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Conjugated microporous polymers (CMPs) are an important class of organic materials with several useful features like, inherent nanoscale porosity, large specific surface area and semiconducting properties, which are very demanding for various sustainable applications. Carbazole building blocks are extensively used in designing photocatalysts due to easy electron donation and hole transportation. In the current study, a new CMP material CBZ-CMP containing carbazole unit used for photocatalytic C═N coupling reaction under blue light irradiation is designed. The CBZ-CMP framework is made through the polycondensation of 4,4'-di(9H-carbazol-9-yl)-1,1'-biphenyl using FeCl 3 as a catalyst. The CBZ-CMP shows very high BET surface area of 1536 m 2 g -1 together with unimodal porosity (ca. 1.7 nm supermicropore), nanowire-like particle morphology (16-18 nm diameter), and low band gap property. The bi-phenyl moiety functions as the electron accepting center and the carbazole unit acts as the donor center, which accounts for the low band gap energy of CBZ-CMP. This nanoporous semiconducting CBZ-CMP material for photocatalytic benzylamine coupling reaction is explored, where it shows good conversion together with high selectivity under mild reaction conditions. This study offers simple method of preparation of a D-A-D-based porous photocatalyst for sustainable synthesis of value-added organics., (© 2024 Wiley‐VCH GmbH.)

Conjugated microporous polymers (CMPs) have unique characteristics and have been used in a range of fascinating applications in separation sciences. In this study, a CMP, designated as CMP-1, was synthesized via the Sonogashira-Hagihara coupling reaction using 1,3,5-triphenylbenzene and 1,4-dibromobenzene as building blocks. CMP-1 features a large surface area, abundant micropore structures, and excellent stability, making it a promising solid-phase extraction adsorbent for the efficient enrichment of neonicotinoid insecticides (NEOs). Under the optimized conditions, CMP-1 was combined with high-performance liquid chromatography and diode array detection to enable the detection of NEOs with a wide linear range (0.5-200 μg·L -1 ), a low detection limit (0.26-0.58 μg·L -1 ), and acceptable precision. The developed method was applied to determine spiked NEOs in three types of environmental water samples, with recoveries of 73.7%-112.0% and relative standard deviations of 0.6%-9.4%., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier B.V.)

The development of highly active, durable, and low-cost metal-free catalysts for the photocatalytic CO 2 reduction reaction (CO 2 RR) is an efficient and environmentally friendly solution to address significant problems like global warming and high energy demand. In the present study, we have demonstrated the design and synthesis of a donor-acceptor based conjugated microporous polymer (CMP), TPA-GFP, by integrating an electron donor, tris(4-ethynylphenyl)amine (TPA), with a green fluorescent protein chromophore analogue ( Z )-4-(2-hydroxy-3,5-diiodobenzylidene)-1-(4-iodophenyl)-2-methyl-1 H -imidazol-5(4 H )-one (o-HBDI-I3) (GFP). In comparison to nondonor 1,3,5-triethynylbenzene (TEB) based TEB-GFP CMP, photocatalytic CO 2 reduction using donor-acceptor based TPA-GFP CMP displays a 3-fold increment of CO production yield with a maximum CO yield of 1666 μmol g -1 at 12 h. Further, the CO selectivity increases significantly from a mere 54% in TEB-GFP to an impressive 95% in TPA-GFP. The impressive CO 2 reduction efficiency and selectivity for TPA-GFP can be attributed to the efficient light-harvesting capability and facile charge separation and migration through donor-acceptor building units of the CMP. The mechanistic aspect of the photocatalytic CO 2 reduction process is explored using in situ DRIFTS and DFT calculation, and a plausible photocatalytic mechanism is proposed.

Particle size is a critical factor for improving photocatalytic reactivity of conjugated microporous polymers (CMPs) as mass transfer in the porous materials is often the rate-limiting step. However, due to the synthetic challenge of controlling the size of CMPs, the impact of particle size is yet to be investigated. To address this problem, a simple and versatile dispersion polymerization route that can synthesize dispersible CMP nanoparticles with controlled size from 15 to 180 nm is proposed. Leveraging the precise control of the size, it is demonstrated that smaller CMP nanoparticles have dramatically higher photocatalytic reactivity in various organic transformations, achieving more than 1000% enhancement in the reaction rates by decreasing the size from 180 to 15 nm. The size-dependent photocatalytic reactivity is further scrutinized using a kinetic model and transient absorption spectroscopy, revealing that only the initial 5 nm-thick surface layer of CMP nanoparticles is involved in the photocatalytic reactions because of internal mass transfer limitations. This finding substantiates the potential of small CMP nanoparticles to efficiently use photo-generated excitons and improve energy-efficiency of numerous photocatalytic reactions., (© 2024 The Author(s). Advanced Materials published by Wiley‐VCH GmbH.)

Engineering a catalytic membrane capable of efficiently removing emerging organic microcontaminants under ultrahigh flux conditions is of significance for water purification. Herein, drawing inspiration from the functional attributes of lymphatic vessels involved in immunosurveillance and fluid transport with minimal energy consumption, a novel hierarchical porous catalytic membrane is engineered. This membrane, based on an innovative nitrogen-rich conjugated microporous polymer (polytripheneamine, PTPA), is synthesized using an electrospinning coupled in situ polymerization approach. The resulting bioinspired membrane with hierarchical channels comprises a thin layer (≈1.7 µm) of crosslinked PTPA nanoparticles covering the interconnected electrospun nanofibers. This unique design creates an intrinsic microporous angstrom-confined system capable of activating peroxymonosulfate (PMS) to generate 98.7% singlet oxygen ( 1 O 2 ), enabling durable and highly efficient degradation of microcontaminants. Additionally, the presence of a thin layer of mesoporous structure between PTPA nanoparticles and macroporous channels within the interwoven nanofibers enhances mass transfer efficiency and facilitates high flux rates. Notably, the prepared hierarchical porous organic catalytic membrane demonstrates enduring high-efficiency degradation performance with a superior permeance (>95% and >2500 L m -2 h -1 bar -1 ) sustained over 100 h. This work introduces an innovative pathway for the design of high-performance catalytic membranes for the removal of emerging organic microcontaminants., (© 2024 The Author(s). Advanced Science published by Wiley‐VCH GmbH.)

Porous iron-nitrogen-doped carbons (FeNC) offer a great platform for construction of cathodic oxygen reduction reaction (ORR) catalysts in fuel cells. However, challenges still remain regarding with the collapse of carbon-skeleton during pyrolysis, uneven distribution of active sites and aggregation of metal atoms. In this work, we synthesized Fe, N co-doped conjugated microporous polymer (FeN-CMP) through a facile bottom-up strategy using 1,3,5-triethynylbenzene and iron-chelated 3,8-dibromo-1,10-phenanthroline as monomers, ensuring the uniform coordination of N with Fe element in network. Then, the resulting FeN-CMP was treated by pyrolysis without structural collapse to obtain porous FeNC electrocatalyst for ORR. The most active catalyst was fabricated under 900 °C, which exhibits remarkable ORR activity in alkaline medium with half-wave potential of 0.796 V (18 mV and 105 mV positive deviation from the commercial Pt/C catalyst and post-doping catalyst), high selectivity with nearly 4e - transfer process and excellent methanol tolerance. Our study first developed porous FeNC electrocatalysts derived from Fe, N-anchoring CMPs based on pre-functionalization of monomers, which exhibits great potential as an alternative to commercial Pt/C catalyst for ORR, and provides a feasible strategy of developing multi-atoms doping catalysts for energy storage and conversion as well as heterogeneous catalysis., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Inc.)

Photocatalytic selective oxidation plays an important role in developing green chemistry. However, it is challenging to design an efficient photocatalyst for controlling the selectivity of photocatalytic oxidation reaction and exploring its detailed mechanism. Here, we synthesized three conjugated microporous polymers (CMPs) with D-A structures, named M-SATE-CMPs (MZn, Cu and Co), with different d-band centers based on different metal centers, resulting in the discrepancy in adsorption and activation capacities for the reactants, which produces the selectivity of β-keto esters being catalyzed into α-hydroperoxide β-keto esters (ROOH) or to α-hydroxyl β-keto esters (ROH). Density functional theory (DFT) calculations also demonstrate that the adsorption and activation capacities of the metal active centers in M-SATE-CMPs (MZn, Cu and Co) for ROOH are the key factors to influence the photocatalytic selective oxidation of β-keto ester. This study provides a promising strategy for designing a metallaphotoredox catalyst whose photocatalytic selectivity depends on the d-band center of metal site in the catalyst., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

Conjugated polymers have attracted significant attention in the field of photocatalysis due to their exceptional properties, including versatile optimization, cost-effectiveness, and structure stability. Herein, two conjugated porous polymers, PhIN-CPP and ThIN-CPP, based on triazines, were meticulously designed and successfully synthesized using benzene and thiophene as building blocks. Based on UV diffuse reflection spectra, the photonic band gaps of PhIN-CPP and ThIN-CPP were calculated as 2.05 eV and 1.79 eV. The PhIN-CPP exhibited a high hydrogen evolution rate (HER) of 5359.92 μmol·g -1 ·h -1 , which is 10 times higher than that of Thin-CPP (538.49 μmol·g -1 ·h -1 ). The remarkable disparity in the photocatalytic performance can be primarily ascribed to alterations in the band structure of the polymers, which includes its more stable benzene units, fluffier structure, larger specific surface area, most pronounced absorption occurring in the visible region and highly extended conjugation with a high density of electrons. The ΔE ST values for PhIN-CPP and ThIN-CPP were calculated as 0.79 eV and 0.80 eV, respectively, based on DFT and TD-DFT calculations, which revealed that the incorporation of triazine units in the as-prepared CMPs could enhance the charge transfer via S1 ↔ T1 and was beneficial to the photocatalytic decomposition of H 2 O. This study presents a novel concept for developing a hybrid system for preparation of H 2 by photocatalysis with effectiveness, sustainability, and economy.

Anthracene- and pyrene-based twisted porous graphene ( AN-Pyre-PG ) with an ordered pore structure has been synthesized through bottom-up solution phase synthesis from a conjugated microporous polymer ( AN-Pyre-CMP ) via a heterogeneous Scholl cyclization reaction. The regular-ordered pores embedded within the graphene structures were analyzed through a Raman spectrum, different morphological analyses, and theoretical studies. A significant change in surface area from AN-Pyre-CMP to AN-Pyre-PG was observed, from 143 to 640 m 2 /g, respectively. Surface area-driven capacitive properties were also observed. Twisted-structure and ordered porous graphene shows better specific capacitance compared to CMP. AN-Pyre-PG shows a specific capacitance of 629 F g -1 at 1 A g -1 , with 91% retention of capacitance after 3000 charge-discharge cycles, whereas AN-Pyre-CMP shows a maximum specific capacitance of 200 F g -1 was observed at 2 A g -1 .

High-quality conjugated microporous polymer (CMP) films with orientation and controlled structure are extremely desired for applications. Here, we report the effective construction of CMP 3D composite films (pZn/PTPCz) with a controlled porosity structure and preferred orientation using the template-assisted electropolymerization (EP) approach for the first time. The structure of pZn/PTPCz composite thin films and nitrophenol sensing performance were thoroughly studied. When compared to the control CMP film made on flat indium tin oxide (ITO) substrates, the as-prepared pZn/PTPCz composite films showed significantly enhanced fluorescent intensity and much better sensing performance for the model explosive. This was attributed to the metal-enhanced fluorescence (MEF) of porous nanostructured zinc (pZn) and the additional macroporosity of the pZn/PTPCz composite films. This work provides a feasible approach for creating oriented 3D CMP-based thin films for advanced applications., (© 2024 Wiley‐VCH GmbH.)

The design and synthesis of organic photocatalysts remain a great challenge due to their strict structural constraints. However, this could be mitigated by achieving structural flexibility by constructing permanent porosity into the materials. Conjugated microporous polymers (CMPs) are an emerging class of porous materials with an amorphous, three-dimensional network structure, which makes it possible to integrate the elaborate functional groups to enhance photocatalytic performance. Here, we report the synthesis of a novel CMP, named TAPFc-TFPPy-CMP, constructed by 1,1'3,3'-tetra(4-aminophenyl)ferrocene (TAPFc) and 1,3,6,8-tetrakis(4-formylphenyl)pyrene (TFPPy) monomers. The integration of the p -type dopant 7,7,8,8-tetracyanoquinodimethane (TCNQ) into the TAPFc-TFPPy-CMP improved the light adsorption performance, leading to a decrease in the optical bandgap from 2.00 to 1.43 eV. The doped CMP (TCNQ@TAPFc-TFPPy-CMP) exhibited promising catalytic activity in photocatalytic CO 2 reduction under visible light, yielding 546.8 μmol g -1 h -1 of CO with a selectivity of 96% and 5.2 μmol g -1 h -1 of CH 4 . This represented an 80% increase in the CO yield compared to the maternal TAPFc-TFPPy-CMP. The steady-state photoluminescence (PL) and fluorescence lifetime (FL) measurements reveal faster carrier separation and transport after the doping. This study provides guidance for the development of organic photocatalysts for the utilization of renewable energy.

Developing efficient oxygen evolution catalysts (OECs) made from earth-abundant elements is extremely important since the oxygen evolution reaction (OER) with sluggish kinetics hinders the development of many energy-related electrochemical devices. Herein, an efficient strategy is developed to prepare conjugated microporous polymers (CMPs) with abundant and uniform coordination sites by coupling the N-rich organic monomer 2,4,6-tris(5-bromopyrimidin-2-yl)-1,3,5-triazine (TBPT) with Co(II) porphyrin. The resulting CMP-Py(Co) is further metallized with Co 2+ ions to obtain CMP-Py(Co)@Co. Structural characterization results reveal that CMP-Py(Co)@Co has higher Co 2+ content (12.20 wt %) and affinity toward water compared with CMP-Py(Co). Moreover, CMP-Py(Co)@Co exhibits an excellent OER activity with a low overpotential of 285 mV vs RHE at 10 mA cm -2 and a Tafel slope of 80.1 mV dec -1 , which are significantly lower than those of CMP-Py(Co) (335 mV vs RHE and 96.8 mV dec -1 ). More interestingly, CMP-Py(Co)@Co outperforms most reported porous organic polymer-based OECs and the benchmark RuO 2 catalyst (320 mV vs RHE and 87.6 mV dec -1 ). Additionally, Co 2+ -free CMP-Py(2H) has negligible OER activity. Thereby, the enhanced OER activity of CMP-Py(Co)@Co is attributed to the incorporation of Co 2+ ions leading to rich active sites and enlarged electrochemical surface areas. Density functional theory (DFT) calculations reveal that Co 2+ -TBPT sites have higher activity than Co 2+ -porphyrin sites for the OER. These results indicate that the introduction of rich active metal sites in stable and conductive CMPs could provide novel guidance for designing efficient OECs.

Developing antibiotic-free treatment strategies to cope with the crisis on drug-resistant bacteria, are urgently needed. Antibiotics-independent physical approaches, especially the non-invasive phototherapies, worked through the assistance of photosensitizer (PS), have geared intensive attention and interests. Here, composite porphyrin-based conjugated microporous polymer/graphene oxide, denoted as GO-TAPP, combining the advantages of each component perfectly, was developed as broad-spectrum antibacterial agent. GO-TAPP, prepared via the self-oxidation coupling of tetraethynyl porphyrin on the surface of graphene oxide, could exert synergistic photothermal (PTT, ascribed to the graphene) and photodynamic (PDT, derived from the Porphyrin polymer) antimicrobial effectiveness. Both the in vivo and in vitro experiments have confirmed GO-TAPP are extremely potent against the Gram-positive (Staphylococcus aureus) and Gram-negative (Escherichia coli) pathogens, which presents a remarkably enhanced sterilizing effect in comparison with its counterparts (the bare GO, and TAPP). Meanwhile, the synergistic effect of GO-TAPP could significantly accelerate the healing of open wound infected by bacterial. Altogether, this work proposed a new approach for the rational preparation of highly biocompatible graphene-based composite materials as antibiotic-free agents with synergistic antibacterial effect to combat bacterial infections., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Baolong Zhou reports financial support was provided by Weifang Medical University. Baolong Zhou reports was provided by National Science foundation of shandong Province. Baolong Zhou reports a relationship with Weifang Medical University that includes: board membership. Baolong Zhou has patent pending to No. There are no conflicts of interest., (Copyright © 2023. Published by Elsevier B.V.)

Herein, we synthesized a conjugated microporous polymer (CMP) decorated C 60 (CMP@C 60 ) with high photoelectric conversion efficiency, in which continuously repeated donor-acceptor (D-A) π electron unit within one molecule of CMP on C 60 could not only effectively increase the mobility of photogenerated carriers with improved electron transmission, but also constitute the cascade energy band matching with reduced electron-hole recombination. Based on the high-performance of CMP@C 60 for producing exciting initial photoelectrochemical (PEC) signal, a sensitive signal-off sensing platform was designed for lead ion (Pb 2+ ) assay by coupling with quencher methylene blue (MB) interacting on efficient long tailed Y-triangular DNA structure (LYTD). The proposed LYTD with a tripod structure could generate six long tails in situ on its side at the same time via a simple hybridization chain reaction (HCR), providing notably grooves on electrode to accommodate quencher MB to significantly depress the signal for sensitive detection of Pb 2+ . As a result, the proposed PEC biosensor revealed excellent analysis capability with a low detection limit of 0.3 fM (S/N = 3). Additionally, it also showed satisfactory stability in the detection of tap water samples, lake water samples and clinical serum samples, manifesting great application prospect in the areas of environmental pollutant detection., Competing Interests: Declaration of Competing Interest We confirm that the manuscript has been read and approved by all named authors and that there are no other persons who satisfied the criteria for authorship but are not listed. We further confirm that the order of authors listed in the manuscript has been approved by all of us. We confirm that we have given due consideration to the protection of intellectual property associated with this work and that there are no impediments to publication, including the timing of publication, with respect to intellectual property. In so doing we confirm that we have followed the regulations of our institutions concerning intellectual property., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Solar-driven interfacial evaporation (SDIE) with excellent photothermal conversion efficiency is emerging as one of the frontier technologies for freshwater production. In this work, novel carbonized conjugate microporous polymers (CCMPs) hollow microspheres-based composite hydrogel membranes (CCMPsHM-CHM) for efficient SDIE are reported. The precursor, CMPs hollow microspheres (CMPsHM), is synthesized by an in situ Sonogashira-Hagihara cross-coupling reaction using a hard template method. The as-synthesized CCMPsHM-CHM exhibit significantly excellent properties, i.e. , 3D hierarchical architecture (from micropore to macropore), superior solar light absorption (more than 89%), better thermal insulation (thermal conductivity as low as 0.32-0.42 W m -1 K -1 in the wet state), superhydrophilic wettability with a water contact angle (WCA) of 0°, superior solar efficiency (up to 89-91%), a high evaporation rate of 1.48-1.51 kg m -2 h -1 under 1 sun irradiation, and excellent stability which maintains an evaporation rate of more than 80% after 10 cycles and over 83% evaporation efficiency in highly concentrated brine. In this case, the removal rate of metal ions in seawater is more than 99%, which is much lower than the ion concentration standard for drinking water set by the World Health Organization (WHO) and the United States Environmental Protection Agency (USEPA). Taking advantage of its simple and scalable manufacture, our CCMPsHM-CHM may have great potential as advanced membranes for various applications for efficient SDIE in different environments.

The consumption of famciclovir (FCV) has been increased dramatically since the outbreak of coronavirus in 2019, and the pollution and harm of FCV in waters are concerned. Here, by utilizing aryl halides on 2, 4, 6-tris(4-bromophenyl)- 1, 3, 5-triazine (BPT) and primary amine groups on benzidine (BZ), a novel conjugated microporous polymer, namely BPT-BZ-CMP, was synthesized by Buchwald-Hartwig coupling reaction and applied in the removal of FCV from aqueous solution firstly. The synthesized BPT-BZ-CMP were characterized by various methods, including FTIR, SEM, BET, and Zeta-potential. Due to the micropore structure and high specific surface area, it took only 30 min for BPT-BZ-CMP to adsorb FCV to reach an equilibrium, and the maximum adsorption capacity was 347.8 mg·g -1 . The Liu and pseudo-second-order kinetic models properly fit the adsorption equilibrium and kinetic data, respectively. The adsorption process was a spontaneous process, and the hydrogen bonding, π-π interaction and C-H···π interaction enhanced the adsorption of FCV on BPT-BZ-CMP. BPT-BZ-CMP maintained a good adsorption capacity after four consecutive adsorption-desorption cycle experiments. This study confirmed the potential of BPT-BZ-CMP as efficient sorbent to remove FCV from aqueous solutions., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (© 2022 Elsevier B.V. All rights reserved.)

Since the 1960s, levodopa (LDA) has been the standard drug for treating of Parkinson's disease. In this study, a novel benzothiadiazole-based conjugated microporous polymer-coated graphene heterostructure (CMP-rGO) was synthesized and used to construct a sensitive photoelectrochemical (PEC) sensor capable of detecting LDA. Under optimal experimental conditions, the intensity of the photocurrent produced by the sensor was linear from 0.005 to 40 μM, and the limit of detection of the sensor was 0.0027 μM. The sensor showed good repeatability, stability, and selectivity for LDA detection. Finally, the constructed sensor was used to detect LDA in levodopa tablets, human serum samples, and urine samples and satisfactory results were obtained. Therefore, the PEC sensor provides a novel platform for the detection of LDA in real samples and broadens the applications of conjugated microporous polymers in PEC sensing.

Lithium-sulfur (Li-S) batteries are very promising high-energy-density electrochemical energy storage devices, but suffer from serious Li polysulfide (LiPS) shuttle and uncontrollable Li dendrite growth. Here, we show in situ polyolefin separator modification with an N-rich conjugated microporous polymer (NCMP) for advanced Li-S battery. In situ polymerization generates an ultrathin NCMP coating on the whole external surface and the internal surface of the separator, which is substantially different from the conventional approaches with thick coatings only on the external surface. The NCMP coating with abundant N-containing groups (-NH 2 and -N═), uniform nanopores (12.294 Å), and π-conjugated structure can simultaneously inhibit LiPS shuttle and regulate uniform nucleation and growth of Li dendrites. Consequently, the NCMP-based separator endows the Li-S battery with significantly enhanced cycling stability at high S loading (5.4 mg cm -2 ), lean electrolyte (E/S = 6.3 μL mg -1 ), and limited Li excess (50 μm).

Substrate accessibility is a key limiting factor for the efficiency of heterogeneous photoredox catalysis. Recently, a high photoactive surface area of conjugated microporous polymer nanoparticles (CMP NPs) has made them promising candidates for overcoming the mass transfer limitation to achieve high photocatalytic efficiency. However, this potential has not been realized due to limited dispersibility of CMP NPs in many solvents, particularly in water. Here, we report a polymer grafting strategy that furnishes versatile hairy CMP NPs with enhanced solvent-specific dispersibility. The method associates hundreds of solvent-miscible repeating units with one chain end of the photocatalyst surface, allowing minimal modification to the CMP network that preserves its photocatalytic activity. Therefore, the enhanced dispersibility of hairy CMP NPs in organic solvents or aqueous solutions affords high efficiency in various photocatalytic organic transformations.

Numerous applications in visible light photocatalysis have been found over conjugated microporous polymers (CMPs) whose function could be rationally designed at the molecular level. In this context, the oxidation of thiols into disulfides entails proton and electron transfer and thus requires both Brønsted base and photocatalysis, which could be both combined into CMPs. With carbazole as a Brønsted base and an electron donor, CMPs were constructed to implement the synergistic deprotonation and oxidation of thiols into disulfides in ethanol (C 2 H 5 OH). Gratifyingly, the bifunctional CMPs could activate molecular oxygen (O 2 ) to superoxide anion (O 2 •- ) and promote the blue light-induced selective oxidation of thiols into symmetrical disulfides with high efficiency in C 2 H 5 OH. More remarkably, the highly selective formation of unsymmetrical disulfides could also be achieved without adding a Brønsted base. This work highlights the feasibility of combining cooperative photocatalysis into CMPs for versatile chemical transformations., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Inc. All rights reserved.)

Inspired by natural photosynthesis, photocatalytic NADH regeneration has drawn increasing interest in the recent decade as it provides a perfect approach for NAD + reduction into NADH, which can be further consumed by oxidordeuctase for enzymatic redox reactions. However, two issues still remain unsolved in this procedure. First, the photocatalytic efficiency in NAD + hydrogenation requires further improvement. Second, the rhodium electron mediator [Cp*Rh(bpy)H 2 O] 2+ ( M ), which is always required for selective 1,4-NADH regeneration, is difficult to recover because of its good solubility in aqueous solution. Given the high price of M , it is highly wasteful and inefficient if it only spends once. Here, we report a Cp*Rh(bpy)Cl implanted conjugated microporous polymer DTS/Rh@CMPs which can be employed as a highly effective visible light photocatalysts for in situ NADH regeneration without using additional M . In addition, the insertion of Rh complex into a polymer skeleton, as demonstrated in UV-vis, fluorescence, photocurrent and electrochemical impedance, dramatically improves the light absorption capacity and the electron separation and transfer efficiency. Compared with that of DTS@CMP-1 with M , an enhanced reaction yield of 33% was determined in DTS/Rh@CMP-1 suggesting that intramolecular electron transfer has a better activity than that of intermolecular electron transfer in photocatalytic NAD + reduction. Moreover, as the Rh complex is rooted firmly in a polymer framework, negligible Rh loss and conversion decrease in NADH regeneration are observed. When the DTS/Rh@CMP-1 was coupled with yeast alcohol dehydrogenase (YADH, from Saccharomyces cerevisiae ), 1.36 mM of methanol was accumulated, implying an excellent biocompatibility of DTS/Rh@CMP-1 and a high feasibility of photobiocatalysis for formaldehyde hydrogenation.

Photocatalytic reduction and removal of toxic uranium(VI) from aqueous solution is a highly economic, non-pollutant and efficient strategy. However, most uranium containing waste waters are highly acidic, but current photocatalysts are still restricted in slightly acidic or neutral media (pH ≥ 4). Herein, a conjugated microporous polymer (CMP), pTTT-Ben, was used for visible light driven photocatalytic reduction of U(VI) in highly acidic condition (pH = 1). A high uranium removal capacity (4710 mg/g) was achieved. The structural information of reduced uranium was investigated by X-ray photoelectron spectroscopy (XPS) and extended X-ray absorption fine structure (EXAFS), revealing the amorphous U(IV) hydrate complex, with an additional interaction between U(IV) and nitrogen atoms on pTTT-Ben. In addition, pTTT-Ben also showed excellent photocatalytic U(VI) reduction performance under natural sunlight irradiation., (Copyright © 2021. Published by Elsevier B.V.)

One sustainable concept emerges to implement the selective oxidation of sulfides with dioxygen (O 2 ) at ambient conditions and has received increasing attention. As such, three donor-acceptor (D-A) type conjugated microporous polymers (CMPs) were connected via robust CC bonds prepared from FeCl 3 -promoted polymerization of monomers of 3,6-di(9H-carbazol-9-yl)-9H-fluorene with the 9H position of the fluorene moiety occupied by 1,1'-biphenyl-, difluoro-, or keto- group, furnishing 9,9'-(9,9'-spirobi[fluorene]-2,7-diyl)-bis-9H-carbazole-CMP (SFC-CMP), 9,9'-(9,9-difluoro-9H-fluorene-2,7-diyl)bis(9H-carbazole)-CMP (FFC-CMP), and 2,7-di(carbazol-9-yl)-fluoren-9-one-CMP (OFC-CMP), respectively. These three carbazole-fluorene CMPs could implement blue light-driven highly selective oxidation of sulfides into sulfoxides with O 2 in methanol (CH 3 OH). Intriguingly, the SFC-CMP imparted the best photocatalytic activity for selective oxidation of sulfides in a broad scope. Besides, the SFC-CMP photocatalyst could be fully recovered even outperforming the fresh one. This work highlights that the properties of CMPs could be regulated by the D-A units like carbazole-fluorene to execute selective chemical transformations ambiently., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier Inc. All rights reserved.)

The exploitation of high-performance filters which can capture and remove airborne particulate matter (PM) in harsh conditions is greatly important to limit the serious effect of PM on human health. Herein, we demonstrate a simple approach for the creation of robust and hierarchically porous filters based on conjugated microporous polymers (CMPs) nanotubes for efficient PM capture. Taking advantage of their inherently superhydrophobic wettability, the CMPs-based filters possess high filtration efficiency of higher than 99.4% for PM 0.3 and 99.9% for PM 2.5 and PM 10 , respectively, even in high humidity environment (RH ≥ 94%). The CMPs-based filters show highly physicochemical and thermal stability, e.g., by calcination at 500 °C for 2 h, the filtration efficiency of the samples still reaches as great as 99.4% for both PM 2.5 and PM 10 with a low-pressure drop of only 10 Pa. In addition, these CMPs-based filters can be easily regenerated and their high PM filtration efficiency remains nearly unchanged by a simple methanol washing. More interestingly, the CMPs-based filters also exhibit superior antibacterial performance, which enables them to sterilize or eliminate the bacteria possibly loaded on PM pollutions, thus showing great potential for various applications such as PM removal, air purification and so on., (Copyright © 2021 Elsevier B.V. All rights reserved.)

A conjugated microporous organic polymer (TPA-Bp) comprised of triphenylamine (TPA) and 2,2'-bipyridine-5,5'-diformaldehyde (Bp) was prepared via the Schiff-base reaction under ambient conditions. TPA-Bp is an amorphous and microporous spherical nanoparticle with very high stability. TPA-Bp suspension in DMF displayed strong fluorescence emission and selective fluorescence quenching response towards Fe 3+ and Fe 2+ ions. The fluorescence intensity of TPA-Bp at 331 nm presents linear relationship with the concentrations of both Fe 3+ and Fe 2+ with low detection limits of 1.02 × 10 -5  M for Fe 3+ and 5.37 × 10 -6  M for Fe 2+ . The results of X-ray photoelectron spectroscopy (XPS) and Fourier Transform infrared spectroscopy (FTIR) confirm the selective coordination of N atoms of pyridine unit with Fe ions. The fluorescence quenching of TPA-Bp upon the addition of Fe 3+ /Fe 2+ ions can be attributed to the absorption competition quenching (ACQ) mechanism and the energy transfer between TPA-Bp and Fe 3+ /Fe 2+ ions. This work demonstrates that the conjugated microporous polymers are promising candidates as luminescent sensor for detection of the special analytes in practical applications., (Copyright © 2021 Elsevier B.V. All rights reserved.)

The development of an efficient, sustainable, and inexpensive metal-free catalyst for oxygen evolution reaction (OER) via photoelectrochemical water splitting is very demanding for energy conversion processes such as green fuel generators, fuel cells, and metal-air batteries. Herein, we have developed a metal-free pyrene-based nitrogen and sulfur containing conjugated microporous polymer having a high Brunauer-Emmett-Teller surface area (761 m 2  g -1 ) and a low bandgap of 2.09 eV for oxygen evolution reaction (OER) in alkaline solution. The π -conjugated as-synthesized porous organic material (PBTDZ) has been characterized by Fourier transform infrared spectroscopy (FT-IR), solid-state 13 C (cross-polarization magic angle spinning-nuclear magnetic resonance) CP-MAS NMR, N 2 adsorption/desorption analysis, field-emission scanning electron microscope (FESEM), high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS) and thermogravimetric analysis (TGA) experiments. The material acts as an efficient catalyst for photoelectrochemical OER with a current density of 80 mA/cm 2 at 0.8 V vs. Ag/AgCl and delivered 104 µmol of oxygen in a 2 h run. The presence of low bandgap energy, π -conjugated conducting polymeric skeleton bearing donor heteroatoms (N and S), and higher specific surface area associated with inherent microporosity are responsible for this admirable photoelectrocatalytic activity of PBTDZ catalyst., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2021 Das, Shyamal, Das, Mondal, Chowdhury, Chakraborty, Dey and Bhaumik.)

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.

High-performance conjugated microporous polymer (CMP)/TiO 2 photocatalytic antibacterial nanocomposites were successfully synthesized by in situ Sonogashira polymerization. TiO 2 was uniformly dispersed onto the surface and within the CMP which show the microporous nature with narrow pore size distribution. The high crystallinity and thermal stability of the CMP/TiO 2 nanocomposites are attractive for use as antibacterial materials. The composites we prepared showed excellent photocatalytic antibacterial properties for the inactivation of Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) under visible light irradiation. The photocatalytic antibacterial rates of nanocomposites against E. coli and S. aureus after 120 min of visible light irradiation were 98.14% and 100%, respectively. The superoxide anion (O 2 - ) was confirmed to be an important substance in the antibacterial process above. The cytocompatibility of the antibacterial agents was studied in terms of cytotoxicity against NIH 3T3 fibroblasts. More than 95% of the cells were still alive in the presence of the nanocomposites, both without and with light irradiation, indicating the good cytocompatibility of the nanocomposites. Judging from the excellent photocatalytic antibacterial properties and ultralow toxicity of nanocomposites, these materials can be used in many fields such as medical treatment, transportation and construction., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Porous organic polymers have been received considerable attention due to their heteroatom-containing structures and high surface areas, which can offer high electrochemical performance in energy applications. The majority of reported Tröger's base-functionalized porous organic polymers have been applied as effective candidates for sensing and gas separation/adsorption, while their use as electrode materials in supercapacitors is rare. Here, a novel covalent microporous organic polymer containing carbazole and Tröger's base CzT-CMOP has been successfully synthesized through the one-pot polycondensation of 9-(4-aminophenyl)-carbazole-3,6-diamine (Cz-3NH 2 ) with dimethoxymethane. The polycondensation reaction's regioselectivity was studied using spectroscopic analyses and electronic structure calculations that confirmed the polycondensation occurred through the second and seventh positions of the carbazole unit rather than the fourth and fifth positions confirmed by first-principles calculations. Our CzT-CMOP exhibited high thermal stability of approximately 463.5 °C and a relatively high Brunauer-Emmett-Teller surface area of 615 m 2 g -1 with a nonlocal density functional theory's pore size and volume of 0.48 cm 3 g -1 and 1.66 nm, respectively. In addition, the synthesized CzT-CMOP displayed redox activity due to the existence of a redox-active carbazole in the polymer skeleton. CzT-CMOP revealed high electrochemical performance when used as active-electrode material in a three-electrode supercapacitor with an aqueous electrolyte of 6 M KOH, and it showed specific capacitance of 240 F g -1 at a current density of 0.5 A g -1 with excellent stability after 2000 cycles of 97% capacitance retention. Accordingly, such porous organic polymer appears to have a variety of uses in energy-related applications.

Introducing nonvolatile liquid acids into porous solids is a promising solution to construct anhydrous proton-conducting electrolytes, but due to weak coordination or covalent bonds building these solids, they often suffer from structural instability in acidic environments. Herein, we report a series of steady conjugated microporous polymers (CMPs) linked by robust alkynyl bonds and functionalized with perfluoroalkyl groups and incorporate them with phosphoric acid. The resulting composite electrolyte exhibits high anhydrous proton conductivity at 30-120 °C (up to 4.39 × 10 -3 S cm -1 ), and the activation energy is less than 0.4 eV. The excellent proton conductivity is attributed to the hydrophobic pores that provide nanospace for continuous proton transport, and the hydrogen bonding between phosphoric acid and perfluoroalkyl chains of CMPs promotes short-distance proton hopping from one side to the other.

Among various organic cathode materials, C═O group-enriched structures have attracted wide attention worldwide. However, small organic molecules have long suffered from dissolving in electrolytes during charge-discharge cycles. π-Conjugated microporous polymers (CMPs) become one solution to address this issue. However, the synthesis strategy for CMPs with rich C═O groups and stable backbones remains a challenge. In this study, a novel CMP enriched with C═O units was synthesized through a highly efficient Diels-Alder reaction. The as-prepared CMP exhibited a fused carbon backbone and a semiconductive characteristic with a band gap of 1.4 eV. When used as an organic electrode material in LIBs, the insoluble and robust fused structure caused such CMPs to exhibit remarkable cycling stability (a 96.1% capacity retention at 0.2 A g -1 after 200 cycles and a 94.8% capacity retention at 1 A g -1 after 1500 cycles), superior lithium-ion diffusion coefficient (5.30 × 10 -11 cm 2 s -1 ), and excellent rate capability (95.8 mAh g -1 at 1 A g -1 ). This study provided a novel synthetic method for fabricating quinone-enriched fused CMPs, which can be used as LIB cathode materials.

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.

Suppressing the operating current in resistive memory devices is an effective strategy to minimize their power consumption. Herein, we present an intrinsic low-current memory based on two-dimensional (2D) hybrid heterostructures consisting of partly reduced graphene oxide (p-rGO) and conjugated microporous polymer (CMP) with the merits of being solution-processed, large-scale, and well patterned. The device with the heterostructure of p-rGO/CMP sandwiched between highly reduced graphene oxide (h-rGO) and aluminum electrodes exhibited rewritable and nonvolatile memory behavior with an ultralow operating current (∼1 μA) and efficient power consumption (∼2.9 μW). Moreover, the on/off current ratio is over 10 3 , and the retention time is up to 8 × 10 3 s, indicating the low misreading rate and high stability of data storage. So far, the value of power is about 10 times lower than those of the previous GO-based memories. The bilayer architecture provides a promising approach to construct intrinsic low-power resistive memory devices.

The existence of Fluoroquinolones (FQs), non-biodegradable pharmacophores, in the natural environment possesses a serious threat. We herein report a novel, rapid, room-temperature synthesis of semiconducting conjugated microporous polymer (CMP) for the decontamination of four second-generation FQs, Norfloxacin, Enrofloxacin, Ciprofloxacin, and Ofloxacin. The CMP demonstrated impressive gas uptake and FQ adsorption ability. Decreased HOMO-LUMO bandgap resulted in enhanced exciton pair generation on visible-light-illumination. Additionally, a high degree of photocurrent response and suitable redox potentials of the material conjointly endorsed its almost quantitative FQ-degradation efficiency. Ofloxacin showed the best removal efficiency with 0.061 and 0.207 min -1 adsorption and degradation rate constants, respectively, one of the highest values reported. The CMP exhibited equipotent activity for other FQs as well. On increasing the concentration of the FQs or decreasing the incident photo-intensity, quantitative removal efficiencies are observed. Changing the pH of the medium from acidic to alkaline did not impart any change in catalytic activity as well. The reactive species involved viz. O 2 - , 1 O 2 , etc. and their roles in the degradation process were determined through control and trapping experiments. A plausible in-depth mechanistic pathway was assessed from the FQ degradation intermediates, and the reactive catalytic species substantiating step-by-step break down of the antibiotic backbone., (Copyright © 2020 Elsevier B.V. All rights reserved.)

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 FeCl 3 -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., (© 2020 Wiley-VCH GmbH.)

Two kinds of fluorescent conjugated microporous polymers containing pyrazine moieties were prepared by the polymerization reaction of 2,5-di-triphenylamine-yl-pyrazine (DTPAPz) and N,N,N',N'-tetrapheny-2,5-(diazyl) pyrazine (TDPz) with 2,4,6-trichloro-1,3,5-triazine (TCT) through Friedel-Crafts reaction using the methanesulfonic acid as a catalysts. Both CMPs have high thermal stability and decomposition temperature reaches above 596 and 248 °C under nitrogen atmosphere, respectively. By right of porous morphology and electron-donating nitrogen, as well as electron-rich π-conjugated structures, the adsorption performance for iodine vapor on the CMPs is very excellent, which can reach 441% and 312%. In addition, fluorescence studies showed that the two CMPs exhibited high fluorescence sensitivity to electron-deficient iodine, o-nitrophenol (o-NP), and picric acid (PA) via fluorescence quenching.

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 cost-effective approaches for fabricating porous carbon (PC) based catalysts with favourable oxygen reduction reaction (ORR) performance is highly significant for fuel-cell devices. Herein, we reported a precursor controlled, molten salt-templated approach to prepare ultrafine CoO nanoparticles embedded nitrogen-doped PC materials with high surface area (1236 m 2 g -1 ) and large pore volume (0.68 cm 3 g -1 ). This method is simple and feasible, which produce CoO nanoparticles that were uniformly distributed on carbon skeleton with diameters in the range of 5-10 nm. The unexpected collapse of porous structures and agglomeration of metal nanoparticles were suppressed in the synthetic process. The as-made sample not only showed efficient catalytic activity towards ORR in alkaline media with a half wave potential (E 1/2 ) of 0.85 V (vs. RHE), but also exhibited better stability and stronger resistance to methanol than Pt/C., (Copyright © 2019 Elsevier Inc. All rights reserved.)

We demonstrate the aggregation-induced electrochemiluminescence (AIECL) generated by 1,1,2,2-tetrakis(4-bromophenyl)ethane (TBPE)-based conjugated microporous polymers (TBPE-CMPs) and its biosensing application. We synthesized three TBPE-CMPs (i.e., TBPE-CMP-1, -2, -3) using three different molecules including tris(4-ethynylphenyl)amine (TEPA), 4,4'-diethynylbiphenyl (DEP), and 2,4,6-tris(4-ethynylphenyl)-1,3,5-triazine (TEPT). The TBPE-CMPs can act as electrochemiluminescence (ECL) emitters to generate AIECL. Among them, TBPE-CMP-1 exhibits the highest ECL efficiency (1.72%) due to the improved electron-hole recombination efficiency and efficient suppression of nonradiative transition. Moreover, the ECL properties of TBPE-CMPs can be tuned by the introduction of different conjugated molecules that can decrease the energy gap to facilitate the injection of an electron into the conjugated polymer backbone. Importantly, TBPE-CMP-1 can be used to construct an ECL sensor for the detection of dopamine, whose electro-oxidation products (e.g., leucodopaminechrome (LDC), dopaminechrome (DC), 5,6-dihydroxyindole (DHI), and 5,6-indolequinone (IDQ)) may function as energy acceptors to quench the ECL emission of TBPE-CMP-1. This ECL sensor exhibits high sensitivity and good anti-interference capability against ascorbic acid and uric acid.

Na-ion batteries (NIBs) have attracted considerable attention in recent years owing to the high abundance and low cost of Na. It is well known that S doping can improve the electrochemical performance of carbon materials for NIBs. However, the current methods for S doping in carbons normally involve toxic precursors or rigorous conditions. In this work, we report a creative and facile strategy for preparing S-doped porous carbons (SCs) via the pyrolysis of conjugated microporous polymers (CMPs). Briefly, thiophene-based CMPs served as the precursors and doping sources simultaneously. Simple direct carbonization of CMPs produced S-doped carbon materials with highly porous structures. When used as an anode for NIBs, the SCs exhibited a high reversible capacity of 440 mAh g -1 at 50 mA g -1 after 100 cycles, superior rate capability, and excellent cycling stability (297 mAh g -1 after 1000 cycles at 500 mA g -1 ), outperforming most S-doped carbon materials reported thus far. The excellent performance of the SCs is attributed to the expanded lattice distance after S doping. Furthermore, we employed ex situ X-ray photoelectron spectroscopy to investigate the electrochemical reaction mechanism of the SCs during sodiation-desodiation, which can highlight the role of doped S for Na-ion storage.

Conjugated microporous polymers (CMPs) with high surface areas, tunable building blocks, and fully conjugated structures have found important applications in optoelectronics. Here, we report a new series of CMPs with tunable band gaps by introducing thiazolo[5,4- d] thiazole as the linkage. Because they are synthetic polymers, the geometries and structures could be rationally designed. Their intrinsic wide visible-light absorption properties and layered architectures endow them with a promising photocatalytic performance. The role of geometries, surface areas, and morphologies of the CMPs in photocatalysis abilities is examined and discussed. The results indicate that geometries have a direct impact on the surface areas and morphologies of the CMPs and thus exert great influence on photocatalysis.

Conjugated microporous polymers (CMPs) have attracted intensive attention owing to their permanent nanoporosity, large surface area and possibility for functionalization, however their application in energy storage suffers from poor conductivity and low hetero-atom content. Here, we demonstrate a hybrid of conjugated microporous polymers and graphene aerogel with improved conductivity. After treating at 800°C in NH 3 , the nitrogen content increases to 9.8%. The resulting microporous carbon exhibits a significant rise in supercapacitive performance up to 325 F g -1 , 55% higher than pristine triazine-based CMPs, with energy density up to 12.95 Wh kg -1 . Moreover, it has high stability with 99% retention after 10,000 cycles at 5 A g -1 . The synergy of hierarchical porous structure, graphene-based conduction path and high percentage of hybridization with nitrogen ensures effective ion/electron transport and diffusion, making NH 3 -treated graphene aerogel/CMP hybrid a promising electrode material in high-performance supercapacitor.

Conjugated microporous polymers (CMPs) with π-conjugated skeletons show great potential as energy storage materials due to their porous structure and tunable redox nature. However, CMPs and the structure-performance relationships have not been well explored for potassium-ion batteries (KIBs). Here, we report the structure-engineered CMP anodes with tunable electronic structures for high-performance KIBs. The results demonstrate that the electronic structure of the CMPs plays an important role in enhancing potassium storage capability, including the lowest unoccupied molecular orbital (LUMO) distribution, LUMO energy level, and band gap, which can be finely tuned by synthetic control. It was revealed that the poly(pyrene- co-benzothiadiazole) (PyBT) with optimized structure delivers a high reversible capacity of 428 mAh g -1 and shows an excellent cycling stability over 500 cycles. Our findings provide a fundamental understanding in the design of CMP anode materials for high-performance potassium-organic energy storage devices.

The novel multifunction materials for bactericides residue enrichment is attractive. Few materials used in bactericides analysis could simultaneously achieve convenient separation, recycling and trace enrichment. Therefore, a magnetic poly (phenylene ethynylene) conjugated microporous polymer (CMP) microspheres with three-dimensional network structure and covalently built-in Fe 3 O 4 nanoparticles was reported. The structure of dense poly (phenylene ethynylene) frameworks would enhance its conjugation system, which could adsorb bactericides with phenyl structure through π-π stacking. The material could be separated from sample matrix conveniently and recycled due to the super paramagnetism from embedded Fe 3 O 4 nanoparticles. After response surface optimization on extraction and desorption conditions, a method for trace analysis of six bactericides determination was developed by collaborative use of ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). The detection limits were in the range of 0.27-3.1 ng / L, and bactericides had been found in vegetables and fruits at concentration among 0.038-0.62 μg/kg. Finally, the method was further applied to analyze the regression equations of bactericide dissipation under natural condition. Effects of different treatment during cleaning process of vegetables and fruits were investigated to seek for the optimal cleaning method. The results revealed that the analytical method based on magnetic CMP which could achieve convenient separation, recycling and trace enrichment, having a great potential for trace analysis of more phenyl pesticides from real samples., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Developing stable and efficient photocatalysts for H 2 production under visible light is still a big challenge. In this work, a novel covalent organic polymer (COP)-based photocatalyst with trace ending groups was prepared by the efficient irreversible kinetic coupling reaction, i.e., nickel(0)-catalyzed Yamamoto-type Ullmann cross-coupling, using pyrene as electron donor and countpart, e.g., phenanthrolene, benzene, pyrazine, as electron acceptor. The newly developed optimal photocatalyst (termed as COP-TP 3:1 ) has a 14-fold improvement in the H 2 evolution rate from 3 to 42 μmol h -1 under visible light compared with the sample without donor-acceptor structure. Moreover, COP-TP 3:1 also performs excellent photocatalytic activity under different water quality (deionized water, municipal water, commercial mineral water, and simulated seawater (NaCl 3 wt %)). Significantly, ignored decrease in H 2 evolution can be observed after 20 hours cycling H 2 production, and the performance is only reduced by about 7% even after discontinuous cycles of photocatalysis and storage for a month. The donor-acceptor units with trace ending groups contribute to suppress electron-holes recombination kinetics and the N coordination sites in electron-acceptors conduce to anchor Pt (as the cocatalyst) onto the surface of photocatalyst, both of which are conducive to the outstanding photocatalytic activity and stability. Accordingly, this work can provide guidance to design a stable and efficient photocatalyst by copolymerization for visible-light-driven H 2 production.

A novel conjugated microporous polymer based on perylene tetraanhydride bisimide (DP 2 A 2 ) has been synthesized through Sonogashira-Hagihara cross-coupling polymerization of tetrabromo-substituted perylene tetraanhydride bisimide derivative (DPBr 2 ABr 2 ) with 1,4-diethynylbenzene, whose Brunauer-Emmett-Teller (BET) specific surface area is about 378 m 2  g -1 . The fluorescence quenching behaviors of the DP 2 A 2 were investigated. It is found that the DP 2 A 2 shows high sensitivity and selectivity to tracing o-nitrophenol (o-NP) in THF with Ks V constant of 2.00 × 10 4  L mol -1 . The detection limit (LOD) is 1.50 × 10 -9  mol L -1 . The possible sensing mechanism for the luminescent quenching of DP 2 A 2 towards o-NP exciting at 365 nm was considered the donor-acceptor electron transfer mechanism, which is a combined result from both dynamic (collisional) and static quenching. Moreover, the static quenching process is dominant for DP 2 A 2 ., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Herein, we reported the fabrication of conjugated microporous polymer (CMP) films based on three thiophene derivatives using a one-step templateless electropolymerization in dichloromethane without any surfactants. The formation of hydrophilic or hydrophobic films with specific morphology is a comprehensive result of the polymerization sites in each monomer, the polymerization rate, and the gas bubble produced in situ during the polymerization process, which can be easily controlled by the experimental conditions, such as electropolymerization method, electrolyte, and "trace water" existed in the organic solvent. Moreover, the electrochemical reduction of metronidazole as a prototypical nitro-analyte at CMP-modified glassy carbon (GC) electrode shows remarkably increased current response compared to nonmodified GC electrode. The process is demonstrated to be typical adsorption-controlled, and the hydrophobic surface of the electrode coating film is more favorable to the absorption and thus reduction of metronidazole. This work provides a new perspective and a breakthrough point for the application of CMPs in the electrochemical sensors.

Humic acid (HA) is a major constituent of natural organic matter (NOM) found in water systems. Although NOM generally does not have any known harmful effects to humans, it imparts repulsive organoleptic properties to water, reacts with disinfectants to produce toxic products, and interferes with the efficiency of water treatment processes. The removal of NOM and related compounds from water is therefore important to render water potable and suitable for other applications. In this work, a hitherto unreported carbonaceous conjugated microporous polymer (CCMP) prepared through the organic-polymeric-precursor-controlled carbonization of hypercrosslinked post-consumer waste polystyrene (WPS) was evaluated for its capacity to remove HA from synthetic wastewater. This advanced material retained the morphology of the precursor material, while its porosity and chemical integrity were significantly improved. The approach is an environmentally friendly way of handling WPS while at the same time remediating NOM-contaminated water. Overall, with a maximum adsorption capacity of 340 mg/g in batch experiments, and a maximum initial removal rate of 95.7% in column experiments, the results showed that CCMP can be used for the remediation of HA-contaminated water at high pH.

Stable controlled release system, conjugated microporous polymers (CMPs) with stimuli-responsive properties can be ideal structures because their 3D microporous matrix structure and possible stimulated response provide inherent switchable acceptor sites to capture and release guest molecules. Herein, the in situ electrochemical deposition of precursors (DTCzAzo) is utilized to construct highly crosslinked photoresponsive CMP films, which can reversibly undergo the trans-to-cis isomerization alternately with irradiation by 355 and 480 nm laser beams. The size of pores in CMP films changes tremendously during the process of trans-cis photoisomerization, to controllably capture, conserve, and release the guest molecules., (© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Iron and nitrogen (Fe/N) co-doped porous carbons have already shown great potential as electrocatalysts for oxygen reduction reaction in alkaline media. However, it still remains a great challenge to finely integrate a hierarchical porous structure and Fe/N co-doping effect into one material at the same time. In this work, a rational design toward Fe/N-codoped hierarchical porous carbon spheres was developed by the formation of an iron-porphyrin-containing conjugated microporous polymer sphere with hollow structure (HCMP) through a silica sphere template directed condensation of pyrrole and 1,4-phthalaldehyde, then etched with NaOH, and treated with FeCl 2 . The resulting HCMP-Fe polymer was readily converted to a series of Fe/N co-doped hierarchical porous carbons (HPC-Fe/N-X, X=700-900) upon pyrolysis at different temperatures and etching treatment. These porous carbons exhibit the high specific surface areas up to 518m 2 g -1 and the contents of N and Fe up to 3.28at.% and 0.85wt.%, respectively. Benefiting from the high surface area, Fe/N co-doping character, HPC-Fe/N-700 exhibited excellent electrochemical catalytic performance for oxygen reduction reaction under alkaline condition (0.1M KOH) with a low half-wave potential (0.84V), a dominant four-electron transfer mechanism (n=3.89 at 0.65V), as well as a high diffusion limiting current density (J L =5.19mAcm -2 ), comparable to those porous carbon-based ORR catalysts with excellent electrochemical performance., (Copyright © 2017 Elsevier Inc. All rights reserved.)