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We present three novel conjugated microporous polymers (CMP@1–3), which were formed by an imidization reaction between tetra-(4-aminophenyl)ethylene and anhydrides. These CMPs exhibited high CO2 and organic vapor capture capacity.

Various photoactive building blocks can be incorporated into porous organic polymers (POPs). The intrinsic properties, such as various synthetic methods, outstanding inherent porosity, easy tunability, rigid conjugated skeletons and high stability, endow the polymeric organic networks with wonderful potential to act as heterogeneous photocatalytic platforms. However, exploitation of efficient synthetic strategies for metal-free and nontoxic heterogenous photocatalysts, and further insights into the photocatalytic process in organic transformations are still necessary. In this context, we report the concise synthesis of two polymeric frameworks (BTP-CMP and TBTP-CMP) incorporated into bithiophene and thiophthene units via a “bottom-up” strategy. BTP-CMP and TBTP-CMP were employed as heterogeneous photocatalysts in the synthesis of benzimidazoles, and exhibited excellent catalytic activity (up to 98% yield, at least 15 iterative runs). Therefore, the thiophene-embedded networks can serve as stable efficient and recyclable heterogeneous photocatalysts. Additionally, based on the catalytic results of control experiments and the energy band structures of the materials and intermediates, a possible photocatalytic reaction mechanism has been proposed.

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

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

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

The development of viable absorbents for highly efficient and selective removal of lead (Pb) ions, which might exist in various waste discharges related to human activities, is considered a long-st...

Metal phthalocyanines (MePc) hold great promises in electrochemical reduction of CO2 to value-added chemicals, whereas the catalytic activity of MePc-containing polymers often suffers from the limited molecular modulation strategy. Herein, we synthesize an ultrathin conjugated microporous polymer sheath around carbon nanotubes by an ionothermal copolymerization of CoPc and H2Pc via the Scholl reaction. Given the H2Pc-mediated regulation in synthesis, Co(II) metal is well preserved in form of single atoms on the polymer sheath of carbon nanotubes. With synergistic effect of H2Pc moieties as proton/electron donors, the composites can selectively reduce CO2 to CO with a high Faradic efficiency ( max. 97% at -0.9 V) in broad potential windows, exceptional turnover frequency (97,592 h-1 at -0.65 V) and large current density (> 200 mA cm-2). It is thus desirable to develop a family of heterogeneous polymerized MePc with molecularly regulating electrocatalytic activity.

Rapid and accurate detection of pesticide and veterinary drug residues is a continuing challenge because of the complex matrix effects. Thus, appropriate sample pretreatment is a crucial step for the effective extraction of the analytes and removal of the interferences. Recently, the development of nanomaterial adsorbents has greatly promoted the innovation of food sample pretreatment approaches. Porous organic frameworks (POFs), including polymers of intrinsic microporosity, covalent organic frameworks, hyper crosslinked polymers, conjugated microporous polymers, and porous aromatic frameworks, have been widely utilized due to their tailorable skeletons and pores as well as fascinating features. This review summarizes the recent advances for POFs to be utilized in adsorption and sample preparation of pesticide and veterinary drug residues. In addition, future prospects and challenges are discussed, hoping to offer a reference for further study on POFs in sample pretreatment.

The modern ages have seen an embarking trend in the technology revolving around the organic solvent nanofiltration (OSN) that employs pressure gradient to separate molecules in the range of 200–1000 g/mol. The OSN technique generally provides better energy efficiency as compared to conventional practices such as chromatography or solvent extraction, primarily under mild condition. This one of the prime reasons the OSN technique is used in commercially viable sectors such as fuel industries and chemical plants. Amidst these advantages, the methodology is still in its evolutionary phase since the fabrication of a material which may be stable is various kinds of solvents is an arduous task for the researchers. Furthermore, a bolstered reproducible result is not obtained from this technique creating several loopholes while considering this operation. This short review refers to the recent works reported by Liang et al. using conjugated microporous polymer membrane fabricated by surface-initiated polymerization. The membranes not only exhibited a much-reinforced resistance to the organic solvents but also exhibited an enhanced efficacy when contrasted to hexane and methanol.

We report the synthesis of two carbazole-thiophene-based conjugated microporous polymers (Cz-3Th and Cz-4Th CMPs) with different degrees of planarity for photocatalytic hydrogen evolution from water. Depending upon the building linker's planarity, we found that the porous structure, hydrogen-evolution rate, and photocatalytic stability of the resultant CMPs varied.

In recent decade, conjugated microporous polymers (CMPs) were treated as one of the superior porous materials for CO2 uptake. Herein, we prepared two azo-linked CMPs namely: azo-carbazole (Azo-Cz) and azo-phenothiazine (Azo-Tz) from the reduction of the corresponding nitro monomers using sodium borohydride (NaBH4). The obtained polymers were well characterized using many spectroscopic techniques. According to TGA and BET analyses, our CMPs owned good specific surface areas (reaching 315 m2 g–1), and a significant thermal stability. It is also possessed pore sizes of 0.79 and 1.18 nm, respectively, and a reasonable char yields (max. 46 %). Based on CO2 uptake measurements, the CO2 adsorption capacities of these CMPs were very good: up to 40 and 94 mg g–1 at the experiment temperatures 298 and 273 K, respectively. The great CO2 uptake is due to high surface areas that facilitate powerful interactions with CO2 molecules. Supplementary information The online version contains supplementary material available at 10.1007/s10965-021-02803-8.

This paper demonstrates the hierarchical design of functional, fibrous polymer monoliths. The monoliths are composed of conjugated microporous polymers that not only are embedded with heteroatoms but also feature fibrous yet compressible structures due to the in situ self-assembly process that occurs during the polymerization process. Therefore, the doped nitrogen atoms can allow the growth of zeolitic imidazolate framework (ZIF) nanocrystals, which causes the homogeneous encapsulation of individual fibers. The resulting hybrid monoliths exhibit enhanced physical properties as well as catalytic activity, allowing the formation of an additional coating layer via a thiol-epoxy reaction. The deliberate inclusion of template molecules during the reaction forms molecularly imprinted sites on the fibers to afford functional monoliths. As a proof of concept, the hierarchically designed materials are able to show effective recognition properties toward diethylstilbestrol, an endocrine disruptor, taking advantage of the binding sites that selectively capture the analyte molecules and the fibrous morphology that increases the accessibility of these binding sites. We envisage that the incorporation of various heteroatoms or nanocrystals will bring about the bespoke design of advanced monoliths with autonomous functions, leading to smart textile systems.

Two tetraphenylethylene-based fluorescent conjugated microporous polymers (TTTPT and TTDAT) were obtained by the Friedel−Crafts polymerization reactions catalyzed 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 with high quenching coefficients of 9.13×103 and 1.31×105 L mol-1, respectively. TTDAT can also sense to dinitrophenol 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 and/or the resonant energy transfer mechanism.

Conjugated microporous polymers (CMPs) are an emerging class of porous organic polymers that combine π-conjugated skeletons with permanent micropores. Since their first report in 2007, the enormous exploration of linkage types, building units, and synthetic methods for CMPs have facilitated their potential applications in various areas, from gas separations to energy storage. Owning to their unique construction, CMPs offer the opportunity for the precise design of conjugated skeletons and pore environment engineering, which allow the construction of functional porous materials at the molecular level. The capability to chemically alter CMPs to targeted applications allows for the fine adaptation of functionalities for the ever-changing environments and necessities. Bifunctional CMPs are a branch of functionalized CMPs that have caught the interest of researchers because of their inherent synergistic systems that can expand their applications and optimize their performance. This review discusses the rational design and synthesis of bifunctional CMPs and summarizes their advanced applications. To conclude, our own perspective on the research prospects of these types of materials is outlined.

Ferrocene is used as a catalytically active site and building block to construct a new conjugated microporous polymer (CMP), named Fc-POP. A corresponding carbon nanotube composite (CNTs@Fc-POP) with tubular structure was obtained through the π–π interaction between multi-walled carbon nanotubes (MWCNTs) and reactive molecules. This innovative modification method of carbon nanotubes provides a way to construct functionalized carbon materials. The two materials can achieve high conversion and selectivity of benzene hydroxylation to phenol under light irradiation using hydrogen peroxide (H2O2) as an oxidant. Due to the synergistic effect between the carbon nanotubes and the ferrocene group, the incorporation of MWCNTs can improve the yield of phenol significantly. This work explores a new photocatalystic system and expands the related photocatalytic application of CNTs.

Herein, we synthesize the thiophene tetraphenylethene-based conjugated microporous polymer (ThT-CMP) using the tetraphenylethylene derivative [i.e., 1,1,2,2-tetrakis(4-bromophenyl)ethane (TPBE)] and 2,5-thiophenediboronic acid as the precursors. The aggregation of TPBE in the ThT-CMP can induce a strong dual-band bipolar electrochemiluminescence (AIECL) emission at 554 nm (anodic) and 559 nm (cathodic) with tri-n-propylamine (TPrA) and S2O82- as the coreactants, respectively. The anodic and cathodic ECL efficiencies are measured to be 11.49 and 3.82% with respect to the standard of the Ru(bpy)32+/TPrA system, respectively. We further develop a dipolar ECL sensor to sensitively detect rhodamine B (RhB) based on resonance energy transfer. This ECL sensor possesses a large dynamic range and high sensitivity. This research provides a new avenue of designing organic structures with the characteristic of bipolar AIECL for the development of luminescent devices.

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 PM0.3 and 99.9% for PM2.5 and PM10, 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 PM2.5 and PM10 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.

Conjugated microporous polymers (CMPs) with robust architectures, facilely tunable pore sizes and large specific surface areas have emerged as an important class of porous materials due to their demonstrated prospects in various fields, e.g. gas storage/separation and heterogeneous catalysis. Herein, two new pyrrole-based CMPs with large specific surface areas and good stabilities were successfully prepared by one-step oxidative self-polycondensation of 1,2,4,5-tetra (pyrrol-2-ly)benzene or 1,3,5-tri (pyrrol-2-ly)benzene, respectively. Interestingly, both CMPs showed very high catalytic activity toward Knoevenagel condensation reaction, which was attributed to the inherent pore channels, high specific surface areas and abundant nitrogen sites within CMPs. Additionally, both CMPs displayed excellent recyclability with negligible degradation after 10 cycles. This work provides new possibilities into designing novel nitrogen-rich high-performance heterogeneous catalysts.

Fully aromatic, organic polymers have the advantage of being composed from light, abundant elements, and are hailed as candidates in electronic and optical devices “beyond silicon”, yet, applications that make use of their π-conjugated backbone and optical bandgap are lacking outside of heterogeneous catalysis. Herein, we use a series of sulfur- and nitrogen-containing porous polymers (SNPs) as real-time optical and electronic sensors reversibly triggered and re-set by acid and ammonia vapors. Our SNPs incorporate donor-acceptor and donor-donor motifs in extended networks and enable us to study the changes in bulk conductivity, optical bandgap, and fluorescence life-times as a function of π-electron de-/localization in the pristine and protonated states. Interestingly, we find that protonated donor-acceptor polymers show a decrease of the optical bandgap by 0.42 eV to 0.76 eV and longer fluorescence life-times. In contrast, protonation of a donor-donor polymer does not affect its bandgap; however, it leads to an increase of electrical conductivity by up to 25-fold and shorter fluorescence life-times. The design strategies highlighted in this study open new avenues towards useful chemical switches and sensors based on modular purely organic materials.

How to efficiently control the metal sites in carriers is of great importance in the design of high-efficiency heterogeneous catalysts, but still remains to be difficult. Herein, we provide an efficient one-pot strategy to design conjugated microporous polymers (CMPs) loaded with superfine palladium (Pd) sites, referring a Pd-catalyzed Suzuki coupling reaction and pyrolysis reduction process. Beneficial from micropore-confinement effect by CMPs, the size of deposited Pd can be well controlled (lower than 2 nm), exhibiting excellent catalytic activity on p-nitrophenol reduction. Super small size of Pd sites and the retainment of pores during the Pd formation is thought to be the main reason for high catalytic activity of the Pd/CMPs catalysts. It expands the exploration and development of heterogeneous catalysts by micropore-confined strategy.

Four truxene-based conjugated microporous polymers (Tr-CMPs) were prepared via different synthetic methods and their structure-property relationships were studied. The polymer networks have high Brunauer-Emmett-Teller (BET) specific surface areas ranging from 554 m2·g−1 to 1024 m2·g−1. Pore sizes of the CMPs with different linkers are mainly located between 0.60 and 1.96 nm. Among all the Tr-CMPs, Tr-CMP4 has the highest BET surface area of 1024 m2·g−1 and exhibits the highest H2 uptake of 0.88 wt%. Tr-CMP2 prepared by Suzuki-Miyaura coupling reaction has the highest photoluminescence quantum yields (PLQYs) of 13.06% and CO2 uptake of 6.25 wt%.

An efficient visible-light-driven photocatalyst with interface charge transfer (IFCT) effect was achieved by assembling Fe-porphyrin based conjugated microporous polymer on TiO2 microspheres. It was revealed that IFCT effect played a crucial role in the enhancement of photocatalytic performance. In addition, the oxygen reduction reaction (ORR) activity of TiO2 was enhanced in the presence of Fe-porphyrin based conjugated microporous polymer and IFCT effect was promoted obviously due to the high ORR activity. It’s speculated that multi-electron ORR could accelerate the consumption of photoinduced electrons, retarding the recombination of photoinduced holes and electrons in the IFCT process, leaving more high-oxidizing photoinduced holes in the valance band of TiO2 for further degradation. What’s more, to further clarify the relationship between multi-electron ORR and IFCT effect, the influence of electron transfer number on the generation of photoinduced holes in the IFCT process was studied, and it was believable that four-electron oxygen reduction process was better able to accelerate the generation of photoinduced holes in the IFCT process than two-electron oxygen reduction process, resulting in higher photocatalytic activity.

Two tetraphenylethylene-based fluorescent conjugated microporous polymers were obtained by the polymerization of a CH3SO3H catalyzed Friedel−Crafts polymerization reaction. The resulting CMPs show high thermal stability with a decomposition temperature above 575 and 487 °C, and have the porosity with BET surface area of 564.8 and 44.1 m2 g−1, respectively. Due to the introduction of tetraphenylethylene units, the CMPs have excellent fluorescence sensing performance for I2 with high Ksv of 1.53 × 105 and 9.07 × 104 L mol−1. Taking advantage of such porosity, effective sorption sites, and charge-transfer interactions, which display excellent I2 adsorption capacity in vapor with the uptake of up to 3.41 and 2.91 g g−1.

BACKGROUND: A magnetic conjugated microporous polymer (MCMP) composite was designed with bromo groups of CMP and amino groups on the surface of Fe₃O₄ nanoparticles that acted as promising adsorbents for wastewater treatment. Fe₃O₄ nanoparticles were successfully bonded on the predesigned CMP material to form the MCMP by means of a new and simple nucleophilic substitution reaction in organic media. RESULTS: The MCMP could be separated by applying an external magnetic field because of the Fe₃O₄ nanoparticles. It exhibited sufficient dye adsorption for methylene blue (MB) with a high sorption capability of 869.43 mg g⁻¹ in aqueous solutions. The recovery and reusability of MCMP were >70% after six cycles of desorption and regeneration, indicating that the MCMP had excellent cycle stability. The magnetization saturation strength of MCMP was 13.5 emu g⁻¹ which was sufficient to be magnetically separated from wastewater using artificial magnetic fields. CONCLUSION: The MCMP possessed excellent adsorption capacity and dispersibility, and good recyclability after banded with functionalized Fe₃O₄ nanoparticles. The excellent properties of MCMP indicated that it could be used as an adsorbent with great application potential for quick separation of water pollutants such as dyes in wastewater treatment. © 2019 Society of Chemical Industry

Simple inorganic salts are used to tune N‐containing conjugated microporous polymers (CMPs) synthesized by Buchwald–Hartwig (BH) cross‐coupling reactions. Poly(triphenylamine), PTPA, initially shows a broad distribution of micropores, mesopores, and macropores. However, the addition of inorganic salts affects all porous network properties significantly: the pore size distribution is narrowed to the microporous range only, mimicking COFs and MOFs; the BET surface area is radically improved from 58 m2 g−1 to 1152 m2 g−1; and variations of the anion and cation sizes are used to fine‐tune the surface area of PTPA, with the surface area showing a gradual decrease with an increase in the ionic radius of salts. The effect of the salt on the physical properties of the polymer is attributed to adjusting and optimizing the Hansen solubility parameters (HSPs) of solvents for the growing polymer, and named the Beijing–Xi'an Jiaotong (BXJ) method.

π-Radical conjugated microporous polymers (CMPs) are highly appealing for optoelectronics, especially optical response-based sensor devices, and their thin film fabrication is demanding for develop...

Various structures of conjugated microporous polymers (CMPs) were synthesized via the Suzuki cross-coupling reaction to detect the explosive compound, picric acid (PA). One of the CMP, CMP-3 showed...

Pyrogenic carbonaceous matter (PCM) is redox-active and promotes both abiotic and biotic reactions in the environment, possibly as a result of its conductivity and phenolic/quinone functional groups. However, due to the complexity of PCM, the contribution of conductivity or phenolic/quinone functional groups to its redox activity is poorly understood, which hinders its potential engineering applications. Here, we synthesized tunable conjugated microporous polymers (CMPs) that possess key properties of PCM, which can be used as PCM analogues to provide insights to PCM reactivity. Specifically, controlled incorporation of phenolic moieties into CMPs during polymer synthesis affected electron-donating capacity, while carbonization of CMPs at various temperatures altered conductivity. Both properties were then correlated with PCM reactivity measured by the decay kinetics of a model pollutant trichloronitromethane. We demonstrate that some of the prepared CMPs enabled transformation of trichloronitromethane, while no decay was observed in the absence of CMPs. Results of further investigation suggest that trichloronitromethane decay occurs by reductive dechlorination, suggesting that CMPs are electron donors and the first dissociative electron transfer from CMPs was likely to be the rate-limiting step. Conductivity but not electron-donating capacity was positively correlated with CMP-mediated trichloronitromethane decay kinetics, suggesting an important role of the electron transfer kinetics at the interface for PCM-mediated transformation of environmental pollutants.

Incorporation of highly extended π-conjugated molecules into conjugated microporous polymers (CMPs) is one of the important aspects in material science. Herein we synthesize conjugated microporous polymers (CMP-Gs) with covalently linked molecular graphenes by an efficient tandem oxidative reaction in one-pot, which comprising Scholl-type cyclodehydrogenation and oxidative polymerization. Oxidation of m- or p-thienyl decorated hexaphenylbenzene derivatives with excess of FeCl3 allowing in situ generation of size-controlled graphitic segments form CMP-G1 and CMP-G2 in high yields, respectively. CMP-Gs possess large surface areas and micropore size from 0.5 to 1.5 nm. Gravimetric hydrogen adsorption isotherms show that the adsorption capacity for hydrogen is up to 2.69 wt% for CMP-G1 and 2.14 wt% for CMP-G2 at 20 bar and 77 K, respectively.

Conjugated microporous polymers (CMPs) with permanent microporosity and extended p-conjugated skeletons have recently shown the fascinating application in separation and enrichment. In this report, porphyrin CMP that possessed microporous structure and nitrogen-rich pyrrole building blocks was successfully synthesized by microwave-assisted method. Then, a novel coating based on porphyrin CMP was fabricated on silica fiber for efficient enrichment volatile organic acids (VOAs). The simulation showed the coating exhibited strong interaction with volatile organic acids based on charge transfer interaction, hydrogen bond and size effect. Hence, we proposed a method for determination of volatile organic acids in tobaccos by headspace solid-phase microextraction (HS-SPME) with porphyrin CMP coating by gas chromatography-mass spectrometry. The results showed that the coating provided high enrichment factors for VOAs ranging from 66,657 to 133,970 and low limits of detection from 4.6 to 22 ng/L. A good linearity was observed for propionic acid and crotonic acid ranging from 0.050 to 8.0 μg/L, 2-methylheptanoic acid ranging from 0.063 to 1.5 μg/L, others ranging from 0.025 to 3.0 μg/L with the determination coefficient (R2) between 0.9900 and 0.9980. The strategy for determination of volatile compounds in complex solid samples was successfully applied to the analysis of volatile organic acids in tobacco leaves. The results showed that the method was accurate and reliable.

Two new spirobifluorene-based conjugated microporous polymers, TS-TAD and TS-TADP, were constructed via Friedel-Crafts coupling reactions. TS-TAD and TS-TADP possess high BET surface area of 828 and 783 m2 g−1, large pore volume of 1.51 and 0.54 cm3 g−1, good stability, and display excellent guest uptake of 4.15 and 3.65 g g−1 in iodine vapour as well as reversible adsorption of iodine in solution. The specific surface areas of CMPs were increased by the introduction of bispirofluorene rings compared with the corresponding parent polymers. TS-TAD has a similar structure to TS-TADP, but possesses larger specific surface area and pore values than TS-TADP, hence, TS-TAD has a higher adsorption capacity for iodine than TS-TADP. Moreover, the adsorption rate of TS-TAD is slower than that of TS-TADP in I2 vapor, while it is faster than that of TS-TADP in cyclohexane solution. We also highlight that the both resulting CMPs exhibit outstanding performance for fluorescent sensing to iodine and nitroaromatic compounds, thus making the resulting CMPs ideal absorbent materials for reversible iodine capture, sensing iodine and nitroaromatic compounds to address environmental issues.

High-performance capturing polar phenoxycarboxylic acids herbicides (PCAs) from water samples remains a great challenge because PCAs form salt easily and dissolve. Polyphenylene-based conjugated microporous polymers (PP-CMPs), a fascinating type of polymers, bear π-conjugation over 3D polyphenylene scaffolds, inherent micropore, and large surface area, which are essential for capturing trace PCAs in complex samples. This work developed a novel approach to quantify trace PCAs using PP-CMPs as an efficient dispersive solid-phase extraction (d-SPE) adsorbent. The developed method based on PP-CMPs achieved high sensitivity with limits of detection of 0.55–3.84 ng L−1, satisfactory correlation coefficients (≥ 0.9912), good linearity (50–10,000 ng L−1), and good precisions (2.0–9.0%). Moreover, this method was used for simultaneous monitoring of the amounts of five PCAs in environmental water samples with satisfactory spiked recoveries (86.9–101.3%). All these fact demonstrated that this new d-SPE technique based on PP-CMPs exhibited a promising potential for highly sensitive analysis of trace PCAs in complex samples.

This work shows that the shape-controlled microporous organic polymer (MOP) can be utilized for the morphological engineering of another class of MOP materials. The morphology of a hyper-cross-linked polymer (HCP) was successfully engineered on the hollow conjugated microporous polymer (CMP). Through the postsynthetic modification of HCP bearing BINOLs (HCP-B) on the hollow CMP-like material (H-CMPL), the HCP bearing BINOL phosphoric acid (HCP-BP) was engineered on the H-CMPL platform. The resultant H-CMPL@HCP-BP showed good catalytic performance as a heterogeneous catalytic system and excellent recyclability in the ring-opening polymerization of ε-caprolactones to poly(caprolactone).

The molecular design of highly photo-functional polymers with high charge separation efficiency and wide spectral absorption are long term quest for photocatalysis. Herein, we design and develop a series of nitrogen-containing conjugated microporous polymers (N-CMPs) with tailored donor-acceptor units for enhancing charge separation and light harvesting for visible light photocatalytic H2 production. By alternating the substitution position (o-, m-, or p-) and the number of electron donor (carbazole, diphenylamine) and acceptor (cyano) units on the 3D-core structure, a series of N-CMPs with adjustable donor-acceptor (D-A) charge separation efficiencies and tuneable band gaps in the range of 1.64–2.29 eV were obtained, enabling the precise control of the photocatalytic activity at the molecular level. The optimized N-CMP (4-CzPN) exhibits a higher visible light H2 production rate at 2103.2 μmol/h·g and the apparent quantum yield (AQY) at 420 nm reaches 6.4%. Furthermore, the 4-CzPN photocatalyst maintains excellent durability and recycling performance under 25 h continued light irradiation. The outstanding photocatalytic performance of the optimized N-CMPs with D -A structure is attributed to the enhanced polarity and conjugated degree of their core structure, which promotes charge separation and light absorption.

Metal-free, visible-light driven, solid organic photocatalysts provide a more green and environmentally friendly alternative to traditional metal-based photocatalysts. Donor-Acceepor (D-A) dyads possess a feature of easy to adjust the photoelectric properties, and enhance their photocatalytic performances. Here we report a fascinating strategy for screening excellent organic porous photocatalysts through oxidative coupling of single D -A based monomer, which has still an important advantage to ensure uniformity of polymer structure except for the inherent characteristics of D -A polymers. According to this strategy, three D -A typed conjugated microporous polymer (DA-CMP) photocatalysts consisting of alternating electron-rich (carbazole) and electron-deficient (benzene, 4,7-diphenyl-2,1,3-benzothiadiazole or anthraquinone) units have been synthesized, and their porosity and photoelectric properties including adsorption, emission, lifetime, optical bandgaps, energy levels and transient photocurrent response as well as photocatalytic activity, were conveniently tuned by selecting different D -A monomers with tunable electron-deficient moiety. These DA-CMPs were exploited as metal-free photocatalysts in the oxidative C-H functionalization reactions in the presence of visible-light and molecular oxygen. They showed excellent photocatalytic activity, extensive substrate adaptability and outstanding reusability, due to combining some key features like permanent porosity, outstanding stability and optoelectronic properties. In addition, the reaction mechanism for DA-CMP photocatalyzed C-H functionalization reactions under visible-light irradiation was investigated in detail. Moreover, to prove in depth the benefits of the heterogeneous photocatalysis, a continuous flow procedure has been conducted with an excellent yield.

Herein, we describe a visible-light-induced radical strategy for the 1,2-formylarylation of N-arylacrylamides via the C–H activation of 1,3-dioxolane using a carbazolic-cyano conjugated microporous...

Syntheses and detailed spectroscopic characterizations of two similar conjugated microporous polymers formed by A4 $+$ B2 and A2 $+$ B3 type functional monomers via Sonogashira--Hagihara polycondensation are presented in this report. The two porous polymeric networks possess mono-, di-, and tri- (1-, 1,4-, and 1,3,5-, respectively) substituted benzene rings and fused thiophenic moieties (dithienothiophenes). Because of the different conjugation patterns, their solid state nuclear magnetic resonance, infrared, and ultraviolet/visible light absorption analyses indicated significant differences. Besides the discussions on the porous properties of the obtained polymeric networks, the presented spectroscopic investigations can be useful for identifying the structure-property relationship of the novel conjugated porous polymeric structures, since the characterization of such nonsoluble compounds by using fundamental techniques is always a challenge.

Carbon dioxide from the combustion of fossil fuels causes many environmental problems, so the capture of CO2 is especially important. Porous organic polymers (POPs) are regarded as a kind of excellent candidate for CO2 capture because of their high surface areas, suitable pore size, low cost, and good physicochemical stability. This review aims to summarize the development of CO2 capture by POPs, including hypercrosslinked polymers, covalent organic frameworks, conjugated microporous polymers, and covalent triazine–based frameworks, in the last two years. The relationship between the characteristic features and CO2 uptake capability is described. The advantages and disadvantages of each type of POPs and their future challenges are also discussed.

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.