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Aromatic polyimide (PI)-based compounds have been widely studied for lithium-ion batteries (LIBs) and sodium-ion batteries (SIBs) due to their higher specific energy density, economical, environmentally friendly and adjustable redox potential window. However, their solubility in aprotic electrolytes, inherently poor conductivity and low active site utilization limit their application in large-scale energy storage system (ESS). Here, we synthesized two aromatic PI-based conjugated microporous polymers (CMPs) and integrated them with multi-walled carbon nanotubes (CNT) (TAPT-NTCDA@CNT and TAPT-PMDA@CNT) for using as cathode materials for LIBs and SIBs. The aromatic PI-based CMP can effectively utilize the redox activity site due to its abundant π-conjugated redox active units, stable imide bond, high specific surface area and clear pore structure. As expected, the optimum TAPT-NTCDA@CNT exhibits good rate performance (89.7 mAh g−1 at 2000 mA g−1) and long cycle stability (87.3% capacity retention after 500 cycles) in LIBs. Also, TAPT-NTCDA@CNT can provide a higher initial capacity of 91.1 mAh g−1 in SIBs at 30 mA g−1. This work provides key insights for the further development of other new organic electrodes for other advanced rechargeable batteries.

Conjugated microporous polymers (CMPs) have shown great promise for use in contemporary energy applications owing to their unique structures and tunable functionality. Here, we report a CMP embedded with a single-atom Co catalyst (Co-CMP) as an electrocatalytic sulfur host for promoting the cathode reactions of lithium−sulfur (Li−S) batteries. The Co-CMP was synthesized by copolymerizing a dibromo salcyen Co complex with tris(ethynylthiophene)triazine using standard Sonogashira coupling methodology. In addition to featuring a single-atom catalyst (SAC), the Co-CMP possesses a high quantity of pyridinic nitrogen atoms and relatively large pore sizes that collectively facilitate sulfur cathode chemistry. The performance displayed by Li−S cells fabricated with the Co-CMP was outstanding when compared with cells that were devoid of a SAC, particularly in terms of specific capacity (1404 vs. 1338 mA h g−1 at 0.1 C), rate capability (766 vs. 613 mA h g−1 at 2 C), and cycling stability (549 vs. 314 mA h g−1 after 1000 cycles at 0.5 C). Density functional theory calculations in conjunction with X-ray absorption near-edge structure spectroscopy measurements revealed that the single-atom Co catalyst lowers the cathode reaction energies by forming bonding interactions with the polysulfide anions as well as the Li cations that are present in sulfur cathodes. Since the methodology is modular and obviates the extreme steps required by other approaches, it can be employed to synthesize new classes of CMPs containing SACs with predictable structures and functions for use in a broad range of contemporary catalytic applications.

Organic phase change materials (PCMs) have attracted considerable attention for thermal energy storage applications because of their non-toxicity, suitable working temperature range and excellent thermal/chemical stability. However, most traditional organic PCMs have small molecular structures and are prone to leakage during fusion. To address this problem and enhance the shape-stability of organic PCMs, nanosphere-shaped porphyrin-ferrocenyl conjugated microporous polymers (PFCMPs) with high porosity (~ 650 m2/g) were solvothermally synthesized using a Diels-Alder reaction between 1,1′-ferrocenedicarboxaldehyde and pyrrole in the presence of glacial acetic acid and anhydrous Lewis acids (FeCl3, AlCl3, and CuCl2). The PFCMPs were then encapsulated with PCMs, that is, 1-octadecanol (ODA), to prepare the composite materials of ODA@PFCMPs. The optimized composite exhibited a high latent heat (up to 153.8 J/g), excellent reversibility (negligible change in latent heat upon 100 cycles of heating–cooling), good shape stability, and long heat storage durability (425 s), making it a promising candidate for solar thermal energy engineering and management.

Recently, conjugated microporous polymers (CMPs) comprised of thiazolo[5,4-d]thiazole (TzTz) linkages have received much attention due to their excellent photoelectric properties. Herein, the polycondensation of dithiooxamide and benzyl aldehydes of C2, C3, and D2h symmetry afforded three TzTz-linked CMPs, namely TzTz-CMP-1, TzTz-CMP-2, and TzTz-CMP-3. Importantly, the porous and flexible characteristics of TzTz-linked CMPs enable the smooth selective aerobic oxidation of amines in ethanol (C2H5OH), a clean but redox-active solvent. All three TzTz-linked CMPs significantly surpass the benchmark mesoporous graphite carbon nitride (mpg-C3N4) photocatalyst. Intriguingly, TzTz-CMP-2 displays the best photocatalytic activity for the blue-light-mediated selective transformation of primary and secondary amines into imines. The conversions of amines were up to 90% with excellent selectivities for imines. This work highlights that CMPs with TzTz linkages may offer efficient photocatalytic selective transformations under genuinely ambient conditions.

Polymer membranes typically possess a broad pore-size distribution that leads to much lower selectivity in ion separation when compared to membranes made of crystalline porous materials; however, they are highly desirable because of their easy processability and low cost. Herein, we demonstrate the fabrication of ion-sieving membranes based on a polycarbazole-type conjugated microporous polymer using an easy to scale-up electropolymerization strategy. The membranes exhibited high uniform sub-nanometer pores and a precisely tunable membrane thickness, yielding a high ion-sieving performance with a sub-1 Å size precision. Both experimental results and molecular simulations suggested that the impressive ion-sieving performance of the CMP membranes originates from their uniform and narrow pore-size distribution.

Using the power of light to drive controlled radical polymerizations has provided significant advances in synthesis of well-defined polymers. Photoinduced atom transfer radical polymerization (ATRP) systems often employ UV light to regenerate copper activator species to mediate the polymerization. Taking full advantage of long-wavelength visible light for ATRP would require developing appropriate photocatalytic systems that engage in photoinduced electron transfer processes with the ATRP components to generate activating species. Herein, we developed conjugated microporous polymers (CMP) as heterogeneous photocatalysts to exploit the power of visible light in promoting copper-catalyzed ATRP. The photocatalyst was designed by cross-linking phenothiazine (PTZ) as a photoactive core in the presence of dimethoxybenzene as a cross-linker via the Friedel-Crafts reaction. The resulting PTZ-CMP network showed photoactivity in the visible region due to the extended conjugation throughout the network because of the aromatic groups connecting the PTZ units. Therefore, photoinduced copper-catalyzed ATRP was performed with CMPs that regenerated activator species under green or red light irradiation to start the ATRP process. This resulted in efficient polymerization of acrylate and methacrylate monomers with high conversion and well-controlled molecular weight. The heterogeneous nature of the photocatalyst enabled easy separation and efficient reusability in subsequent polymerizations.

Of various atomically dispersed metal catalysts, those based on single Ni atoms are among the most efficient electrocatalysts for CO2 reduction. However, the activity of these catalysts is determined by the coordination environment of Ni sites. Here, N and S co-coordinated Ni sites were successfully prepared using a nickel phosphorus trisulfide two-dimensional template to form a sandwich-like conjugated microporous polymer. As-prepared Ni single atom–based porous carbon nanosheets were proved to possess N/S co-coordination via X-ray absorption spectroscopy. As electrocatalysts for CO2 reduction, the prepared porous carbon nanosheets achieved over 95% CO selectivity rate and −7.8 mA cm−2 current density (−0.8 V vs. reversible hydrogen electrode). This performance could be attributed to the sheet-like morphology of the nanosheets with long-distance conductivity and the rich single N/S-coordinated Ni atoms with high activity. The fundamental understanding of manipulating such a coordination environment revealed in this study can be used to create versatile single-metal atom–based catalysts for high-efficient energy conversion.

In this study, we prepared a series of conjugated microporous polymers (CMPs) through Sonogashira-Hagihara cross-couplings of a tetrabenzonaphthalene (TBN) monomer with pyrene (Py), tetraphenylethylene (TPE), and carbazole (Car) units and examined their chemical structures, thermal stabilities, morphologies, crystallinities, and porosities. TBN-TPE-CMP possessed a high surface area (1150 m2 g-1) and thermal stability (Td10 = 505 °C; char yield = 68 wt %) superior to those of TBN-Py-CMP and TBN-Car-CMP. To improve the conductivity of the TBN-CMP materials, we blended them with highly conductive single-walled carbon nanotubes (SWCNTs). Electrochemical measurements revealed that the TBN-Py-CMP/SWCNT nanocomposite had high capacitance (430 F g-1) at a current density of 0.5 A g-1 and outstanding capacitance retention (99.18%) over 2000 cycles; these characteristics were superior to those of the TBN-TPE-CMP/SWCNT and TBN-Car-CMP/SWCNT nanocomposites.

Conjugated microporous polymers (CMPs) represent an important type of functional materials. In this area, morphological engineering has remained a major challenge. Here, we report the synthesis of porphyrin-based CMP tubes (CMP-1) through a template-free protocol. A mechanism study reveals that the CMP tubes are formed by the scrolling and closing of ribbon-like structures. The tubes possess a high specific surface area of 495 m(2)/g, along with improved optical properties including broadened absorption in the visible-light region, longer triplet-state lifetime, and more stable photocurrent, compared to those of the irregular solid CMP counterpart. When serving as a metal-free photocatalyst for an undocumented visible-light-driven thiocyanation of anilines, CMP-1 exhibits excellent photocatalytic performance, with single chemoselectivity and high yields for the conversion of 25 types of anilines at ambient conditions. This study fills in the gap of the tubular morphological engineering of CMPs and broadens the scope of their potential applications.

Developing cheap, highly efficient, metal-free heterogeneous photocatalysts remain a great challenge in photoredox reactions. Herein, we utilize a typical Suzuki coupling of low-cost triphenylamine derivative and 9,10-dibromoanthracene to synthesis a donor–acceptor type conjugated microporous polymer (denoted as PAA-CMP). As expected, heterogeneous PAA-CMP exhibits excellent photocatalytic performance, good functional group tolerance and satisfying recyclability in metal-free aerobic oxidative coupling of amines to imines driven by visible light, which is due to its absolute energy level positions and good physicochemical stability. More excitingly, PAA-CMP can enable the gram-scale air-oxidized photocatalytic conversion under natural sunlight irradiation, yielding the desired imine product with an isolated yield of 65% for 48 h. The current work provides a great application prospect for CMPs in low-cost and large-scale organic industrial production in the future. The prepared donor-acceptor (D-A) type conjugated microporous polymer (PAA-CMP) as a metal-free and heterogeneous photocatalyst enable the gram-scale air-oxidized photocatalytic conversion of benzylamine into N-benzylidenebenzylamine under natural sunlight irradiation, yielding the desired imine product with an isolated yield of 65%.

Luminescent conjugated network polymer is one of the most promising chemo-sensors owing to their good chemical/optical stability and multiple functionalization. Herein, three conjugated network polymers were prepared by using aggregation-induced emission active 1,1,2,2-tetrakis(4-formyl-(1,1′-biphenyl))-ethane (TFBE) unit as monomer and hydrazine as linker. Through regulating the synthetical condition, the polymeric network can form either uniform two-dimensional azine-linked nanosheets (A-NS), conjugated microporous polymers (A-CMP) or covalent organic frameworks (A-COF). All of these polymers exhibited good stability and high fluorescence quantum efficiency with the quantum yield of 6.31% for A-NS, 5.26% for A-CMP, and 5.80% for A-COF, as well as fast and selective fluorescence quenching response to 2,4,6-trinitrophenol (TNP). And the best TNP sensing performance with the Stern-Volmer constants (Ksv) values up to 8 × 105 L/mol and a detection limit of 0.09 μmol/L was obtained for A-NS. The study explores various strategies to construct conjugated polymers with different nanoarchitectures based on the same building block for sensitive detection of explosives.

The development of functional materials with better flame-retardant and thermal insulation properties has attracted considerable attention for energy storage applications in modern society. Here, we describe a facile approach for the preparation of conjugated microporous polymer hollow spheres (CMP-HSs) by using SiO2 nanoparticles as a template via the Sonogashira-Hagihara cross-coupling reaction. The as-synthesized CMP-HSs have good thermal stability with a thermal decomposition temperature of up to 281 °C, high porosity (the BET specific surface area is measured to be approximately 666 m2 g−1) along with lipophilic and hydrophobic characteristics. To further improve their flame retardancy, CMP-HSs were treated with dimethyl phosphonate (DMMP) though an immersion method to prepare the CMP-HSs composite (CMP-HSs-DMMP) flame-retardants. By introducing CMP-HSs-DMMP into the epoxy resin (EP) matrix, the as-prepared EP composites showed excellent flame-retardant properties, e.g., the peak heat release rate (pHRR) and total heat release (THR) value of EP composites containing only 0.2% CMP-HSs-DMMP flame-retardant were 650.9 kW m−2 and 79.4 MJ m−2 respectively, in the range of 0 °C − 650 °C, which are 19.6 ± 2% and 19.1 ± 5% lower than that of pure EP within the same temperature range. Considering the significant enhancement of its flame retardancy with only a slight dosage of CMP-HSs-DMMP, such CMP hollow sphere-based flame-retardant composites may have great potential as functional bulk materials or coatings in a variety of fireproofing applications.

Incorporation of organic chromophores into conjugated micro/mesoporous polymers (CMPs) provides a promising avenue for developing recyclable heterogeneous photocatalysts by overcoming tedious separation and low reusability of homogeneous organic dye-based photocatalysts. However, the design principle and the underlying structure–property relationship for fabricating and selecting various organic dye-embedded CMPs for efficient photocatalysis have not been well-constructed so far. In this study, we described the rational fabrication of two new CMPs via the one-step Sonogashira coupling using β-diketone boron difluoride dye as the key linker and commonly used building blocks (triphenylamine/triphenylbenzene) as the cores. The resulting boron-dye containing CMPs were efficiently employed as the metal-free photocatalysts in two typical aerobic oxidative organic transformations including coupling of benzylamine and oxidation of aryl boronic acids to corresponding aryl phenols, which have never been explored with other boron-dye-embedded CMPs. They exhibited superior photocatalytic performance compared to their boron-free counterparts due to their wide visible-light absorption, narrow optical bandgaps, and extended π-conjugation due to boron-complexation. The present study establishes β-diketone boron difluoride dyes as efficient building blocks for fabricating new CMP-based photocatalysts.

Two-dimensional conjugated microporous polymers (2D CMPs) are sheet/film-like CMPs with amorphous, permanent porous and π-conjugated structures, which have attracted considerable attention over the past few years. Owing to the excellent optoelectronic properties of conjugated polymers together with their microporous, sheet/film-like structures, 2D CMPs have several applications in molecular separation, energy storage, gas sensing, and optoelectronics. This review focuses on the latest advances in fabrication strategies and potential applications of 2D CMPs, with a particular emphasis on optoelectronic device applications. The current challenges and possible future research directions of 2D CMPs are also discussed briefly.

The polymers based on thiophene armed triazine and different thiophene derivatives including thiophene (Th), thieno[3,2-b]thiophene (TT), dithieno[3,2-b:2′,3′-d]thiophene (DTT) or thieno[2′,3':4,5]thieno[3,2-b]thieno[2,3-d]thiophene (TTTT) are synthesized through a Stille coupling reaction. By introducing thiophene derivatives with increasing sizes as the linkage units (from thiophene, DT to DTT, TTTT), the band gaps (Eg) of the resultant polymers decrease continuously. Then the composite materials (polymer@C) between polymers and Vulcan XC-72 carbon are prepared by in situ polymerization to test their electrochemical performances in lithium ion batteries. The synthesized composites show distinct morphologies due to the different linkage units of thiophene or fused cyclothiophene derivatives and the cross-linked structure can be found in composites with the longer thiophene derivatives (bridging molecules) like PTT-3@C and PTT-4@C, which are expected to be beneficial to improve the performances of the electrode materials. The specific capacities of the composites are 495 mA h g−1, 671 mA h g−1, 707 mA h g−1, and 772 mA h g−1 for PTT-1@C, PTT-2@C, PTT-3@C and PTT-4@C at a current density of 100 mA g−1, respectively. In particular, benefiting from the enlarged conjugation length and planarity of the linkage units, the conjugated microporous polymers could deliver continuously improved capacities.

A localized electron density modulation strategy is proposed to enhance the intrinsic surface catalytic proton reduction reaction by introducing dual pyridinic nitrogen (N) atoms into the polymer skeleton. Theoretical calculations suggest that the increased localized electron density at the N site can enhance the electron density of states around the Fermi level, which would lower the energy barrier to H adsorption and activation during the photocatalytic hydrogen evolution (PHE) process. Moreover, the increased localized electron density also contributes to accelerating the photo-induced charge separation and transportation. Resultingly, an apparent quantum yield of 35.5% of the newly developed conjugated polymer (termed as COP-PB-N2) can be achieved at a polymer concentration of 1 mg mL−1, which is the highest value achieved for conjugated microporous polymers to date. This work provides a new strategy through modulating the electronic properties of catalytically active sites for boosting the intrinsic photocatalytic performance.

This work introduces, for the first time, the energy harvesting performance of conjugated microporous polymers (CMPs) as tribo-positive materials for triboelectric nanogenerators (TENGs). Various nano or submicron CMP particles (CMP-X) were prepared by the Sonogashira coupling of 1,3,5-triethynylbenzene with 1,4-diiodoarenes. Optimized CMP-X nanoparticles in a polyurethane (PU) matrix showed excellent triboelectrification performance, displaying peak-to-peak voltages of up to 411 V and a maximum power density of 0.80 mW cm−2. Moreover, an optimized 5.0% CMP-H@PU-based TENG could be utilized as a power source for the charging of an electrolytic capacitor and for the operation of 100 LEDs.

Metal-free conjugated microporous polymers (CMPs) as visible-light active and recyclable photocatalysts offer a green and sustainable alternative to classical metal-based photosensitizers. However, the strategy for screening CMP-based heterogeneous photocatalysts has not been interpreted up to now. Herein, we present a general strategy for obtaining excellent solid photocatalysts, which is to implement bandgap engineering in the same series of materials. As a proof of concept, three conjugated porous materials containing benzo[1,2-b:3,4-b′:5,6-b′′]trithiophene building blocks (BTT-CMP1, BTT-CMP2 and BTT-CMP3) were successfully constructed. They possess permanent porosity with a large specific surface area and excellent stability. By changing the linker between benzotrithiophene units, the bandgaps, energy levels and photoelectric performances including the absorption, transient photocurrent responses and photocatalytic performances of BTT-CMPs could be handily modulated. Indeed, BTT-CMP2 displayed the best catalytic activity for visible-light-induced synthesis of benzimidazoles among the three CMP materials, even higher than that of small molecule photocatalysts. As a metal-free photocatalyst, interestingly, the screened BTT-CMP2 also showed extensive substrate applicability and outstanding recyclability. Additionally, we have the opinion that this strategy will prove to be a guiding principle for screening superior CMP-based photocatalysts and broaden their application fields.

The fabrication of single atomic photocatalysts via a simple pathway is a crucial challenge to enable the efficient production \ud of hydrogen. Herein, we demonstrate a gaseous diffusion strategy to construct single atomic photocatalysts by using the \ud intrinsic nanopore of pyridyl-functionalized conjugated microporous polymer (PCMP) to host nickel (Ni) or cobalt (Co) atoms. \ud Comprehensive microscopy and spectroscopy characterizations were carried out to understand the morphology and \ud structure variations of Ni or Co single atomic anchored PCMP as photocatalysts. The experimental results show that Ni or \ud Co present as single atoms anchoring with pyridyl nitrogen, which prominently alter the electronic structures of PCMP and \ud delocalize the charge density of the metal atom to promote proton adsorption. The outcome of the single atomic anchoring \ud substantially reduces the energy barrier of photocatalytic water splitting. As a result, Ni or Co single atomic photocatalysts \ud exhibit efficient hydrogen evolution performance with a rate of 1.72 mmol g-1 h\ud -1\ud (AQE=2.05% at 420 nm) under visible-light \ud irradiation beyond pure PCMP. Moreover, the photocatalysts show excellent stability with negligible decreases in the rate \ud of hydrogen evolution upon long-term cycling (25 h). Our findings offer a rational way for the engineering of single atomic \ud photocatalysts for energy and environment-related applications.

Conjugated microporous polymers (CMPs) are porous polymers that have attracted enormous scientific and technical interest in gas adsorption and heterogeneous catalysis. However, most of these conjugated porous polymers involve transition-metal catalysis, and the transition-metal-free radical polymerization method has rarely been investigated. Here, we report the synthesis of conjugated poly(phenylene butadiynylene) polymers by an efficient transition-metal-free radical homocoupling polymerization method. The materials synthesized by this method can achieve high surface areas of up to 1477 m2 g−1, which are superior to those of the reported transition-metal catalysis methods. These highly porous materials showed an excellent capacity for carbon dioxide and hydrogen uptake. This work provides a new methodology to construct high-surface-area organic porous materials.

Airborne particulate matter (PM) has received increasing attention as it causes serious environmental pollution and huge health risk for humans. Herein, we demonstrate the synthesis of tubular conjugated microporous polymers (CMPs) via a one-step cross-coupling reaction for the removal of PM from the air. Tubular CMPs possess a large specific surface area (>484 m2 g−1), high physicochemical stability and mechanical flexibility and robustness. Benefiting from their abundant porosity, CMP-based filters show desirable ability for the capture of PM with a high efficiency of greater than 99% for both PM2.5 and PM10. In combination with their interestingly intrinsic hydrophobicity, a high filtration efficiency for PM2.5 greater than 99.97% can be obtained even under high-humidity conditions (relatively 96 ± 2%), which can be maintained unchanged during a 12 h continuous test, making them highly advantageous over those hydrophilic filters that usually lose their filtration efficiency in a humid environment. Based on their simple fabrication, inherently hydrophobic wettability and high filtration efficiency, the as-synthesized CMP-based filters would hold great potential as promising filters for PM elimination in a humid environment under harsh conditions by taking the advantage of the intrinsically robust physicochemical properties of CMPs. More interestingly, due to the designable flexibility of CMPs, which makes it possible for fine-tuning their pore size or chemical composition, the tailored-design of advanced CMP-based filters for a specific purpose could be anticipated only by rationally varying the size or structure of their building blocks.

Photocatalytic hydrogel composites were prepared by using multifunctional microporous polymer particles as a reinforcing agent and also as a catalytic species. A benzothiadiazole-based conjugated microporous polymer (BTCMP) was synthesized by the Sonogashira-Hagihara reaction between 4,7-dibromo-2,1,3-benzothiadiazole and 1,3,5-triethynylbenzene as insoluble particles. BTCMP particles were functionalized with acryl groups via the thiol-yne click reaction with 2-aminoethanethiol and subsequent reaction with acryloyl chloride. Acrylated BTCMP particles were polymerized with acrylamide in a glass mold to yield a highly elastic hydrogel composite sheet. The tensile test results showed that covalently incorporated BTCMP particles significantly enhanced the mechanical properties of the hydrogels compared with a pure polyacrylamide hydrogel. A possible application of the hydrogel composites for the removal of a dye in water was studied using methylene blue as an exemplary dye. The maximum methylene blue adsorption capacity of the hydrogel composite containing 2 wt% of BTCMP particles was 2.6 times higher than that of the pure Polyacrylamide hydrogel. The hydrogel composite with photocatalytic activity originated from benzothiadiazole groups degraded adsorbed methylene blue molecules in an aqueous solution upon UV irradiation. The hydrogel composite could be reused for the methylene blue removal without any significant decrease in adsorption capacity and catalytic activity.

This work reports a de novo synthesis of novel bifunctional conjugated microporous polymers (CMPs) exhibiting a synergistic-effect involved coordination behavior to uranium. It is highlighted that the synthetic strategy enables the engineering of the coordination environment within amidoxime functionalized CMP frameworks by specifically introducing ortho-substituted amino functionalities, enhancing the affinity to uranyl ions via forming synergistic complexes. The CMPs exhibit high Brunauer-Emmett-Teller (BET) surface area, well-developed three-dimensional (3D) networks with hierarchical porosity, and favorable chemical and thermal stability because of the covalently cross-linked structure. Compared with the amino-free counterparts, the adsorption capacity of bifunctional CMPs was increased by almost 70%, from 105 to 174 mg/g, indicating evidently enhanced binding ability to uranium. Moreover, new insights into coordination mechanism were obtained by in-depth X-ray photoelectron spectroscopy (XPS) analysis and density functional theory (DFT) calculation, suggesting a dominant role of the oxime ligands forming a 1:1 metal ions/ligands (M/L) coordination model with uranyl ions while demonstrating the synergistic engagement of the amino functionalities via direct binding to uranium center and hydrogen-bonding involved secondary-sphere interaction. This work sheds light on the underlying principles of ortho-substituted functionalities directed synergistic effect to promote the coordination of amidoxime with uranyl ions. And the synthetic strategy established here would enable the task-specific development of more novel CMP-based functional materials for broadened applications.

A popular practice in Li-S battery research is to utilize highly nanostructured hosts and excessive electrolytes to enhance sulfur-specific capacities. However, from the perspective of commercialization, this is a less meaningful approach in the pursuit of high-energy Li-S batteries. Herein, we report the fabrication of a nanoskin composed of a conjugated microporous polymer by electropolymerization to create a closed system for a sulfur cathode. The nanoskin is ultrathin, conductive, continuous, and contains uniform micropores of approximately 0.8 nm. The nanoskin sealing prevents the shuttling of polysulfide species without using the absorption effect, enhances the utilization of electrolytes, and allows a fast transport of lithium ions. As a result, the Li-S batteries comprising the cathode with nanoskin exhibit superior stability (∼86% capacity retention) under lean electrolyte conditions and a prolonged lifetime (1000 cycles). At a low electrolyte/sulfur ratio of 4 μL mg-1, the designed cathode delivered a practical energy density of over 300 Wh kg-1 without using any sophisticated hosts.

Organic redox-active materials have emerged as a class of electrode materials for rechargeable batteries due to their high redox activity, low cost, structure diversity and flexibility. However, the high solubility of organic small molecules in organic electrolytes commonly leads to the fast capacity decay with cycling. Herein, we report a redox-active conjugated microporous polymer of poly(pyrene-co-anthraquinone) (PyAq) cathode material consisting of pyrene and anthraquinone units. Benefiting from the highly cross-linked polymer structure with insoluble nature in organic electrolytes, the high surface area and the plentiful redox-active carbonyl groups, the PyAq cathode demonstrates outstanding electrochemical performances for both lithium-ion batteries (LIBs) and potassium-ion batteries (KIBs). Specifically, the PyAq cathode for LIBs delivers a high reversible capacity of 169 mAh g−1 at the current density of 20 mA g−1, a high rate capability (142 mAh g−1 at 1000 mA g−1) and an excellent cycling stability for 4000 cycles. Additionally, the PyAq cathode for KIBs also exhibits a high reversible capacity of 143 mAh g−1 with a long cycling life over 800 cycles. The excellent electrochemical performance demonstrates that the newly developed PyAq could be an attractive cathode material for the advanced energy storage technologies.

Recently, photobiocatalysis with oxidoreductases, inspired by natural photosynthesis, has drawn increasing attention due to its high catalytic efficiency and selectivity. However, although an impor...

The efficient conversion of CO2 to chemical fuels driven by solar energy is still a challenging research area in photosynthesis, in which the conversion efficiency greatly relies on photocatalytic ...

Conjugated microporous polymer (CMP)-based energy-storage materials were developed for pseudocapacitors. Nanoparticulate CMP (N-CMP) with an average diameter of 41±4 nm was prepared through kinetic growth control in the Sonogashira coupling of 1,3,5-triethynylbenzene with 1,4-diiodobenzene. The N-CMP is rich in a diphenylacetylene moiety in its chemical structure. Through the FeCl3 -catalyzed oxidation of diphenylacetylene moieties, N-CMP with benzil moieties (N-CMP-BZ) was prepared and showed enhanced electrochemical performance as an electrode material of pseudocapacitors, compared with CMP, CMP-BZ, and N-CMP. In model studies, the benzil was redox active and showed two-electron reduction behavior. The excellent electrochemical performance of N-CMP-BZ is attributable to the enhanced utilization of functional sites by a nanosize effect and the additional redox contribution of benzil moieties.

Metal phthalocyanine-linked conjugated microporous polymers (MPc-CMPs) have huge potential applications in energy conversion and storage systems. However, the inherent low conductivity limits their practical application. Herein, the MPc-CMPs are hybridized with highly conductive carbon nanotubes (CNTs) via the easy vacuum filtration method. Interestingly, the composite (denoted as CoPc-CMP/CNTs) shows the flexible feature, which can be served as the flexible binder-free electrode for supercapacitors (SCs). As expected, the flexible CoPc-CMP/CNTs exhibits a high specific capacitance of 289.1 F g−1 at a current density of 1 A g−1 and good capacity retention of 82.4% over 1350 cycles at a high current density of 10 A g−1. Furthermore, First-principle calculations are used to elucidate the superiority of CoPc-CMP to other analogues. The good electrochemical performance could be attributed to the synergistic effect from the high pseudocapacitance and good conductivity of CoPc-CMP as well as the capacitive contribution and good conductivity of CNTs. Our strategy provides a new avenue to develop the high-performance SCs via rational integration of MPc-CMPs with highly conductive CNTs.

Redox-active organic compounds have become promising electrode materials for the development of more sustainable, economical, and safer batteries. However, their high electrochemical performance is...

Salen-porphyrin-based conjugated microporous polymers(CMPs) have been demonstrated to be an attractive material platform for predesigned structures and promising applications. Herein, a new salen-porphyrin-based conjugated microporous polymer(SP-CMP-L) was solvothermally prepared by porphyrin-forming condensation reaction of pyrrole and salen-dialdehyde derivative. The SP-CMP-L was characterized by spectroscopy technologies, and also exhibited excellent thermal and chemical stability. The porosity of SP-CMP-L was examined by N2 adsorption/desorption isotherms. The BET specific surface area of the CMP material was calculated to be 290.4 m2/g with the pore volume of 0.19 cm3/g. The microstructure property of the resulting material was further evaculated by scanning electron microscopy(SEM) and transmission electron microscopy(TEM). The SP-CMP-L with salen and porphyrin multidentate coordination sites was proposed to serve as an initiator to promote the cross-coupling between aryl halides with unactivated arenes under base-mediated conditions. The transition-metal-free catalytic protocol provided high catalytic activity for direct C-H arylation reaction of unactivated arenes, and thus offered a convenient and efficient alternative for the construction biaryl scaffolds. In addition, the salen-porphyrin-based CMP material possessed remarkable adsorption capability for the removal of organic amines from water.

Fiber-shaped supercapacitors (FSCs) are promising energy storage devices that meet the growing demands for the miniaturization, flexibility and compatibility of wearable electronics. However, when compared with batteries, the low energy density remains the main limitation to practical applications. Conjugated microporous polymer (CMP) network synthesized using Buchwald-Hartwig cross-coupling reactions, featured tailorable porous structures, reversible redox chemistry and demonstrated highly efficient capacitive performance. Herein CMP network grafted on carbon nanotube fibers (CNF@CMP) with high areal specific capacitance (671.9 mF cm-2 at a current density of 1 mA cm-2) were successfully achieved for polytriphenylamine (PTPA)-based network. All-solid-state symmetrical twisted CNF@PTPA FSCs fabricated with PVA/H3PO4 as gel electrolyte exhibited a high specific areal capacitance of 398 mF cm-2 (0.28 mA cm-2), a maximal operating voltage of 1.4 V, and an energy density of 18.33 μWh cm-2. Moreover, they showed excellent flexibility and mechanical stability retaining 84.5% of the initial capacitance after 10000 bending cycles. These materials provide a new route to high-performance wearable supercapacitors (HPWS), with wide potential applications in wearable electronics, as shown by the examples provided.

Herein, a facile and highly efficient synthetic method to prepare organic photothermal materials with high photo-stability and outstanding photothermal performance is reported. Through direct polymerization of commercial aromatic monomers in the presence of anhydrous aluminium chloride and dichloromethane, four kinds of conjugated microporous polymers (CMPs) were obtained. Detailed structural analysis confirmed that the resultant CMPs possessed abundant micropores with an extended π-conjugated skeleton. Under near-infrared (NIR) light irradiation (808 nm, 1.0 W cm−2), all the CMPs showed fast heating-up behavior with their maximum temperatures higher than 150°C. Moreover, the efficiency of photothermal conversion ( η ) of the CMPs was found to increase linearly with the increase in the number of conjugated benzene rings within the monomer. Poly-TPE from tetraphenylethylene (TPE) and Poly-TP from o -terphenyl (TP) showed high η values of over 47%. Poly-TPE was additionally used as a photothermal filler to remotely and spatially control the shape recovery of thermal-sensitive shape memory polymers (SMPs), while its introduction (1 wt%) had little influence on the thermal and mechanical properties of the polymer matrixes. Owing to their excellent NIR photothermal performance as well as a one-step synthetic preparation, these CMPs may be promising photothermal materials for practical applications.

In order to study the energy transfer between the conjugated polymer and rare-earth ions, a series of conjugated microporous polymers (CMPs) CMP-COOH@M (M=Eu3+ , Tb3+ , La3+ , and Sm3+ ) with different kinds of rare-earth ions was synthesized, in which the conjugated networks can effectively improve the luminescence of rare-earth ions due to the effective energy transfer from the CMP network to the rare-earth ions centers. The absolute quantum yield of CMP-COOH (ΦFL ) is 29.1 %, while the ΦFL value of CMP-COOH@Eu, CMP-COOH@Tb, CMP-COOH@La, and CMP-COOH@Sm is 9.4, 8.6, 14.3, and 9.1 %, respectively. This result indicates that the quantum efficiency of CMPs network is 1/2-1/3 of the original one due to the coordination of rare earth ions, that is, rare-earth ions can be recognized as fine modulators to adjust the emission color of CMPs in a controlled manner through controlling the species of rare-earth ions.

Construction of porous organic polymers (POPs) with high surface areas, well-defined nanopores, and excellent stability remains extremely challenging because of the unmanageable reaction process. Until now, only a few reported POPs have Brunauer-Emmett-Teller (BET) surface areas (SBET ) exceeding 3000 m2 g-1 . Herein, we demonstrate a molecular expansion strategy to integrate high surface areas, large nanopore sizes, and outstanding stability into POPs. A series of hyper-crosslinked conjugated polymers (HCCPs) with exceptional porosity are synthesized through this strategy. Specially, HCCP-6 and HCCP-11 exhibit the highest surface areas (SBET >3000 m2 g-1 ) and excellent total pore volumes (up to 3.98 cm3 g-1 ) among these HCCPs. They present decent total CH4 storage capacities of 491 and 421 mg g-1 at 80 bar and 298 K, respectively. Meanwhile, they are highly stable in harsh environments. The facile and general molecular expansion strategy would lead to improved synthetic routes of POPs for desired functions.

Conjugated microporous polymers (CMPs) as emerging porous materials with diverse structures and tunable building-units have attracted much attention in the electrochemical field. Herein, we designed phthalocyanine-porphyrin-based conjugated microporous polymers as precursors for fabrication of Co, Fe, N tri-doped graphene composites towards oxygen reduction and evolution reaction (ORR/OER). As expected, the elements cobalt and iron are well dispersed in graphene carbon and interact with the nitrogen sites, thereby providing extra electrocatalytic active sites and enhancing its overall conductivity. Benefiting from its unique design and structure, the obtained catalyst affords a superior bifunctional catalytic activity with a positive onset potential of 0.957 V for ORR, and a low overpotential of 0.36 V for OER. More attractively, the CoFeNG is employed as an air cathode catalyst in Zn-air batteries, showing a maximum current density of 215 mA cm-2 and good cycle stability for 20000 s. The rational design of phthalocyanine-porphyrin-based derivatives provides a feasible route for the construction of high-performance ORR/OER catalysts.

Design and synthesis of solid-state photochromic materials remain a challenge because of high structural constrain. However, this can be mitigated in attaining structural flexibility by introducing permanent porosity into the system. Here, we report for the first time the design and synthesis of a photochromic conjugated microporous polymer (pcCMP) by assembling photochromic dithienylethene aldehyde and benzene-1,3,5-tricarbohydrazide. The yellow photo-isomer pcCMP-O gets converted to a deep-green photo-isomer pcCMP-C by UV-light irradiation, which can be reverted to pcCMP-O by visible light or thermal treatment. Owing to the thermo-irreversible nature, the pcCMP is found to be suitable for designing an INH functioning logic gate. pcCMP-C shows highly enhanced conductivity (92 times) because of enhanced conjugation compared to pcCMP-O. Furthermore, we demonstrate the bio-inspired photo-switchable pcFRET process by encapsulation of a red-emissive green fluorescent protein (gfp) chromophore analogue into the pcCMP. This material shows high processibility and has been exploited further for secret writing.

Developing efficient and wide spectrally acting photocatalysts for light-driven hydrogen production from water is highly desirable for solar energy conversion. Herein, diketopyrrolopyrrole (DPP) is...

The designing and development of heterogeneous catalysts for conversion of renewable energy to chemical energies by electrochemical as well as photochemical processes is at the forefront of energy research. In this work, two new donor-acceptor-based redox-active conjugated microporous polymers (CMPs) (TAPA-OPE-mix and TAPA-OPE-gly) are synthesized through Schiff base condensation reaction using a microwave synthesizer. Notably, the asymmetric and symmetric bola-amphiphilic nature of the OPE struts results in distinct nanostructuring and morphologies in the CMPs. Interestingly, both CMPs show impressive heterogeneous catalytic activity toward electrochemical O2 reduction and photocatalytic H2 evolution reactions, and therefore, act as bimodal electro- and photocatalytic porous organic materials. Furthermore, the redox-active property of the CMPs is exploited for in situ generation and stabilization of platinum nanoparticles (Pt), and these Pt@CMPs exhibit significantly enhanced photocatalytic activity.

Precise control of ion transport is a fundamental characteristic for the sustainability of life. It remains a great challenge to develop practical and high-performance artificial ion-transport system that can allow active transport of ions (protons) in an all solid-state nanoporous material. Herein, we develop a Janus microporous membrane by combining reduced graphene oxide (rGO) and conjugated microporous polymer (CMP) for controllable photodriven ion transport. Upon light illumination, a net ionic current is generated from the CMP to the rGO side of the membrane, indicating that the rGO/CMP Janus membrane can realize photodriven directional and anti-gradient ion transport. Analogously to the p-n junction in photovoltaic devices, light is firstly converted into separated charges to trigger a transmembrane potential, which subsequently drives directional ion movement. For the first time, this method enables integration of a photovoltaic effect with an ionic field to drive active ion transport. With the advantages of scaled up production and easy fabrication, the concept of photovoltaic ion transport based on Janus microporous membrane may find wide application in energy storage and conversion, photodriven ion-sieving, and water treatment.

A new photoinitiating system for the metal-free preparation of conjugated microporous polymers (CMPs) is reported. In this approach, irradiation of solutions containing an electroactive monomer, possessing both carbazole and fluorene units, 9,9′-(9,9-dihexyl-9H-fluorene-2,7-diyl)bis-9H-carbazole (CFD), and the iodonium salt (Ph2I+PF6–) as the oxidizing agent resulted in the formation of CMPs. Photoinduced step-growth polymerization proceeded through the successive electron transfer between the excited CFD and iodonium salt, proton release, and coupling reactions. The polymers formed were characterized by FT-IR and 1H NMR analyses. The electrochemical and optical properties of CMPs before and after the dedoping process were evaluated by cyclic voltammetry, differential pulse voltammetry, and UV–vis absorption and photoluminescence techniques. The porous structure of the obtained polymers was confirmed by atomic force microscopy and scanning electron microscopy studies.

With rigid π-conjugated skeletons and permanent micropores, conjugated microporous polymers (CMPs) have attracted increasing interest. Nevertheless, most current studies for CMPs are largely focuse...

Commercial ultrafiltration membranes have proliferated globally for water treatment. However, their pore sizes are too large to sieve gases. Conjugated microporous polymers (CMPs) feature well-developed microporosity yet are difficult to be fabricated into membranes. Herein, we report a strategy to prepare molecular-sieving membranes by partitioning the mesoscopic channels in water ultrafiltration membrane (PSU) into ultra-micropores by space-confined polymerization of multi-functionalized rigid building units. Nine CMP@PSU membranes were obtained, and their separation performance for H2 /CO2 , H2 /N2 , and H2 /CH4 pairs surpass the Robeson upper bound and rival against the best of those reported membranes. Furthermore, highly crosslinked skeletons inside the channels result in the structural robustness and transfer into the excellent aging resistance of the CMP@PSU. This strategy may shed light on the design and fabrication of high-performance polymeric gas separation membranes.

Solar energy is a clean and sustainable energy source. Natural photosynthesis has existed for millions of years, which can convert solar energy into chemical energy needed by living things. Inspired by natural photosynthesis, scientists have developed a series of artificial photosynthetic systems that can use solar energy efficiently for humans. Conjugated microporous polymers (CMPs) are a new class of materials that can be used in artificial photosynthetic systems. This review illustrates the light-harvesting capability and the energy transfer phenomena within the supramolecular structure of CMPs to provide guidelines for the rational design of these polymers with excellent photocatalytic properties and systematically discusses the applications of these materials in the field of photocatalysis including photocatalytic water splitting, CO2 reduction, organic conversion, environmental remediation, and medical health. Finally, this review points out the major challenges in this topic and suggests the next feasible development direction.

The construction of a donor–acceptor (D–A) organic photocatalyst is a facile approach to improve photocatalytic performances because of the efficient separation of light-generated electrons and holes. The rational design of molecular skeletons and the selection of functional groups are of great importance to an organic photocatalyst with a high photocatalytic activity. Herein, we designed two D–A conjugated microporous polymers (CMPs) with different substituent groups of fluorine atoms and methyl groups on the acceptor unit of dibenzothiophene-dioxide (DBTDO). This study reveals that the introduction of fluorine atoms with strong electron-withdrawing ability onto the acceptor unit can further enhance the electron acceptability of the DBTDO unit, leading to the efficient separation of light-generated electrons and holes, while the introduction of methyl with electron-pushing ability decreases the electron acceptability of the acceptor unit, suppressing the separation of light-generated charge carriers. As a result, the polymer PyDF with fluorine atoms shows an excellent photocatalytic activity compared to PyDM with methyl groups. Under UV/Vis light irradiation, PyDF shows an attractive photocatalytic hydrogen generation rate of 18.93 mmol h−1 g−1, which is much higher than that of PyDM (3.96 mmol h−1 g−1), implying that the functional group acts as a vital role in the catalytic activity of polymer semiconducting photocatalysts.

Here we expand our recently reported Bristol–Xi'an Jiaotong (BXJ) approach using simple salts to fine-tune the porosity of conjugated microporous materials synthesized by various reaction approaches, including Buchwald–Hartwig (BH), Sonogashira–Hagihara, oxidative coupling and Suzuki cross-coupling. The surface area and the porosity of the produced conjugated microporous polyanilines (CMPAs) acquired from the non-salt-added BH coupling are optimized by the addition of inorganic salts. BXJ-salt addition provides a facile route to radically improve the BET surface area from 28 to 901 m2 g−1 for PTAPA and from 723 m2 g−1 to 1378 m2 g−1 for PAPA in a controllable manner. In addition, the surface area shows a gradual decrease with an increase in the ionic radius of salts. We furthermore show high compatibility of this approach in the synthesis of typical CMPs, further increasing the surface area from 886 to 1148 m2 g−1, 981 to 1263 m2 g−1, and 35 to 215 m2 g−1 for CMP-1, PTCT and p-PPF, respectively. More importantly, the BXJ approach also allows the broad PSD of the CMPs to be narrowed to the microporous range only, mimicking COFs and MOFs. With the porosity optimized, CO2 uptakes are dramatically improved by >300% from 0.75 mmol g−1 to 2.59 mmol g−1 for PTAPA and from 2.41 mmol g−1 to 2.93 mmol g−1 for PAPA. Careful addressing of Hansen solubility parameters (HSPs) of solvents and resulting polymers through salt addition has the potential to become an important design tool for the preparation of fully tuneable porous materials. We are currently exploring further methods to tune both structure and function in a wide range of organic porous materials.

Efficient catalytic system with low energy consumption exhibits increasing importance due to the upcoming energy crisis. Given this situation, it should be an admirable strategy for reducing energy input by effectively utilizing incident solar energy as a heat source during catalytic reactions. Herein, aza-fused π-conjugated microporous polymer (aza-CMP) with broad light absorption and high photothermal conversion efficiency was synthesized and utilized as a support for bimetallic AuPd nanocatalysts in light-driven benzyl alcohol oxidation. The AuPd nanoparticles anchored on aza-CMP (aza-CMP/AuxPdy) exhibited excellent catalytic performance for benzyl alcohol oxidation under 50 mW/cm2 light irradiation. The improved catalytic performance by the aza-CMP/AuxPdy is attributed to the unique photothermal effect induced by aza-CMP, which can promote the catalytic benzyl alcohol oxidation occurring at AuPd. This work presents a novel approach to effectively utilize solar energy for conventional catalytic reactions through photothermal effect.

[EN]Two-dimensional fused aromatic networks (2D FANs) have emerged as a highly versatile alternative to holey graphene. The synthesis of 2D FANs with increasingly larger lattice dimensions will enable new application perspectives. However, the synthesis of larger analogues is mostly limited by lack of appropriate monomers and methods. Herein, we describe the synthesis, characterisation and properties of an expanded 2D FAN with 90-ring hexagons, which exceed the largest 2D FAN lattices reported to date. This work was carried out with support from the Basque Science Foundation for Science (Ikerbasque),POLYMAT, the University of the Basque Country,Gobierno Vasco (BERC programme) and Gobierno de España (Ministerio de Economía y Competitividad CTQ2016-77970-R).This work was performed under the Maria de Maeztu Units of Excellence Programme–Grant No.CEX-2019-000919-M Ministry of Science, nnovation and Universities.Technica land human support provided by SGIker of UPV/EHU and European funding (ERDFand ESF) is acknowledged.This project has received funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme (GrantAgreementsNo.722951andNo.714122).This project has received funding from the European Union's Horizon 2020 research and innovation programme under grant agreements No.664878 and No.899895. In addition,support through the project IF/00894/2015,the advanced computing project CPCA/A2/2524/2020 granting access to the Navigator cluster at LCA-UC and within the scope of the project CICECO-Aveiro Institute of Materials,UIDB/50011/2020&UIDP/50011/2020 funded by national fund sthrough thePortuguese Foundation for Science andTechnologyI. P./MCTES is gratefully acknowl-edged.The Nanoscale & Microscale Research Centre (nmRC), University of Nottingham,is acknowledged fore nabling access to electron microscopy facilities.

Developing efficient adsorbents for uranium enrichment is of great significance for resource sustainability and environmental safety. This study presents a facile and adaptable post-synthetic strategy to prepare highly efficient uranium adsorbents via engineering the π-conjugated skeletons of homocoupled conjugated microporous polymers (HCMPs). Taking advantage of the diyne units in the π-conjugated skeletons, bis-amidoxime uranophiles, one of the state-of-the-art ligands of uranyl ions, were introduced to the frameworks of HCMPs. The functionalized HCMPs preserved the interconnected 3D microporous networks and rigid conjugated skeletons with abundant bis-amidoxime ligands uniformly distributed in the pore channels. Such structural advantages of the adsorbents afforded very fast adsorption kinetics within 15 min to reach the equilibrium and high capacity of uranium (450 mg/g). Moreover, DFT calculation suggests a synergistic coordination as the most energetically favored coordination mode of the uranyl/bis-amidoxime complexes. This study contributes new insights into the underlying mechanism responsible for the highly efficient adsorption ability of the bis-amidoxime-functionalized HCMPs toward uranium. Meanwhile, the synthetic methodology established here could be extended to task-specific design and skeleton engineering of more functional HCMPs for broadened applications.

We report the design and preparation of hierarchical hollow-pore nanostructure bilayer conjugated polymer films for high-performance resistive memory devices. By taking the merits of chemical and structural stabilities of a two-dimensional conjugated microporous polymer (2D CMP), a poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) film with a hollow surface was spin-coated onto 2D CMP nanofilm directly, constructing a bilayer heterojunction. A two-terminal diode with a configuration of indium tin oxide/2D CMP/hollow MEH-PPV/Al was fabricated by employing the prepared bilayer heterojunction. The device poses flash feature with a high on/off ratio (>105) and a long retention time (>3.0 × 104 s), which is higher than that of most of the reported conjugated polymers memories. Our work offers a general guideline to construct high on/off ratio polymer memories via hierarchical nanostructure engineering in memristive layer.