segregated structure is essential to achieve high-performance touchless sensing. We further show that the composite can be assembled into capacitors to precisely identify surrounding objects via capacitive proximity sensing. Moreover, an intelligent prosthetic hand is fabricated by integrating piezoresistive and capacitive sensing modes together, demonstrating that the newly developed polymer composite holds great potential for practical touchless sensing by simultaneously perceiving the location and the temperature of the target.

Protonation-Assisted Exfoliation of N-Containing 2D Conjugated Polymers.

Ultrathin 2D conjugated polymer nanosheets are an emerging class of photocatalysts for solar-to-chemical energy conversion. Until now, the majority of ultrathin 2D polymer photocatalysts are produced through exfoliation of layered polymers. Unfortunately, it still remains a great challenge to exfoliate layered polymers into ultrathin nanosheets with high yields. In this work, a liquid-phase protonation-assisted exfoliation is demonstrated to enable remarkably improved exfoliation yields of various 2D N-containing conjugated polymers such as g-C3 N4 , C2 N, and aza-CMP. The exfoliation yields are only 2-15% in pure water whereas they can be substantially improved to 41-56% in 12 m HCl. The exfoliated ultrathin nanosheets possess average thicknesses less than 5 nm and can be easily dispersed in aqueous solutions. More importantly, the exfoliated nanosheets exhibit significantly enhanced photocatalytic activity toward photocatalytic water splitting compared to their bulk counterparts. Further characterizations and computational calculations reveal that protonation of the heterocyclic nitrogen sites in the conjugated polymer frameworks can lead to strong hydrogen bonding between the polymer surfaces and water molecules, resulting in facilitated exfoliation of polymers into the liquid phase. This study unveils an important protocol toward producing ultrathin 2D N-containing conjugated polymer nanosheets for future solar energy conversion.

Tumor Reoxygenation and Blood Perfusion Enhanced Photodynamic Therapy using Ultrathin Graphdiyne Oxide Nanosheets.

Both diffusion-limited and perfusion-limited hypoxia are associated with tumor progression, metastasis, and the resistance to therapeutic modalities. A strategy that can efficiently overcome both types of hypoxia to enhance the efficacy of cancer treatment has not been reported yet. Here, it is shown that by using biomimetic ultrathin graphdiyne oxide (GDYO) nanosheets, both types of hypoxia can be simultaneously addressed toward an ideal photodynamic therapy (PDT). The GDYO nanosheets, which are oxidized and exfoliated from graphdiyne (GDY), are able to efficiently catalyze water oxidation to release O2 and generate singlet oxygen (1O2) using near-infrared irradiation. Meanwhile, GDYO nanosheets also exhibit excellent light-to-heat conversion performance with a photothermal conversion efficiency of 60.8%. Thus, after the GDYO nanosheets are coated with iRGD peptide-modified red blood membrane (i-RBM) to achieve tumor targeting, the biomimetic GDYO@i-RBM nanosheets can simultaneously enhance tumor reoxygenation and blood perfusion for PDT. This study provides new insights into utilizing novel water-splitting materials to relieve both diffusion- and perfusion-limited hypoxia for the development of a novel therapeutic platform.

Multilayer Polypyrrole Nanosheets with Self-Organized Surface Structures for Flexible and Efficient Solar-Thermal Energy Conversion.

Converting solar energy into concentrated heat is very appealing for various applications. Polypyrrole (PPy) is known to possess excellent photothermal property with low thermal conductivity, and thus is an ideal candidate for solar-thermal energy conversion. However, solar-thermal materials based on PPy or other conducting polymers still exhibit limited energy conversion efficiency due to the lack of effective light-trapping schemes. Here, it is demonstrated that multilayer PPy nanosheets with spontaneously formed surface structures such as wrinkles and ridges via sequential polymerization on paper substrates can dramatically enhance broadband and wide-angle light absorption across the full solar spectrum, leading to an impressive solar-thermal conversion efficiency of 95.33%. The intriguing solar-thermal properties and structural features of multilayer PPy nanosheets can be used for solar heating and photoactuators. Meanwhile, when used for solar steam generation, the measured efficiency could achieve ≈92% under one sun irradiation. The hierarchically multilayer structure is mechanically flexible and robust, holding great potential for practical solar energy utilization. This study provides a simple and straightforward approach toward engineering light-weight and thermally insulating polymers into efficient solar-thermal materials for emerging solar energy-related applications.

Enabling Visible-Light-Driven Selective CO2 Reduction by Doping Quantum Dots: Trapping Electrons and Suppressing H2 Evolution.

Quantum dots (QDs), a class of promising candidates for harvesting visible light, generally exhibit low activity and selectivity towards photocatalytic CO2 reduction. Functionalizing QDs with metal complexes (or metal cations through ligands) is a widely used strategy for improving their catalytic activity; however, the resulting systems still suffer from low selectivity and stability in CO2 reduction. Herein, we report that doping CdS QDs with transition-metal sites can overcome these limitations and provide a system that enables highly selective photocatalytic reactions of CO2 with H2 O (100 % selectivity to CO and CH4 ), with excellent durability over 60 h. Doping Ni sites into the CdS lattice leads to effective trapping of photoexcited electrons at surface catalytic sites and substantial suppression of H2 evolution. The method reported here can be extended to various transition-metal sites, and offers new opportunities for exploring QD-based earth-abundant photocatalysts.