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It is a significant issue to develop silicon/carbon composite anode with high‐capacity and long cycling stability for lithium‐ion batteries. However, the huge volume expansion of silicon during lithiation leads to severe pulverization of silicon, resulting in serious capacity fading over cycles. Herein, nano silicon integrated hard carbon (20Si@HC, 20 wt% nano silicon) is prepared by pyrolyzing nano silicon in‐situ coated a conjugated microporous polymer (CMP). CMP‐derived hard carbon coating features developed porous structure, which not only deliver a high lithium storage capacity, but also provide enough space for the volume expansion of nano silicon. When evaluated as an anode for lithium‐ion batteries, the 20Si@HC delivers an impressive 1037 mAh g−1 at 0.1 A g−1 and a capacity retention ratio of 72.07% for 100 cycles at 0.6 A g−1, providing some reference for designing high‐capacity silicon/carbon composites. [ABSTRACT FROM AUTHOR]

Heterocyclic organic semiconductors have attracted significant attention as photocatalysts for hydrogen evolution due to excellent absorbency and abundant active sites. Herein, we developed a dual heterocyclic (O/S) conjugated microporous polymer Py-Th-Fu, consisting of both the furan and thiophene heterocycles, for photocatalytic H 2 evolution. Compared with the furan O-heterocycle Py-Fu and thiophene S-heterocycle Py-Th, the Py-Th-Fu with the dual heterocyclic structure is more outstanding in regulating the optoelectronic properties, morphological properties, electric charge shift kinetics, and photocatalytic H 2 evolution activity. Computational analysis also elucidates the smallest hydrogen adsorption free energy of Py-Th-Fu, which suggests it is the most advantageous for hydrogen mass transfer in this dual heterocycle polymer. As a result, the synergistic combination of two different heteroatom catalytic sites enables the dual heterocycle Py-Th-Fu to afford enhanced catalytic activity with an optimal rate of 23.28 mmol g−1 h−1, which is nearly equal to 5.06 and 1.58 times that of the corresponding O- and S-containing single heterocycles Py-Fu and Py-Th under visible lighting (λ > 420 nm). Our study demonstrates that the dual heterocyclic strategy using ternary copolymerization to tune the optoelectronic properties may open the horizon for fabricating high-performance photocatalytic water splitting via sunlight-driven hydrogen evolution. [Display omitted] • We developed a CMP photocatalyst with double heterocyclic strategy. • This strategy regulated the morphological properties and charge transfer kinetics. • Double heterocycle exhibited better HER than the single heterocycle in CMPs. [ABSTRACT FROM AUTHOR]

Vanillin is often used in food and medicine because of its unique flavor and pharmacological effects. However, excessive vanillin intake can harm human health; therefore, rapid and simple vanillin detection methods are required. In this study, porphyrin‐based conjugated microporous polymer‐grafted graphene (CMP‐rGO) was synthesized via the Sonogashira–Hagihara coupling reaction and assembled into an electrochemical sensor for vanillin detection. Due to the enhanced electrical conductivity and electrocatalytic characteristics of CMP‐rGO, the sensor demonstrated a low detection limit of 0.07 μM and a broad response range of 0.08–20 μM. Furthermore, this reusable sensor exhibited acceptable recoveries when evaluating vanillin in pharmaceuticals and human serum. This study offers technological assistance for the rapid detection of vanillin in pharmaceuticals and broadens the application of CMP‐rGO. [ABSTRACT FROM AUTHOR]

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 (1O2), 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. [ABSTRACT FROM AUTHOR]

Novel Fe N C electrocatalysts derived from conjugated microporous polymers based on pre-functionalization of monomers was developed, which exhibits great potential for cathodic oxygen reduction reaction in fuel cell and provides a feasible strategy of developing multi-atoms doping catalysts for heterogeneous catalysis. [Display omitted] Porous iron–nitrogen-doped carbons (Fe N C) 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 Fe N C 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 Fe N C 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. [ABSTRACT FROM AUTHOR]

Photocatalytic oxygen (O2) reduction to hydrogen peroxide (H2O2) is considered to be a promising method for energy storage. However, it suffers from the rapid recombination of carriers, the limited solubility and slow diffusion of O2, and the self‐decomposition of H2O2 in traditional diphase systems. Here, a self‐floating carbon dots/conjugated microporous polymer (CDs/CMP) photocatalytic system is established for H2O2 production and organic synthesis. Due to the D–π–A structure, porous structure, and hydrophobicity, CMP induced the intramolecular charge transfer, exposed abundant reaction sites, and enhanced O2 adsorption. CDs act as "bridges" for electron transmission and regulate the surface hydrophobicity of CMP, further improving charge transfer and optimizing the reaction interface. CDs/CMP system exhibits a high H2O2 production of 8542.6 µmol g−1 h−1 and concurrent furoic acid production at 2.22 mm h−1. This H2O2 production rate is ≈90% higher than that in the diphase system, exceeding all previously reported photocatalysts in triphase systems. Notably, the CDs/CMP system achieves the relative separation of the photocatalysts and H2O2, suppressing the generated H2O2 self‐decomposition. Theoretical calculations and in situ characterizations reveal the mechanism of H2O2 and furoic acid evolution. This self‐floating system provides insights into exploring the application of metal‐free photocatalysts in heterogeneous reactions. [ABSTRACT FROM AUTHOR]

Three multiphase metallaphotoredox catalysts M−Salen−CMP (M Zn, Cu and Co) with dual-catalytic functions were constructed by linking M−salen (M Zn, Cu and Co) and 2, 4, 6-tris(4-ethylphenyl)-1, 3, 5-triazine (TEPT) monomer via covalent bonds. The catalysts M−SATE−CMP (M Zn, Cu and Co) have different d-band centers based on different metal active centers, resulting in the difference of the optical property as well as their adsorption and activation capacities for the reactants. Therefore, they can selectively photocatalytically oxidize β-keto esters to α-hydroperoxide β-keto esters (ROOH) or α-hydroxyl β-keto esters (ROH), where ROOH is an intermediate of ROH. [Display omitted] 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 (M Zn, 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 (M Zn, 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. [ABSTRACT FROM AUTHOR]

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 ΔEST 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 H2O. This study presents a novel concept for developing a hybrid system for preparation of H2 by photocatalysis with effectiveness, sustainability, and economy. [ABSTRACT FROM AUTHOR]

Abstract 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 (1O2), 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.

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. [ABSTRACT FROM AUTHOR]

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 CO2 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 CH4. 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. [ABSTRACT FROM AUTHOR]

In this study, cobalt phosphide (CoP 2) was synthesized onto a Nickel foam (NF) support via phosphorylation under an N 2 atmosphere. The resulting material was then coated with tetrahydroxyquinone (THQ), a conjugated microporous polymer, using a hydrothermal method. The as-synthesized CoP 2 /THQ@NF showed remarkable electrocatalytic performance for the hydrogen evolution reaction and excellent durability in acidic electrolytes. This was attributed to the synergistic effect of the NF support, CoP 2 , and THQ, which led to a modified electronic structure of CoP 2 and a high electron transfer rate of THQ. A low overpotential of 137 mV was required in a 0.5 M H 2 SO 4 solution to achieve a current density of 10 mA cm−2. • Integration of electrically conjugated polymers with non-precious metal phosphates boosts HER catalytic efficiency. • The development of CoP 2 /THQ@NF hybrid electrocatalysts through systematic methodological approaches is overviewed. • Merging organic polymers with inorganic materials elevates the catalytic prowess of non-precious metal catalysts. [ABSTRACT FROM AUTHOR]

The development of hard carbon with high capacity and long cycling stability is a significant issue for lithium ion batteries. Herein, thiophene-containing conjugated microporous polymer (SCMP) was synthesized using 1,3,5-triethynylbenzene 2,5-dibromothiophene by Sonogashira-Hagihara crosscoupling reactions. Then, high sulfur doped hard carbon (SHC) and KOH activated SHC (SHC-K) are prepared by direct carbonization and KOH-assisted carbonization of SCMP, respectively. Both samples were then investigated by SEM, elemental analysis, FTIR, XPS and Nitrogen adsorption/desorption. Taking advantages of sulfur content and abundant porosity, SHC-K delivers a first charge specific capacity of 842.2 mAh g−1 at 0.1 A g−1 and a specific charge capacity of 565.9 mAh g−1 after 500 cycles at 0.6 A g−1. [ABSTRACT FROM AUTHOR]

Abstract Conjugated microporous polymers (CMPs) are considered promising sensing materials for the detection of nitroaromatics. Unfortunately, the photoluminescence (PL) sensing application in water media is limited, owing to the poor solubility/dispersion in aqueous media. Here, two novel CMPs named poly(dimethylfluorene‐co‐tetrakis(4‐phenyl)silane)s (P4SiF) and poly(dimethylfluorene‐co‐tetrakis(3‐phenyl)silane)s (P3SiF) nanoparticles based on fluorene group and tetraphenylsilane unit are prepared using Suzuki coupling in water/toluene miniemulsion. P4SiF and P3SiF possess spherical particle morphology with sizes of 45 and 60 nm, respectively, and porous structure with pore diameters of both 1.9 nm. PL sensing experiments based on P4SiF and P3SiF nanoparticles in aqueous media show a sensitive and selective detection toward 2,4,6‐trinitrophenol (TNP). It is worth noting that the PL quenching effect toward TNP is not significantly changed after the addition of other nitro compounds, proving the excellent anti‐interference characteristic and highly selective detection of the polymers in water. Moreover, the t‐test indicates that the PL sensing method using P4SiF and P3SiF nanoparticles as sensing materials realizes the reliable detection of TNP in actual water samples at a 95% confidence level. Finally, the PL sensing mechanism is investigated, showing that the inner filter effect is the main factor in the PL quenching process of TNP in aqueous media.

Conjugated microporous polymers (CMPs) have found extensive applications in various fields such as optoelectronics, CO2 capture, and catalysis. However, their potential in electrochemical supercapacitors as energy storage and H2 production systems remains relatively unexplored. This limited exploration can be attributed to certain challenges, including issues related to structural and electrochemical stability, as well as the relatively modest specific capacitance. Additionally, many of the CMPs discovered thus far have exhibited lower energy densities, further contributing to this underexplored aspect of their utility. In this study, we prepared two different CMPs [TPET-TTh and PyT-TTh CMPs] containing thienyltriazine units (TTh) for the redox mechanism and constructed electrodes for supercapacitor applications. The synthesized TPET-TTh and PyT-TTh CMPs displayed exceptionally high specific surface areas of 545 and 528 m² g⁻¹, respectively. Furthermore, their pore sizes were very similar, centered at approximately 0.39 and 0.36 nm, respectively. To evaluate their electrochemical properties, the TTh-CMPs were examined using cyclic voltammetry (CV) and galvanostatic charge/discharge (GCD). The resulting CV curves exhibited rectangular shapes, indicative of the characteristic behavior of electric double-layer capacitors, across a range of potential and scan rates. These TPET-TTh and PyT-TTh CMPs delivered nominal specific capacitances of 74 and 76 F g−1 at 0.5 A g−1, respectively. In addition, they exhibited outstanding capacity retentions of 95.2 and 97.30 % even after 2000 cycles [analyzed at 10 A g−1]. The TTh-CMPs also exhibited excellent light-capture capabilities. The PyT-TTh CMP has faster charge separation and lower charge recombination rates than TPET-TTh CMP. This results in a higher hydrogen evolution rate from the water decomposition reaction. The H2 production rate of PyT-TTh CMP could be as high as 18,533 μmol g−1 h−1, which is approximately 4-fold that of TPET-TTh CMP. This study offers a strategy for the design of TTh-containing CMPs that exhibit exceptional energy storage application and photocatalytic efficiency for H2 evolution.

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 ΔEST 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 H2O. This study presents a novel concept for developing a hybrid system for preparation of H2 by photocatalysis with effectiveness, sustainability, and economy.

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 CO2 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 CH4. 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.

Conjugated microporous polymers (CMPs) with highly ordered catalytic units have demonstrated potential in sustainable catalysis. A salen-based conjugated microporous polymer (CMP-Salen-Zn) was firstly synthesized by condensation polymerization of dialdehyde derivative of Salen-Zn and pyrrole. The resulting CMP-Salen-Zn with excellent thermal stability was fully accessed by a combination of spectroscopy techniques. The CMP-Salen-Zn exhibited a fair porosity with a Brunauer–Emmett–Teller (BET) surface area of up to 444.6 m2 g−1. The CMP-Salen-Zn also exhibited high CO2 uptakes with 59.5 mg g−1 at 273 K and 1 bar and an outstanding catalytic performance for cycloaddition of CO2 with epoxides. The catalytic systems feature atom economy, environmental friendliness, low catalyst loading and mild reaction conditions for the synthesis of a wide range of cyclic carbonates. Moreover, the catalytic system was found to be recycled up to eight times without significant loss of catalytic activity. The resulting CMP catalyst was also found to catalyze Knoevenagel condensation reaction between aromatic aldehyde and malononitrile in excellent conversion with environmentally friendly solvent. These results offered a promising strategy for screening the correlation between structural features and catalytic properties through the fine-tuning of active centers on CMP catalysts. [ABSTRACT FROM AUTHOR]

Conjugated microporous polymers (CMPs) have great potential in the field of CO2 adsorption due to their high specific surface area and molecular structure designability, and the introduction of polar heteroatoms can further improve their CO2 adsorption performance. Boronic acid-based conjugated microporous polymers (BACMPs) rich of N and B heteroatom were obtained by Buchwald-Hartwig coupling reaction with tris(4-aminophenyl)amine (TA) and 3,5-dibromophenylboronic acid (BA). The pore size of BACMPs can be controlled by changing the monomer reaction ratio. The structure and morphology of BACMPs were characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, scanning electron microscopy and N2 adsorption and desorption tests, and the CO2 adsorption and desorption tests of BACMPs were carried out to explore their CO2 adsorption properties. The results show that the obtained BACMPs have a large number of micropores, the Brunauer-Emmett-Teller specific surface area can reach up to 475 m²/g, and the CO2 adsorption mass fraction can reach up to 8.53% at 100 kPa and 273 K, which has the application prospect of CO2 adsorption. [ABSTRACT FROM AUTHOR]

Incorporating redox active units in a 3D porous network is an encouraging strategy to enhance electrochemical performance of organic electrode materials. Herein, a new hybrid composed by phenazine‐based conjugated microporous polymer (IEP‐27‐SR, stand for IMDEA Energy Polymer number 27) and single‐walled carbon nanotubes (SWCNTs) and graphene oxide (RGO) is synthesized, fully characterized and tested electrochemically in different aqueous electrolyte conditions, i. e., at various pH values (1–12) and also with different charge carriers (H+ in acidic, and Li+, Na+, K+ in neutral and alkaline electrolytes). Although the IEP‐27‐SR is found to be very versatile showing very good electrochemistry both in alkaline and acidic solution, it exhibits best specific capacity, redox kinetics and cycle stability in acidic electrolyte. Then encouragingly, when IEP‐27‐SR is combined with an activated carbon (AC) counter electrode to construct a proof‐of‐the‐concept device, the IEP‐27‐SR//AC demonstrates high specific capacity (168 mAh g−1 at 2 C), impressive rate performance (96 mAh g−1 at 60 C) and ultra‐long cycle stability (76 % capacity retention over 28800 cycles at 10 C; 2690 h) in 1 M H2SO4. [ABSTRACT FROM AUTHOR]

Metal–organic framework (MOF) and conjugated microporous polymers (CMP) are two groups of supramolecular structures with potential applications for artificial photosynthesis though their catalytic activities are yet to be improved. A MOF/CMP hybrid photocatalyst NU@FNBZ with markedly higher catalytic activity for CO2 reduction to CO is hereby reported. The hybrid catalyst benefits from the high CO2 adsorption capacity of NU and the high visible light response of FNBZ. Moreover, the covalent bonding facilitates the formation of type II heterojunction that allows electron transfer from FNBZ to NU, leading to improved catalytic activity in the electron rich NU and enhanced CO2 adsorption in the electron depleted FNBZ. This work manifests that multiple synergy effects can be achieved by rational design of hybrid supramolecular photocatalysts. [ABSTRACT FROM AUTHOR]

Abstract Metal–organic framework (MOF) and conjugated microporous polymers (CMP) are two groups of supramolecular structures with potential applications for artificial photosynthesis though their catalytic activities are yet to be improved. A MOF/CMP hybrid photocatalyst NU@FNBZ with markedly higher catalytic activity for CO2 reduction to CO is hereby reported. The hybrid catalyst benefits from the high CO2 adsorption capacity of NU and the high visible light response of FNBZ. Moreover, the covalent bonding facilitates the formation of type II heterojunction that allows electron transfer from FNBZ to NU, leading to improved catalytic activity in the electron rich NU and enhanced CO2 adsorption in the electron depleted FNBZ. This work manifests that multiple synergy effects can be achieved by rational design of hybrid supramolecular photocatalysts.

Non-Pt electrocatalysts for oxygen reduction reactions (ORR) have been developed using metal and nitrogen co-doped carbon electrocatalysts. However, challenges remain regarding the porosity of the catalyst, distribution of active sites, and the easy aggregation of the metal components. Herein, we report a bottom-up preparation strategy to obtain a porous ethynyl-linked conjugated microporous polymer (CMP) precursor containing triazine units and bipyridine, ensuring high N content and coordination with Fe3+. The Fe doped CMP is then carbonization into a Fe, N co-doped nanoporous carbon material (BPCMP-Fe-800), which can be taken as the electrocatalyst in ORR. BPCMP-Fe-800 catalyst exhibits electrocatalytic performance dominated by 4e− transfer mechanism with the onset potential of 0.97 V, half-wave potential of 0.85 V, and higher kinetic current density of 11.3 mA cm−2 (0.8 V). In addition, when applied as cathode electrocatalyst in zinc-air batteries, BPCMP-Fe-800 displays more competitive power density (179.5 mW cm−2) and specific capacity (790.5 mAh g−1) compared with Pt/C. Our study demonstrates a general and facile approach for porous Fe, N co-doped carbon with the potential as alternatives to Pt catalysts for efficient ORR catalytic performances and provides new insights of multi-atom catalysts for other energy conversion related catalytic reactions. [Display omitted] [ABSTRACT FROM AUTHOR]

The partial self-coupling of donor or acceptor unit during donor-acceptor (D-A) type CMPs synthesis is often overlooked for the effect on photocatalytic activity. Herein, we developed three D-A type CMPs, named SATE-CMP-n (n=1–3) , which were constructed from triazine (TEPT) unit (A) and three salen units (D). With the rigidity of salen units increasing (the rigidity: salen-1 < salen-2 < salen-3), the self-coupling proportion of TEPT decreases. The experiments and DFT calculations reveal that salen-1 has the stronger electron-donating ability compared to salen-2 and salen-3 , and that the self-coupling of TEPT units also enhances the electron-accepting ability. Therefore, SATE-CMP-1 exhibits the strongest D-A interaction and the highest separation and transfer efficiency of charge carriers, and has been used a photocatalyst for S−S and S−N coupling reactions. This work proves that the self-coupling of monomers in the construction of CMPs is not overlooked for adjusting the photocatalytic activity of catalyst. [Display omitted] • An effective method for detecting the proportion of monomer self-coupling in CMPs has been developed. • Three D-A type salen-based CMPs with different self-coupling proportion of acceptor unit were designed and synthesized. • In D-A type CMPs, partial self-coupling of acceptor units can improve photocatalytic efficiency. • The S-S and S-N coupling reactions can be efficiently catalyzed using D-A type salen-based CMPs as photocatalysts. [ABSTRACT FROM AUTHOR]

• CMP-1 was synthesized by Sonogashira-Hagihara cross-coupling. • CMP-1 exhibited a large surface area of 788 m2·g−1 and abundant micropore structures. • This SPE method was applied to quantify NEOs in groundwater, tap water, and surface water. • The material shows excellent accuracy and application in NEOs monitoring. 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%. [ABSTRACT FROM AUTHOR]

A series of D-π-A type large cyclic polymeric skeletons conjugated microporous polymers (CMPs) are constructed with the TPA as strong electron donors (D), thiophene as "π-bridge" (T), and BTDO as strong electron acceptors (A) units, and the polymers show characteristics of adjusted geometrical and energy adaptability of polymeric structure for the highly improved photocatalytic hydrogen production (PHP) activity (65.41 mmol h−1 g−1) under visible light condition. [Display omitted] • A series of D-π-A type large cyclic polymeric skeletons CMPs are constructed. • The CMPs show highly improved PHP activity (65.41 mmol h−1 g−1) in visible light. • The "bimodal distribution" phenomenon of PHP activity appears twice for the CMPs. • The coplanarity of polymer backbone of CMPs is promoted by structure adjusting. • The geometrical and energy adaptability of the CMPs is associated on PHP activity. Conjugated microporous polymers (CMPs) with a donor–acceptor (D-A) molecular structure usually express the properties of well light-induced electron/hole separation efficacy and high photocatalytic activity. The triphenylamine (TPA) with a special three-dimensional propeller structure was chose as the electron donor, and the dibenzothiophene sulfone (BTDO) groups as the chain scaffold and electron acceptor to construct and prepare a unique "macrocyclic structure" D-A type CMPs photocatalyst (TPA-BTDO) for photocatalytic hydrogen production (PHP). In order to further improve the conjugation degree of the CMPs and enhance the electron transfer capacity and light absorption, the thiophene units was introduced as "π-bridge" to form a macrocyclic D-π-A type CMPs photocatalyst (TPA-T-BTDO). The results show that the addition of thiophene greatly improves the coplanarity between the donor–acceptor units, and the prepared TPA-T-BTDO-1 exhibited an amazing PHP efficiency of 65.41 mmol h−1 g−1 in the visible light region. More importantly, the PHP efficiency also reaches up to 39.63 mmol h−1 g−1 under the natural light conditions. Both the characterizations and DFT simulation results prove that the twisted structure of the TPA donor decreases the dihedral angle between the benzene rings of BTDO and TPA, which improves the coplanarity of polymer skeleton and then prevents the charges transfer along the polymer chain for recombination. This study highlights the significant influence of the geometry of the electron donor on the photocatalytic activity, as well as the strategy of the structure adjusting by adding suitable bridges between the donor–acceptor units. [ABSTRACT FROM AUTHOR]

We synthesized a porphyrin-functionalized conjugated microporous polymer by a simple Schiff base reaction and used it as an artificial protective coating for the Zn anode of aqueous zinc ion batteries. Due to the electronegativity and hydrophobicity of the polymer, the protective coating not only effectively inhibits the growth of Zn dendrites and the generation of corrosion reactions, but also promotes uniform Zn deposition, thereby achieving a stable Zn anode. [Display omitted] • Conjugated microporous polymer (ZnTAPP-TFTA) is rich in F and N elements. • The ZnTAPP-TFTA coating significantly improves the stability of the Zn anode. • The assembled full cell shows impressive electrochemical performance. • Theoretical calculations confirm that ZnTAPP-TFTA can promote uniform Zn deposition. In this paper, a multifunctional porphyrin-functionalized conjugated microporous polymer (ZnTAPP-TFTA) coating was prepared to achieve a stable dendritic-free Zn anode. The chemical structure of ZnTAPP-TFTA is rich in F and N elements. Through the interaction with Zn2+ ions, the transfer kinetics of Zn2+ ion are improved, the two-dimensional diffusion of Zn2+ ion is limited, and the rapid desolvation of hydrated Zn2+ ion is promoted, which not only inhibits the generation of hydrogen evolution reaction and inert by-products, but also induces uniform Zn deposition. Therefore, the ZnTAPP-TFTA@Zn symmetric cell exhibits a stable cycle life of 1100 h in comparison to the bare Zn symmetric cell. In addition, the ZnTAPP-TFTA@Zn//Cu asymmetric cell can maintain a coulombic efficiency of 98.7 % after cycling for 800 h. What's more, the full battery assembled with NH 4 V 4 O 10 cathode has higher specific capacity and excellent cycle stability. The strategy of realizing dendritic-free Zn anode by constructing functionalized CMPs points out a new way for the study of stable AZIBs. [ABSTRACT FROM AUTHOR]

Combining Brønsted base and photocatalysis into conjugated microporous polymers conducts the blue light-induced oxidation of thiols into disulfides with oxygen. [Display omitted] 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. [ABSTRACT FROM AUTHOR]

Two tetraphenylethylene-based fluorescent conjugated microporous polymers (TTTPT and TTDAT) were obtained by the Friedel−Crafts polymerization reactions catalysed by CH3SO3H. In virtue of containing tetraphenylethylene, triphenylamine and s-triazine units in their porous skeletons, the resulting TTTPT and TTDAT show excellent fluorescence sensing performance for trinitrophenol (TNP) with high quenching coefficients of 1.66 × 104 and 1.31 × 105 l mol–1, respectively. TTDAT can also sense to dinitrophenol (DNP) with the Ksv of 2.70 × 104 l mol–1. The fluorescent quenching mechanisms of TTTPT and TTDAT for selective detecting TNP attribute to conventional photoinduced electron-transfer mechanism, absorption competition quenching mechanism and/or the resonant energy transfer mechanism. [ABSTRACT FROM AUTHOR]

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.)

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.)

Metal nanoparticles have high surface area as well as good catalytic activity and have shown broad applications in organic synthesis, electronic devices, and optical devices. However, the controlled synthesis of ultrafine nanoparticles still represents a challenging task. Herein, we reported the synthesis of three phenylene–ethynylene-based conjugated microporous polymers (CMPs) via the sila-Sonogashira–Hagihara reaction. Upon postfunctionalization of these CMPs with N-acetylcysteine (NAC), 3-mercapto-propionic acid (MPA), and 1-propanethiol (PT) through thiol–yne addition, the resulting NAC–CMP, MPA–CMP, and PT–CMP were used as the templates to direct the growth of ultrafine Pd nanoparticles, respectively. The nanoparticles grown inside the pores of CMPs exhibit relatively narrow size distribution (1.7 ± 0.2 nm in NAC–CMP, 1.6 ± 0.3 nm in MPA–CMP, and 1.7 ± 0.3 nm in PT–CMP). PdNPs–NAC–CMP exhibits the highest catalytic activity and stability in Suzuki–Miyaura coupling compared with the other two PdNPs–CMPs and commercial Pd/C catalyst. The strong binding interactions between NAC–CMP's functional groups and Pd nanoparticles as well as good solvent–polymer affinity are playing critical roles in stabilizing Pd nanoparticles and enhancing the reaction rate. This study shed light on the effect of different directing groups on controlled growth of ultrafine metal nanoparticles and their catalytic activity and recyclability. [ABSTRACT FROM AUTHOR]

Two kinds of hard carbons with controllable nitrogen contents (N1HC and N2HC) were prepared from 2,5-dibromopyridine and 2,5-dibromopyrazine, respectively. The nitrogen contents of N1HC and N2HC are 3.75 wt% and 5.08 wt%, respectively. The pore structure of N2HC was further improved by KOH activation and the activated N2HC is designated as N2HC-K. The specific surface area of N2HC-K is considerable 1328.3 m2 g−1, which is distinctly higher than that of N2HC. The rich nitrogen content and developed pores make N2HC-K afford a high lithium storage capacity, rate performance, and excellent cycling performance. The initial reversible capacity of N2HC-K is 604.8 mAh g−1 at a current density of 0.1 A g−1. The specific capacity of N2HC-K after 500 cycles at 0.6 A g−1 is still as high as 488.2 mAh g−1. [ABSTRACT FROM AUTHOR]

By using 4,7-dibromo-2,1,3-benzothiadiazole as photoactive group, the Sonogashira coupling between 4,7-dibromo-2,1,3-benzothiadiazole and 1,3,5-triethynylbenzene results in benzothiadiazole functionalized conjugated microporous polymer (CMP), named CMP-3-BT. The obtained CMP-3-BT shows hierarchical structures, which consists of microspheres and curved nanobelts. Moreover, CMP-3-BT is semiconductive porous materials with band gap of 2.24 eV. By using 425 nm LED (3 W) as light source, assisted by H2O2, CMP-3-BT enables the oxidation of thioanisole bearing various substituents to their corresponding sulfoxides under O2 atmospheres at room temperature with high efficiency and excellent selectivity. EPR spectra indicate that the 1O2 and O·- 2 are the active oxygen species for the photo-oxidation of thioanisole. Importantly, the catalytic activity of CMP-3-BT remains unchanged after 6 cycles, indicating the excellent structural stability and catalytic activity of CMP-3-BT serving as a reusable green catalyst.

A novel cationic pyrimidine-modified conjugated microporous polymer (BPyMe-CMP) has excellent photoelectric effect, which can produce ROS with the assistance of visible light. BPyMe-CMP possesses bioactivities to kill bacteria, adjust macrophage polarization, promote angiogenesis, and accelerate cell migration, which promotes wound healing. [Display omitted] • A novel cationic pyrimidine-modified conjugated microporous polymer (BPyMe-CMP) was prepared. • BPyMe-CMP exhibited outstanding antibacterial ability against drug-resistant bacteria. • BPyMe-CMP promoted fibroblast migration, angiogenesis and M2 macrophage polarization to inhibit inflammation. • BPyMe-CMP exhibited great promise for MRSA infected wound healing. Pathogenic bacterial invasion leads to severe inflammation that hinders wound healing, and it has become a major medical threat worldwide. Photodynamic therapy (PDT) has emerged as a promising strategy for treating microbial infection; however, developing a dressing with PDT effect and excellent biological functions poses a formidable challenge. Herein, a novel cationic pyrimidine-modified conjugated microporous polymer, BPyMe-CMP, was rationally designed and synthesized via a Sonogashira-Hagiwara and S N2 substitution reaction. The BPyMe-CMP exhibited weak interfacial charge transfer resistance and demonstrated superior photoinducible carrier separation, thereby displaying an excellent photoelectric response. Consequently, the BPyMe-CMP could readily generate reactive oxygen species under visible light irradiation to kill bacteria. In addition to enhancing the photogenerated electron transfer process, BPyMe-CMP also provided abundant attraction sites for bacteria to reinforce the antibacterial ability. The deposition of BPyMe-CMP onto polyvinyl alcohol-modified silk fibroin (SF/PVA) film served as a wound dressing to promote healing. The in vitro and in vivo experiments revealed that the SF/PVA@BPyMe-CMP induced M2-type macrophage polarization, promoted L929 fibroblast migration, exhibited bactericidal activity, and induced angiogenesis, which synergistically accelerated the healing of methicillin-resistant Staphylococcus aureus -infected wounds. This study provides data support to advance the construction of a multi-functional wound dressing based on pyrimidination and cationization for the treatment and rapid healing of infected wounds. [ABSTRACT FROM AUTHOR]

Copyright of Journal of Donghua University (Natural Science Edition) is the property of Journal of Donghua University (Natural Science) Editorial Office and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

Porous organic polymers hold great promise for molecular sieving membrane separation. Although the inclusion of functional ionic liquid (IL) in the pores offers a facile way to manipulate their separation properties, the IL leaching during the separation process is difficult to avoid. Herein, we report a strategy to in-situ encapsulate ILs into the micropores of the conjugated microporous polymer membrane via a 6-min electropolymerization and further seal the aperture of the pores to prevent ILs leaching by solvent-assisted micropore tightening (SAMT). Upon screening the binding energy between different ILs and gas molecules, two ILs were selected to be incorporated into the membrane for CO2/CH4 and O2/N2 gas separations. The resultant separation performances surpass the 2008 Robeson upper bound. Notably, the ILs can be locked in the micropores by a facile high surface tension solvent treatment process to improve their separation stability, as evidenced by a 7-day continuous test. This simple and controllable process not only enables efficient and steady separation performance but also provides an effective strategy for confining and sealing functional guest molecules in the porous solids for various applications. [ABSTRACT FROM AUTHOR]

[Display omitted] 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 C C bonds prepared from FeCl 3 -promoted polymerization of monomers of 3,6-di(9 H -carbazol-9-yl)-9 H -fluorene with the 9 H 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-9 H -carbazole-CMP (SFC-CMP), 9,9′-(9,9-difluoro-9 H -fluorene-2,7-diyl)bis(9 H -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. [ABSTRACT FROM AUTHOR]

Membranes with fast and selective ion transport have great potential for use in water‐ and energy‐related applications. The structure and material design of the membranes play a key role in improving their performance. Conjugated microporous polymers (CMPs) as emerging membrane materials have shown uniform pore size, high surface area, and excellent chemical stability, but their mechanical properties are poor due to their brittleness. Herein, a flexible ionic CMP membrane with precisely tailored pore architecture and chemistry prepared by a coelectropolymerization (COEP) strategy is reported. The structure contains rigid monomers to maintain structural uniformity and flexible and charged monomers to enhance mechanical flexibility and improve ion selectivity by combining precise size sieving and Donnan effect. The resulting 40 nm thick CMP membranes show equivalent ion conductance compared to the commercial Nafion 117 membrane, but an order of magnitude higher ion selectivity for ion systems such as K+/Mg2+ and Li+/Mg2+. [ABSTRACT FROM AUTHOR]

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%. [ABSTRACT FROM AUTHOR]

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 m2 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 13C (cross-polarization magic angle spinning-nuclear magnetic resonance) CP-MAS NMR, N2 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/cm2 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.

Copyright of Journal of Materials Engineering / Cailiao Gongcheng is the property of Journal of Materials Engineering Editorial Office and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

Thermal energy storage with phase change materials (PCMs) offers a high thermal storage density for energy saving and management in greenhouses. However, the leakage of PCMs during the phase change process hinders their applications. Herein, to tackle this problem, PCM material of 1-octadecanol (ODA) was encapsulated in hierarchical porous carbon spheres (HCSPs) derived from a spirofluorene- and aniline-linked conjugated microporous polymer (SACMP) with a high specific surface area of～476.1 m2/g. The HCSPs showed an optimal heating rate of 0.14 °C/s, which was comparable to the charging rate of pure ODA, signifying a great potential for the thermal energy storage. The obtained HCSP/ODA composites had a high package of ODA (up to 80 wt%) and excellent shape stability without the leakage of ODA. The optimized HCSP/ODA composites show a high phase change enthalpy (～184.4 J/g) and good thermal cycling stability (169.5 J/g after 50 heating/cooling cycles), indicating a great potential for the stable thermal energy storage. [Display omitted] [ABSTRACT FROM AUTHOR]

Developing novel carbon anode materials combining Mn-based compounds for excellent lithium-ion storage performance is very sensible. Herein, MnF 2 and MnO are inserted into hard carbon to construct an efficient anode (MFO@HC-3) by a simple pyrolysis of the mixture of F-containing conjugated microporous polymer and manganous acetate. When evaluated as an anode for lithium-ion batteries, the MFO@HC-3 delivers an impressive 743 mA h g−1 at 0.1 A g−1 and 239 mA h g−1 at an ultrahigh current density of 5 A g−1. This probably attributes to the incorporation of both hard carbon and Mn-based compounds, which improves electrochemical performance by combining the advantages and preferably resolves the pulverization issue of Mn-based compounds. This work provides original insights into the incorporation of transition metal compounds and carbon materials. [Display omitted] • In-situ synthesis of MnF 2 and MnO inserted hard carbon (MFO@HC-3) through one-step pyrolysis. • Mn-salts adsorbed on F-containing conjugated microporous polymer act as the precursor and internal F source. • MnF 2 and MnO nanoparticles provide fast electrochemical response. • CMP-derived hard carbon undertakes buffer and stable Li-storage capacity. [ABSTRACT FROM AUTHOR]

[Display omitted] • The unique n-n type conductive polymers PorCoPc-CMP gas sensor was fabricated. • High sensitivity, stability, selectivity, and low LOD for NO 2 gas sensing were obtained. • The periodic n-n type heterojunction and porous structure enhanced sensing performance. Today's society has an unprecedented demand and requirement for sensors, and the research of toxic gas sensors is its top priority. In this paper, a chemiresistive sensor for NO 2 sensing based on a porphyrin-cobalt phthalocyanine-based conjugated microporous polymer (PorCoPc-CMP) was fabricated. Benefiting from the periodic intramolecular n-n type heterojunction and the sufficiently exposed active sites on the 2D sheet-like structure, the prepared chemiresistive sensor exhibited liner response in the range of 0.1–0.5 ppm with the lower limit of detection (30 ppb) and higher sensitivity (22.91 % ppm−1) than that of the monomers. Moreover, the PorCoPc-CMP also possessed good selectivity, long-term stability, and excellent recovery towards the detection of NO 2. This work certified the potential of conjugated microporous polymers for gas sensing applications and provided an alternative approach for the long-term detection of NO 2 gas. [ABSTRACT FROM AUTHOR]

[Display omitted] • A novel CMP photocatalyst incorporated with Cu for CO 2 reduction was constructed. • The highly selective production of C 2 H 4 was realized by Cu 0.012 @CMP photocatalysis. • Cu 0.012 @CMP showed efficient charge separation where Cu prolonged electron lifetime. • In situ DRIFTS revealed the CO 2 reaction processes and C–C coupling to form C 2 H 4. Selective conversion of CO 2 to fuels and chemicals has been considered one of the key challenges in the photocatalytic CO 2 reduction reaction. The multi-electron reduction reaction requires the design of photocatalysts that can adsorb CO 2 and transfer electrons. Herein, Cu single atoms are confined in a conjugated microporous polymer (CMP) to construct Cu n @CMP photocatalyst for CO 2 reduction to produce C 2 H 4 and CH 4. By adjusting Cu loading, Cu 0.012 @CMP exhibited a high performance with production yields of 236.81 μmol·g−1·h−1 for C 2 H 4 , and 78.2 % selectivity for C 2 H 4 formation. DFT calculations displayed the band structure and confirmed Cu–N together with characterization. The in situ DRIFTS revealed *CH 2 and *C 2 H 4 as key reaction intermediates to form CH 4 and C 2 H 4 , respectively. The synergy effect in Cu single-atoms and CMP contributed greatly to C–C coupling and interfacial charge transfer, thus achieving excellent activity for conversion of CO 2 to C 1 /C 2. This work highlights the potential for constructing Cu single atoms on CMP to produce highly selective C 2 H 4. [ABSTRACT FROM AUTHOR]