ChemInform Abstract: Conjugated Microporous Polymers: Design, Synthesis and Application

Photocatalytic degradation of tetracycline hydrochloride with visible light-responsive bismuth tungstate/conjugated microporous polymer

Conjugated microporous polymer membranes for chemical separations

Chemical sensing of harmful species released either from natural or anthropogenic activities is critical to ensuring human safety and health. Over the last decade, conjugated microporous polymers (CMPs) have been proven to be potential sensor materials with the possibility of realizing sensing devices for practical applications. CMPs found to be unique among other porous materials such as metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) due to their high chemical/thermal stability, high surface area, microporosity, efficient host-guest interactions with the analyte, efficient exciton migration along the π-conjugated chains, and tailorable structure to target specific analytes. Several CMP-based optical, electrochemical, colorimetric, and ratiometric sensors with excellent selectivity and sensing performancewere reported. This review comprehensively discusses the advances in CMP chemical sensors (powders and thin films) in the detection of nitroaromatic explosives, chemical warfare agents, anions, metal ions, biomolecules, iodine, and volatile organic compounds (VOCs), with simultaneous delineation of design strategy principles guiding the selectivity and sensitivity of CMP. Preceding this, various photophysical mechanisms responsible for chemical sensing are discussed in detail for convenience. Finally, future challenges to be addressed in the field of CMP chemical sensors are discussed.

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

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

Designing fluorene-based conjugated microporous polymers for blue light-driven photocatalytic selective oxidation of amines with oxygen

Ultra-stable hollow nanotube conjugated microporous polymer incorporating fluorenyl moieties for Co-capture of PM and CO2

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

Improved energy storage performance of lead-free BaTi0.96Li0.04O2.94 ceramics via domain structure engineering

MXene‐based organic material hybrids present huge potential for energy storage applications. However, the compatibility of hydrophilic MXenes with organic materials and their subsequent processing still remain elusive. Herein, a MXene‐based 2D sandwich‐like conjugated microporous polymer (MX‐CMP) manifesting high specific surface area and layered structure using a functionalized MXene as a 2D structure‐directing template is developed. The MX‐CMP is used as a robust organic precursor for preparing a MXene‐coupled nitrogen‐doped porous carbon (MX‐MC‐N) hybrid. The interconnected porous networks and large aspect ratio of MX‐MC‐N enhances the electrochemical active surface area and boosts the long‐distance charge transport. This leads to excellent performance for a three‐electrode, flexible all‐solid‐state supercapacitor (ASSC) and an asymmetric supercapacitor (ASC) with an expanded voltage window (1.6 V) and long‐term cyclability (>5000 cycles) compared to many state‐of‐the‐art analogous materials and hybrids. It is believed that the synthetic strategy presented for the MX‐MC‐N hybrid will indubitably pave a path for the development of novel MXenes and heteroatom‐doped porous hybrid materials for sustainable energy applications.

Comprehensive energy-storage performance enhancement in relaxor anti-ferroelectrics via strengthening local polarization

Excellent energy storage and hardness performance of Sr0.7Bi0.2TiO3 ceramics fabricated by solution combustion-synthesized nanopowders

Microbial fuel cell (MFC) technology can potentially recover bioelectricity from wastewater. However, its practical applications have been limited because of its low power density and since the energy generated from an MFC cannot be stored. In this study, manganese dioxide (MnO2) coupled with carbon nanotubes (CNT) was chosen to in situ modify carbon felt (CF) as a capacitive bioanode (CF/CNT/MnO2) to improve the power generation and energy storage of MFCs. The maximum power density of the MFC with the MnO2-CNT-modified bioanode reached 3471.6 mW m3, which was 1.96 times higher than that of the CF/CNT anode (1772.6 mW m−3). During the experiment of charging for 30 min and discharging for 30 min, the MFC with a capacitive bioanode had a total charge of 8777.1 C m−2, 2.74 times higher than that of the CF/CNT anode. The excellent electricity-producing and energy storage performance of the MFC equipped with the CF/CNT/MnO2 anode is attributed to the composite materials, which can be due to their better biocompatibility, large capacitance, and high specific surface area. This study provides a new way to improve the performance of electricity generation and energy storage of MFCs.

Antiferroelectric domain modulation enhancing energy storage performance by phase-field simulations

High conductivity Ni12P5 nanowires as high-rate electrode material for battery-supercapacitor hybrid devices