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The multiple mortise‐and‐tenon joint parts are the core factors to provide the structural stability and diversity of Chinese Luban locks; however, constructing such structures is very challenging. Herein, single crystals of a covalent organic nanoribbon (named CityU‐27) are prepared through the assembly of hexahydroxytriphenylene (HHTP), 4,4′‐vinylenedipyridine (BYE), and phenylboronic acid (BA) together through dative boron←nitrogen (B←N) bonds. The single‐crystal X‐ray diffraction analysis indicates that CityU‐27 has a covalent organic nanoribbon structure, where each nanoribbon forms multiple and tight π–π interactions with four neighboring others to generate a Luban lock‐like configuration. CityU‐27 has been demonstrated to be an efficient photocatalyst in a one‐pot tandem reaction of hydrogen evolution reaction (HER) and semi‐hydrogenation reaction of alkynes in series to produce olefins without any additional photosensitizers and co‐catalysts (metal‐free). [ABSTRACT FROM AUTHOR]

Diphenylalanine(FF)-Zn self-assembly (FS) confined in covalent organic polymers (FS@COPs) with efficient fluorescence was synthesized for fluorescence sensing of biogenic amines, which was one of the most important indicators for monitoring food freshness. FS@COPs combined excellent biodegradability of self-assembled dipeptide with chemical stability, porosity and targeted site recognition of COPs. With an optimal excitation wavelength of 360 nm and an optimal emission wavelength of 450 nm, FS@COPs could be used as fluorescence probes to rapidly visualize and highly sensitive determination of tryptamine (Try) within 15 min, and the linear range was from 40 to 900 μg L−1 with a detection limit of 63.08 μg kg−1. Importantly, the FS@COPs showed a high fluorescence quantum yield of 11.28%, and good stability, solubility, and selectivity, which could successfully achieve the rapid, accurate and highly sensitive identification of Try. Furthermore, we revealed the mechanism of FS@COPs for fluorescence sensing of targets. The FS@COPs system was applied to the fluorescence sensing of Try in real samples and showed satisfactory accuracy of 93.02%-105.25%. [ABSTRACT FROM AUTHOR]

In recent years, the massive use of pharmaceuticals has led to the detection of a large number of relevant residues in water. As emerging contaminants, pharmaceuticals residues in the environment pose a major threat to human health and ecosystems. Covalent organic polymers (COPs) possess high stability, uniform pore size, and easy functionalization, which have attracted great attention in water treatment. In this study, a novel covalent organic polymer was successfully studied by a simple synthesis method, combining p-phenylenediamine (Pd) and isophthalaldehyde (Is) via a Schiff-base (referred to PdIs-COP), which was used as an absorbent for the removal of indomethacin from aqueous solutions. The composite was characterized with scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) specific surface area and thermogravimetric (TGA) analysis. The effect of changes in the pH values and the adsorption time on the adsorption capacity was also investigated. The results of this study indicated that the absorbent had a high adsorption capacity for indomethacin. The adsorption capacity of PdIs-COP for indomethacin is 92.86 mg g−1 at pH of five and a contact time of 2 min. This shows that PdIs-COP is a novel material with good affinity for pharmaceuticals. [ABSTRACT FROM AUTHOR]

The covalent organic frameworks/polymers configurated with metal‐N4 conjugated structures offer an exceptional platform for efficient electrochemical CO2 reduction reaction (eCO2RR). However, understanding the impact of the structure‐mediated local microenvironment and integrating CO2 electroreduction with follow‐up utilization toward extending chemical valorization of CO2 are still far from sufficient. Herein, a set of covalent phenanthroline‐porphyrin polymers are designed to decode the microenvironment modulation originating from built‐in structures, and the optimized one delivered an extraordinary performance for eCO2RR with ≈100% Faradaic efficiency of CO under stabilized CO2‐electrolysis of 70 h. The experimental and theoretical analyses suggest that the regulation of the Co‐N4 electronic structures and microenvironment convoys the stabilized formation of key reaction intermediate *COOH. Furthermore, through CO‐mediated electro/thermocatalytic tandem processes, the aminocarbonylation of aryl iodides and amines with high yields has been convincingly implemented over the coordinated Pd sites, which is remarkably helpful to propel extending chemical valorization of CO2. [ABSTRACT FROM AUTHOR]

The covalent organic frameworks/polymers configurated with metal‐N4 conjugated structures offer an exceptional platform for efficient electrochemical CO2 reduction reaction (eCO2RR). However, understanding the impact of the structure‐mediated local microenvironment and integrating CO2 electroreduction with follow‐up utilization toward extending chemical valorization of CO2 are still far from sufficient. Herein, a set of covalent phenanthroline‐porphyrin polymers are designed to decode the microenvironment modulation originating from built‐in structures, and the optimized one delivered an extraordinary performance for eCO2RR with ≈100% Faradaic efficiency of CO under stabilized CO2‐electrolysis of 70 h. The experimental and theoretical analyses suggest that the regulation of the Co‐N4 electronic structures and microenvironment convoys the stabilized formation of key reaction intermediate *COOH. Furthermore, through CO‐mediated electro/thermocatalytic tandem processes, the aminocarbonylation of aryl iodides and amines with high yields has been convincingly implemented over the coordinated Pd sites, which is remarkably helpful to propel extending chemical valorization of CO2. [ABSTRACT FROM AUTHOR]

The first flow‐type solar and seawater co‐mediated sodium‐air rechargeable battery (SSRB) for efficient solar‐to‐electrochemical energy conversion/storage is established. Such SSRB is enabled by a robust self‐regulated CEP/ZnWO4/WO3 heterojunction photoelectrochemical electrodes (PE) by passivating predesigned crown ether‐rich photoresponsive covalent organic polymer (CEP) layers onto ZnWO4‐modified WO3 nanosheet arrays. The PE design utilizes the previously‐unexplored self‐mediated effect of CEP to endow PE with superior stability, facilitated electrode reaction kinetics, and high efficiency of spatial charge separation simultaneously. This leads to remarkable light‐enhanced oxygen evolution catalysis with impressive photocurrent density up to 6.1 mA cm−2 at 1.23 V versus RHE in seawater – surpassing metal‐oxide‐based PEs ever reported for seawater splitting. Thus, the SSRB breaks the limit of the equilibrium voltage (3.47 V) of conventional seawater sodium‐air cells to deliver a low charge voltage of 2.71 V along with stable photo‐charge over 100 h and good photo‐charge/normal discharge cycling stability over 240 h – superior to almost all existing light‐involved air batteries. Combined experimental and modeling studies for the first time unveil the multi‐regulation effects of CEP passivation which prevents detrimental Cl‐corrosion, and promote oxygen evolution kinetics. [ABSTRACT FROM AUTHOR]

The FePc-based covalent organic polymers (COP FePc) polymerized in situ on the functionalized multiwalled carbon nanotubes (R-MWCNT) were synthesized (COP FePc /R-MWCNT, R = COOH, OH or NH 2) for ORR under pH-universal conditions. The carbon nanotubes with electron-withdrawing or electron-donating groups induce charge redistribution around the active center Fe, tuning the ORR activity. The COP FePc /COOH-MWCNT catalyst exhibited an impressive ORR activity with half-wave potentials of 0.92, 0.78, and 0.72 V in alkaline, acidic, and neutral electrolytes, respectively. [Display omitted] Iron phthalocyanine (FePc) is an attractive nonprecious metal candidate for electrocatalytic oxygen reduction reaction (ORR). However, its low catalytic performance under acidic and neutral conditions limits its practical application. Herein, the FePc-based covalent organic polymers (COP FePc) polymerized in situ on the functionalized multiwalled carbon nanotubes (R-MWCNT) containing different electron-withdrawing or electron-donating groups (COP FePc /R-MWCNT, R = COOH, OH or NH 2) were synthesized for ORR. Among them, COP FePc /COOH-MWCNT exhibited the best ORR performance under pH-universal conditions (acidic, neutral, and alkaline). Density-functional theory (DFT) calculations demonstrate that the electron-withdrawing or electron-donating effect of the functional groups in COP FePc /R-MWCNT causes charge redistribution of the active center Fe. The COOH functional group with an electron-withdrawing ability shifts the d -band center of Fe away from the Fermi energy level and reduces the binding strength of oxygen-containing intermediates, accelerating the ORR kinetics and optimizing the catalytic activity. [ABSTRACT FROM AUTHOR]

Covalent organic polymers (COPs) have emerged as a promising class of materials for memory devices due to their unique electronic properties and potential for tunability. This review highlights recent advances in the field of COPs‐based thin films for memory applications, with a focus on the synthesis and characterization of COP thin films, their electronic properties, and their performance as memory devices. The potential of COPs‐based thin films as flexible memory devices is also discussed. Overall, the recent progress in COPs‐based thin films for memory applications suggests that these materials may have a significant impact on the development of next‐generation memory technologies. [ABSTRACT FROM AUTHOR]

Growing single crystals of covalent organic polymers (COPs) for single‐crystal X‐ray diffraction analysis is very important and highly desirable because such strategy provides a deep understanding of crystallization kinetics and the structure‐property relationship of COPs. Based on the strategy that dynamic covalent bonds can allow self‐correction of structures during crystal growth, single crystals of two COPs (CityU‐15 and CityU‐16) based on dative boron‐nitrogen (B─N) bonds have been successfully obtained. Detailly, tetra(4‐pyridyl)tetrathiafulvalene (TTF(py)4) and tetra(4‐pyridyl)porphine (TPYP) are employed as N‐donor ligands to react with 1,4‐bis(benzodioxaborole) benzene to prepare single crystals of COPs, named as CityU‐15 and CityU‐16, respectively. CityU‐16 exhibits enhanced stability compared to CityU‐15, and the size of CityU‐16 single crystals can reach up to 0.7 cm. CityU‐15 shows good recyclability and reveals noticeable photosensitivity upon iodine doping. After treatment with iodine, both crystals display obvious color changes. Specially, the device based on I2‐treated CityU‐15 exhibits excellent low‐voltage operation and low energy consumption of 3.3 fJ, facilitating the development of artificial vision. This work highlights the successful introduction of functional groups into B‐N‐containing COPs, opening up new avenues for expanding their applications. [ABSTRACT FROM AUTHOR]

Covalent organic polymers (COPs) memristors with multilevel memory behavior in harsh environments and photoelectric regulation are crucial for high‐density storage and high‐efficiency neuromorphic computing. Here, a donor–acceptor (D–A)‐type COP film (Py‐COP‐3), which is initiated by keto–enol tautomerism, is proposed for high‐performance memristors. Satisfactorily, the indium tin oxide (ITO)/Py‐COP‐3/Ag device demonstrates multilevel memory performance, even in high temperatures, acid‐base corrosion, and various organic solvents. Moreover, the performance can be modulated by the photoelectric effect to maintain a great switching behavior. By contrast, Py‐COP‐0, with similar structure and chemical composition to Py‐COP‐3 but without keto–enol tautomerism, exhibits binary storage performance. Further studies unravel that both the formation of conductive filaments and charge transfer within D‐A Py‐COP‐3 film contribute to the resistive switching behavior of memory devices. [ABSTRACT FROM AUTHOR]

Sodium ion‐batteries (SIBs) are considered as a class of promising alternatives to lithium‐ion batteries (LIBs) to overcome their drawbacks of limited sources and safety problems. However, the lack of high‐performance electrode materials hinders the wide‐range commercialization of SIBs. Comparing to inorganic counterparts, organic electrode materials, which are benefitted from flexibly designable structures, low cost, environmental friendliness, and high theoretical gravimetric capacities, should be a prior choice. Here, a covalent organic polymer (COP) based material (denoted as CityU‐9) is designed and synthesized by integrating multiple redox motifs (benzoquinone and thioether), improved conductivity (sulfur induction), and intrinsic insolubility (rigid skeleton). The half‐cell SIBs exhibit ultrahigh specific capacity of 1009 mAh g−1 and nearly no capacity drop after 650 cycles. The first all‐COP symmetric full‐cell shows high specific capacity of 90 mAh g−1 and excellent rate capability. This work can extend the selection of redox‐active moieties and provide a rational design strategy of high‐performance novel organic electrode materials. [ABSTRACT FROM AUTHOR]

A novel disulfide functionalized nitrogen-rich covalent organic polymer (S-COP) directly synthesized by a solvothermal method were characterized by XRD, SEM, FT-IR, N2 adsorption–desorption and XPS techniques. The as-synthesized polymer shows efficient adsorption performance for Au(III) from aqueous solution. The adsorption equilibrium of the adsorbent could be achieved within 5 h, and the as-synthesized S-COP exhibits an exceedingly high Au(III) uptake capacity of 1506 mg·g−1. Furthermore, S-COP has satisfactory selectivity and reusability, which is a highlight of adsorption materials. [ABSTRACT FROM AUTHOR]

Covalent organic polymers (COPs) membranes have been widely investigated in recent years for the application and preparation of composite nanofiltration (NF) membranes due to the abundant pore structure. However, there are still difficulties in the easy and reliable preparation of scalable and highly permeable COPs membranes. In this work, the polyaminophenylene (PAP) layer was constructed on polysulfone (PSF) ultrafiltration membranes by diazonium-induced anchoring process (DIAP), and then used as a substrate to prepare ultra-thin and highly permeable COPs NF membranes by interfacial polymerization (IP) in only 20 ​s. The presence of PAP layer increases the aqueous phase monomer storage to promote the forward progression and limits the reaction zone of IP, thus resulting in ultrathin and highly crosslinked COPs membranes. In addition, the PAP layer covalently grafted onto the PSF molecular chain also participates in the IP reaction, thus the separation layer is connected to the substrate as a whole for better stability and can operate for long periods of time in an alcohol-based organic solvent environment. The methanol permeance of optimal NF-PAP membrane prepared based on the above strategy can reach 362-398 ​L−1m−2h−1bar−1, which almost achieves an order of magnitude enhancement relative to other reported COPs organic solvent nanofiltration (OSN) membranes. The retention rate of the COPs composite membrane for naphthol green B (Mw ​= ​878) dye was about 98.5 ​%, demonstrating good alcohol recovery ability. In conclusion, this study offers a potential strategy for the development and application of COPs OSN membranes.

Abstract Sodium ion‐batteries (SIBs) are considered as a class of promising alternatives to lithium‐ion batteries (LIBs) to overcome their drawbacks of limited sources and safety problems. However, the lack of high‐performance electrode materials hinders the wide‐range commercialization of SIBs. Comparing to inorganic counterparts, organic electrode materials, which are benefitted from flexibly designable structures, low cost, environmental friendliness, and high theoretical gravimetric capacities, should be a prior choice. Here, a covalent organic polymer (COP) based material (denoted as CityU‐9) is designed and synthesized by integrating multiple redox motifs (benzoquinone and thioether), improved conductivity (sulfur induction), and intrinsic insolubility (rigid skeleton). The half‐cell SIBs exhibit ultrahigh specific capacity of 1009 mAh g−1 and nearly no capacity drop after 650 cycles. The first all‐COP symmetric full‐cell shows high specific capacity of 90 mAh g−1 and excellent rate capability. This work can extend the selection of redox‐active moieties and provide a rational design strategy of high‐performance novel organic electrode materials.

Owing to the poor treatment efficiency of wastewater containing fluoroquinolones (FQs), effective removal of such pollutants has become a significant issue in waste management. In this study, a ternary covalent organic polymer anchored with SO3H (COP-SO3H) was designed using the Schiff reaction and a multicomponent solvent thermal method. The synthesized COP-SO3H polymer possesses multiple functional binding sites, including amide groups, sulfonic groups, and aromatic frameworks, enabling it to effectively adsorb ciprofloxacin (which belongs to FQs) through mechanisms such as pore-filling effects, electrostatic interactions, hydrogen bonding, π-π electron donor–acceptor (EDA) interactions, and hydrophilic–lipophilic balance. COP-SO3H demonstrated outstanding adsorption performance for ciprofloxacin, exhibiting a high adsorption capacity, broad pH stability, strong resistance to ionic interference, and good regenerability. Moreover, it displayed preferential selectivity toward fluoroquinolone antibiotics. The present study not only investigates the intricate structural and functional design of COP-SO3H materials but also presents potential applications for the efficient adsorption of specific antibiotics. [ABSTRACT FROM AUTHOR]

The side reactions related to water are the major issue hindering practical application of Zn metal batteries. To exclude the trouble from interfacial water, a covalent organic polymer (COP) layer with N, N′‐Bis(salicylidene)ethylenediamine structure is designed, whose strong coordination ability with Zn2+ enhances the de‐solvation kinetics of solvated Zn2+ which is conducive to interfacial water removal thus alleviating the side reactions related to water. This function has been certified by density functional theory along with molecular dynamics analysis. Moreover, measurements including in situ electrochemical gas chromatography, in situ optical microscopy, in situ X‐ray diffraction and in situ Raman spectroscopy verify the weakened side reactions (including hydrogen evolution and corrosion) along with homogenous Zn deposition contributed from the covalent organic polymer layer. Benefiting from these merits, when assemble into cells based on common ZnSO4‐based aqueous electrolyte, the COP layer‐decorated anode exhibits excellent electrochemical performance of a high average Coulombic efficiency value 99.5% at a high capacity of 5.0 mA h cm−2. What's more, the symmetric cells can operate at −20 °C and the full cell with N/P ratio as low as 1.2 can cycle stably for 100 cycles, which would carry forward the promising practical application of Zn metal batteries. [ABSTRACT FROM AUTHOR]

Transition metal‐nitrogen‐carbon (M‐N‐C) catalysts with CoN4 centers have attracted great attention as a potential alternative to precious metal catalysts for bifunctional oxygen electrocatalysis. However, the asymmetric charge environment of the active site of MN4 obtained by conventional pyrolysis strategy makes the unbalanced adsorption of oxygen molecules, which restricts the activities of both oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). Herein, a series of well‐defined quasi‐phthalocyanine conjugated 2D covalent organic polymer (COPBTC‐M) is developed with MN4+4 active sites through a pyrolysis‐free strategy. Compared to CoN4 site, the additional subcentral N4 atoms in MN4+4 site in COPBTC‐Co catalyst balance the charge environment and form a symmetric charge distribution, which changes the antibonding orbital of the active metal and regulate the oxygen species adsorption, thus improving the activity of the bifunctional oxygen electrocatalysis. In Silico screening demonstrates that cobalt has the best ORR and OER activity for COPBTC‐M with MN4+4 sites, which can be attributed to the fewer anti‐bonding orbital below the Fermi level, which weakens the oxygen species adsorption. Both theoretical and experimental results verify that the COPBTC‐Co possesses unique CoN4+4 active sites and the harmonious coordinating environment can lead to superior bifunctional oxygen catalytic activity with a high bifunctional oxygen catalytic activity (ΔE [Ej10 – E1/2] = 0.76 V), which is comparable with the benchmark Pt/C‐IrO2 pairs. Accordingly, the as‐assembled Zn–air battery exhibits a maximum power density of 157.7 mW cm −2 with stable operation for >100 cycles under an electric density of 10 mA cm −2. This study provides a characteristic understanding of the intrinsic active species toward MNx centers and could inspire new avenues for designation of advanced bifunctional electrocatalysts that catalyze ORR and OER processes simultaneously. [ABSTRACT FROM AUTHOR]

A soft‐pyrolysis strategy by heating Co–N‐implanted covalent organic polymer combining on carbon nanotubes at ≤500 °C has been developed to obtain efficient Co–N–C electrocatalysts for oxygen reduction reaction (ORR). The prepared Co–N–C is highly active for ORR with a half‐wave potential of 0.91 V versus RHE in 0.1 m KOH electrolyte, superior to most of previously reported Co‐based electrocatalysts. When employing it as cathode electrocatalyst, the homemade Zn–air battery shows a peak power density of 304.2 mW cm−2, comparable to the parallel power density (250 mW cm−2) of Zn–air battery with Pt/C (20 wt%) electrocatalyst at cathode. The soft‐pyrolysis strategy not only helps to generate high density Co–Nx active sites on carbons but also facilitates the optimizing balance between active site densities, graphitization degree, and pore structure of Co–N–C catalysts. Herein, a simple and energy‐effective low‐temperature pyrolysis strategy to obtain high‐performance ORR electrocatalyst is provided. [ABSTRACT FROM AUTHOR]

Covalent organic polymers (COPs), quasi-ordered porous network materials synthesized through irreversible chemical bonding, have garnered significant attention in electrocatalytic energy conversion, including fuel cells, electrolytic water systems, and CO2 electrolysis cells. In this article, we have described the key factors that influence the electrocatalytic activity of COPs, including intrinsic conductivity, activity, and mass transfer, along with an overview of recent developments in COPs. In addition, we discuss possible future research directions for improving continuous performance, including controlled construction of high performance active centers for higher current density at high voltage conditions, new processing technologies for membrane electrode assembly to avoid uneven distribution and incomplete exposure of active centers, further exploration of the electrocatalytic mechanism of COPs, and multi-factor analysis tools to track multiple influencing factors across different scales. Such strategies are expected to improve the intrinsic electrocatalytic activity of COPs, overcome challenges in stability, mass transfer, and apparent activity, and promote further research and development of COPs as electrocatalysts.

Two-dimensional (2D) covalent organic polymers (COPs) featuring large surface areas and exposed active sites are desirable in the modification of electrode materials for electrochemical reactions. However, the rigid and planar conformation of 2D COPs limits the wrap of one-dimensional electrodes. Herein, we have proposed a molecular strategy to regulate in situ encapsulation of carbon nanotubes (CNTs) with 2D polyphosphazene. The stoichiometric control over the nucleophilic substitution reaction between hexachlorocyclophosphazene and amines allows for the oriented evolution around the surface of CNTs. The formed COP sheath is an ultrathin and uniform coating without granular deposition. Upon carbonization, the well-defined core/shell CNT composite was converted into the N,P-codoped carbon, exhibiting outstanding electrocatalytic oxygen reduction performance with a diffusion-limiting current density of 5.4 mA cm–2 and an electron transfer number of 3.97. The improved electrocatalytic activity originates from a high content of active N,P-containing catalytic sites uniformly distributed on porous carbon. This study provides a viable strategy to develop functional composite materials by modulating the flexibility of 2D COPs for 1D substrates, contributing to broad applicability. [ABSTRACT FROM AUTHOR]

Accurate structure‐designed single‐metal‐atom doped covalent organic polymers (COPs) are expected to be one of the most promising nitrogen reduction reaction (NRR) electrocatalysts due to their adjustable metal center coordination environment.[1–3] However, pyrolysis of the material is often required to overcome the intrinsically low conductivity of COPs materials, resulting in undesirable structural changes.[4,5] Moreover, the ligand portion connected to the monomer can modulate the electronic state of the catalytic center of the monomer to achieve enhanced kinetics parts of the reaction.[6–8] To overcome this shortcoming, this study reports hybrid electrocatalysts formed by self‐assembling pristine covalent organic polymers (COPs) with oxidized carbon nanotubes (O‐CNT). The electrical conductivity of the hybridized COP/O‐CNT materials can be increased by the O‐CNT. The catalyst attains a FE of 26.8 % and a large NH3 yield rate of 12.3 ug−1 h−1 cm−2 at −0.3 V versus a reversible hydrogen electrode. DFT calculations show that the NRR process tends to choose alternation paths. Therefore, the synthesized PCuPc/O‐CNT as a stable, high‐efficiency NRR catalyst offers a valuable reference for single‐atom COPs electrocatalyst research in electrochemical nitrogen fixation. [ABSTRACT FROM AUTHOR]

Reducing the particle sizes of transition metals [TMs] and avoiding their aggregation are crucial for increasing the TMs atom utilization and enhancing their industrial potential. However, it is still challenging to achieve uniform distributed and density-controlled TMs nanoclusters [NCs] under high temperatures due to the strong interatomic metallic bonds and high surface energy ofNCs. Herein, a series ofTMs NCs with controllable density and nitrogen-modulated surface are prepared with the assistance of a selected covalent organic polymer [COP], which can provide continuous anchoring sites and size-limited skeletons. The prepared Ir NCs show superior hydrogen evolution reaction [HER] and oxygen evolution reaction [OER] activities than commercial Pt/C and Ir/C in both acid and alkaline media. In particular, the as-prepared Ir NCs exhibit remarkable full water splitting performance, reaching a current density of 10 mA cm-2 at ultralow overpotentials of 1.42 and 1.43 V in alkaline and acidic electrolyte, respectively. The excellent electrocatalytic activities are attributed to the increased surface atom utilization and the improved intrinsic activity ofIr NCs. More importantly, the Ir NCs catalyst shows superior long-term stability due to the strong interaction between Ir NCs and the N-doped carbon layer. [ABSTRACT FROM AUTHOR]

[Display omitted] • Covalent organic polymer functionalized by photoactive pyridinium units was developed as a heterogeneous photocatalysis. • The transformation of hydrocarbon into ketone was without any additives or stoichiometric oxidants except for atmospheric. • Photoinduced proton-coupled electron transfer, and 1O 2 and O 2 − play a key role in the photocatalytic reaction. Using oxygen in the air as the sole oxidant to oxidize hydrocarbons into high value-added compounds is a highly promising synthesis strategy with economic advantages. However, the oxidation of hydrocarbons with molecular oxygen under mild conditions is challenging due to the large C–H bond energy in hydrocarbons. Herein, a metal-free two-dimensional covalent organic polymers (COP) functionalized by photoactive pyridinium units has been developed for heterogeneous photocatalytic oxidation of hydrocarbons. This is the first kind of COPs material that can achieve photocatalytic oxidation of hydrocarbons without any additives or stoichiometric oxidants except for the oxygen in the air. [ABSTRACT FROM AUTHOR]

Covalent organic polymers (COPs) have emerged as a unique class of luminescent polymers with pre-designed quasi-ordered architectures. However, their layered stacks and limited solubility preclude further processing for large-scale applications in devices, especially optoelectronic equipment. Herein, a universal strategy to adjust the electron donor–acceptor (D-A) moieties of the building blocks in COPs is proposed, achieved by in situ charge exfoliation of COP blocks into few-layer true solutions in (Lewis) acid and base media. The electron D-A moieties of the building blocks endow the COPs with the ability to accept or donate electrons, by altering the electron cloud distribution as well as the relative energy levels of the frontier molecular orbitals. The resultant soluble COPs can easily be processed into a uniform film by solution processing via the spin-coat method. The obtained COP-N achieves efficient and stable perovskite electroluminescence as a novel hole injection material on indium tin oxide, and the operating lifetime for a perovskite quantum dot light-emitting diodes device exceeds that of a poly(ethylene dioxythiophene):polystyrene sulphonate counterpart. This straightforward electronic regulation strategy provides a new avenue for the rational synthesis of processable reticular molecular polymers for practical electronic devices.

Covalent organic polymers are an emerging class of amorphous microporous materials that have raised increasing concerns in analytical chemistry due to their unique structural and surface chemical properties. However, the application of covalent organic polymers as mixed‐mode stationary phases in chromatographic separations has rarely been reported. Herein, novel spherical silica hydroxyl‐functionalized covalent organic polymer composites were successfully prepared via a layer‐by‐layer approach. The structure and morphology of the materials were carefully characterized by elemental analysis, Fourier‐transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, X‐ray diffraction, thermogravimetric analysis, Brunauer‐Emmett‐Teller, and contact angle measurements. Baseline separations of various alkylbenzenes, polycyclic aromatic hydrocarbons, and nucleosides and bases were achieved on the prepared stationary phase under reversed‐phase/hydrophilic interaction mode. The column efficiencies of 23 853 and 36 580 plates/m were obtained for butylbenzene and uracil, respectively, and the relative standard deviation of the retention time for continuous injections was less than 1.38% (n = 10), suggesting satisfactory column efficiency and repeatability. Additionally, this novel stationary phase realized the complete separation of the endocrine‐disrupting chemicals in river water. This work affords a new route for synthesizing covalent organic polymers‐based mixed‐mode stationary phase and further reveals their great potential in chromatographic separation. [ABSTRACT FROM AUTHOR]

Through accumulation, mercury contamination in aquatic systems still poses serious health risks despite the strict regulations on drinking water and industrial discharge. One effective strategy against this is adsorptive removal, in which a suitably functionalized porous material is added to water treatment protocols. Thiol (SH) group‐grafted structures perform commendably; however, insufficient attention is paid to the cost, scalability, and reusability or how the arrangement of sulfur atoms could affect the HgII binding strength. We used an inexpensive and scalable porous covalent organic polymer (COP‐130) to systematically introduce thiol functional groups with precise chain lengths and sulfur content. Thiol‐functionalized COP‐130 demonstrates enhanced wettability and excellent HgII uptake of up to 936 mg g−1, with fast kinetics and exceptionally high selectivity. These Hg adsorbents are easily regenerated with HCl and can be used at least six times without loss of capacity even after treatment with strong acid, a rare performance in the domain of Hg‐removal research. [ABSTRACT FROM AUTHOR]

The construction of a Z‐scheme photocatalytic system is significant in realizing efficient water splitting for hydrogen (H2) evolution. Herein, a novel donor–acceptor covalent organic polymer (COP) is introduced to construct a COP‐ZnIn2S4 (ZIS) heterostructure via in situ condensation reaction. The COP‐ZIS heterostructure with platinum (Pt) as cocatalyst delivers a high hydrogen evolution rate of 5.04 mmol g−1 h−1, which is 16 and 3 times higher than ZIS and Pt/ZIS, respectively. The built‐in field between the highest occupied molecular orbital of COP and the valence band (VB) of ZIS forms a Z‐scheme heterostructure, realizing efficient charge separation. Based on density functional theory calculations, the porphyrin molecule in COP act as electron donor that provides compensating electrons to ZIS. The cocatalyst boosts the utilization of electrons in ZIS. The rate‐limiting steps for H2 evolution with ZIS are overcome by improving charge separation with the Z‐scheme heterostructure and speeding up the reaction with cocatalyst. Therefore, the COP‐ZIS heterostructure with Pt exhibits optimized H2 evolution. This study will inspire to construct novel organic and inorganic Z‐scheme photocatalysts for efficient green energy production. [ABSTRACT FROM AUTHOR]

[Display omitted] • COPs with unique donor–acceptor staggered and large conjugation structures were designed and synthesize. • TBN-1 is capable of sensitive detection and effective removal of nitro-aromatics. • LUMO and HOMO energies reveals the quenching mechanism and DFT analysis elucidates adsorption sites and forces. Creating suitable monitoring probes that exhibit strong fluorescence properties for sensitive detection and effective removal of nitro-aromatics remains a challenge. Herein, triazine-based N-rich donor–acceptor covalent organic polymers (TBN-COPs) with unique electron-rich channels, tunable pore size distribution, and outstanding specific surface areas were rational designed and synthesized for the highly selective detection and effective removal of nitro-aromatics. The sensing properties for electron-deficient benzene derivatives were explored. Compared with other types of TBN-COP candidates, TBN-1 showed a better luminescence response to nitro-aromatics, especially for picric acid (PA). The 0.15 ppm detection limits and 2.89*105 as K sv could be realized for PA detection by TBN-1. Besides, there were no additional fluorescence responses to the electron rich benzene derivatives, demonstrating the specific selectivity of nitro-aromatics by TBN-1. The energy and charge transfer mechanisms for the hyper nitro-aromatics sensing properties of TBN-1 were further elucidated according to the energy level simulation, and to both the spectroscopic and electrochemical analysis. The merits of TBN-1 are unreservedly manifested when further testing the adsorption performance of TBN-1 for nitro-aromatics removal. The mechanism for the excellent nitro-aromatics adsorption performance of TBN-1 is revealed by coupling model fitting and chemical computation, which indicates the π-π stacking interaction and high electron density of the material to facilitate its combination with nitro-aromatics. Therefore, TBN-1 is a promising candidate to selectively detect and effectively remove nitro-aromatics, and can hence be applied in security checking and environmental conservation. [ABSTRACT FROM AUTHOR]

[Display omitted] • The core–shell hybrid MOG@COP is successfully prepared by the solvothermal method. • The MOG@COP is immobilized in sodium alginate to achieve excellent recyclability and shaping appearance. • Adsorption and co-adsorption of CTC and Cr(Ⅵ) by MOG@COP and MOG@COP/SA beads are investigated. • The adsorption/fluorescence mechanism of CTC and Cr(Ⅵ)/Cr(Ⅵ) is proposed. • The MOG@COP/SA beads realize the co-removal of CTC and Cr(Ⅵ), on-site RGB detection of Cr(Ⅵ) and optical anti-counterfeiting in binary system. Co-contamination of antibiotics and heavy metals in water environment has provoked considerable toxicological concerns. Meantime, residue detection of heavy metals as well as national anti-counterfeiting safety also have driven attempts in wastewater treatment. In this paper, a core–shell hybrid MOG@COP is designed with behaviors superior to pristine components by combining a Zr-based metal–organic gel and a guanidine-based covalent organic polymer, for co-adsorption and mono-detection in chlortetracycline hydrochloride (CTC)-Cr(Ⅵ) co-contamination system and efficient anti-counterfeiting. In single/binary system, the adsorption capacities of CTC and Cr(Ⅵ) behave as 133.69 and 63.45 mg·g−1/181.82 and 64.47 mg·g−1, and the high sensitivity and low detection limit of Cr(Ⅵ) render as 1.46*105 M−1 and 0.20 μM/1.49*102 M−1 and 0.63 mM, respectively. In addition, to solve the powder shortcomings of easy agglomeration and difficult recycling, MOG@COP is fixed into sodium alginate (SA) matrix to fabricate MOG@COP/SA beads, yielding reinforced adsorption performance of CTC/Cr(Ⅵ) in both single system (152.91/92.25 mg·g−1) and binary system (174.83/75.30 mg·g−1). More importantly, a self-constructed adsorption-detection-anti-counterfeiting (ADA) platform is ingeniously developed with the MOG@COP/SA beads as the backfills for continuously processing CTC-Cr(Ⅵ) co-contaminated water, realizing real-time visualization of Cr(Ⅵ) adsorption process and optical anti-counterfeiting protection. In conclusion, this work is expected to not only trigger the reasonable design of the core–shell hybrid MOG@COP/SA beads with versatile performances of simultaneous luminescence monitor, capture and anti-counterfeiting, but also allow the original exploration for all-in-one platform. [ABSTRACT FROM AUTHOR]

Radioactive iodine is a high proportion of the fission product of nuclear power, and it is crucial to fabricate materials for capturing iodine from both vapor and solution media. The large-scale synthesis of materials in low-temperature deoxidation and high-temperature with long-time environments presented significant challenges. The Chichibabin pyridine coupling reaction was employed to design and synthesize a nonporous piperazine-linked COP (PIPCOP) under atmospheric pressure within a short reaction time of only 2 h. The PIPCOP material had a comparatively low BET surface area measurement of 4.28 m2 g−1 with an exceptionally low pore volume of 0.0083 cm3 g−1. However, it had a high ability to accept iodine vapor and iodine in hexane, with a capacity of 5.18 g g−1 and 1.95 g g−1, respectively. A novel proposal is presented in this study for the synthesis of functional nonporous polymers with enhanced iodine absorption capacity, aiming to address environmental concerns. [Display omitted] • The PIPCOP shows a lower specific surface area and lower pore volume, regarded as nonporous polymer. • Highly effective adsorption of iodine vapor and solution by nonporous materials. • Easy to synthesize by Chichibabin pyridine coupling reaction. [ABSTRACT FROM AUTHOR]

Owing to the poor treatment efficiency of wastewater containing fluoroquinolones (FQs), effective removal of such pollutants has become a significant issue in waste management. In this study, a ternary covalent organic polymer anchored with SO3H (COP-SO3H) was designed using the Schiff reaction and a multicomponent solvent thermal method. The synthesized COP-SO3H polymer possesses multiple functional binding sites, including amide groups, sulfonic groups, and aromatic frameworks, enabling it to effectively adsorb ciprofloxacin (which belongs to FQs) through mechanisms such as pore-filling effects, electrostatic interactions, hydrogen bonding, π-π electron donor–acceptor (EDA) interactions, and hydrophilic–lipophilic balance. COP-SO3H demonstrated outstanding adsorption performance for ciprofloxacin, exhibiting a high adsorption capacity, broad pH stability, strong resistance to ionic interference, and good regenerability. Moreover, it displayed preferential selectivity toward fluoroquinolone antibiotics. The present study not only investigates the intricate structural and functional design of COP-SO3H materials but also presents potential applications for the efficient adsorption of specific antibiotics.

Porphyrins are selected as building units to synthesize porphyrin‐based covalent organic polymers (COPs), which can combine the excellent properties of covalent organic polymers with the fantastic catalytic effect of porphyrin to obtain a heterogeneous catalyst with excellent catalytic activity. In this work, the novel benzimidazole‐linked porphyrin COPs MPp‐BTA (M = 2H, Zn, Co) were synthesized using a new porphyrin with aldehyde group peripherally MPp (M = 2H, Zn, Co) and 1,2,4,5‐tetraminobenzene tetrahydrochloride (BTA) as monomers. The synthesized MPp‐BTA were carefully characterized by FT‐IR, UV–vis, SEM, TEM, TG, and PXRD. As heterogeneous catalyst, MPp‐BTA (M = Zn, Co) shows the high catalytic activity and stability for cycloaddition of CO2 with phenyl glycidyl ether (PGE) under mild conditions (80°C, 0.1 MPa CO2), and the yield of cyclocarbonate can reach 95% and 92% respectively. In addition, the recycling stability of ZnPp‐BTA was investigated, and the yield of cyclocarbonate was still remained at 86% after five cycles. Furthermore, MPp‐BTA (M = 2H, Zn, Co) can be used directly as heterogeneous photocatalysts for selective oxidation of thioanisole to methyl phenyl sulfoxide. To our delight, H2Pp‐BTA shows satisfactory photocatalytic performance, and the yield of methyl phenyl sulfoxide can reach 93% in 4 h. [ABSTRACT FROM AUTHOR]

Halocarbons have important industrial applications, but because of their contribution to global warming and the fact that they can cause ozone depletion, they are considered highly toxic. Hence, the techniques that can capture and recover the used halocarbons with energy-efficient methods have been recently received greater attention. In this contribution, we report the capture of dichlorodifluoromethane (R12), which has high global warming and ozone depletion potential, using covalent organic polymers (COPs). The defect-engineered COPs were synthesized and demonstrated outstanding sorption capacities, ~226 wt % of R12 combined with linear-shaped adsorption isotherms. We further identified the plausible microscopic adsorption mechanism of the investigated COPs via grand canonical Monte Carlo simulations applied to non-defective and a collection of atomistic models of the defective COPs. The modeling work suggests that significant R12 adsorption performance is attributed to a gradual increment of porosities due to isolated/interconnected micro-/meso-pore channels and the change of the long-range ordering of both COPs. The successive hierarchical-pore-filling mechanism promotes R12 molecular adsorption via moderate van der Waals adsorbate-adsorbent interactions in the micropores of both COPs at low pressure followed by adsorbate-adsorbate interactions in the extra-voids created at moderate to high pressure ranges. This continuous pore-filling mechanism makes defective COPs as promising sorbents for halocarbon adsorption., (© 2024 The Authors. ChemPhysChem published by Wiley-VCH GmbH.)

A sensitive and accurate analysis of organochlorine pesticide (OCP) residues in dairy products poses a significant challenge. Herein, a novel covalent organic polymer, Azo-COP-1, was synthesized for the enhanced extraction of OCPs in dairy products. The solid phase microextraction fiber coated with Azo-COP-1 demonstrated excellent extraction performance for the OCPs via hydrogen bonding, halogen bonding, π-π stacking, and electrostatic interactions. Coupled with gas chromatography-electron capture detection, we developed a facile and reliable method for detecting OCPs in six types of dairy products with low limits of detection (2.0-400 pg g -1 ) and high method recoveries (82.6-113%). Azo-COP-1 coatings exhibited good stability and durability. The results verified the feasibility of using Azo-COP-1-based SPME to extract OCP residues in dairy product samples, highlighting its potential for routine monitoring of pesticide residues and food safety assessments.

Current research strives to create sustainable and ecofriendly organic electrode materials (OEMs) due to the rising concerns about traditional inorganic electrode materials that call for substantial resource consumption in battery manufacturing. However, OEMs often exhibit unbalanced performance, with high capacity conflicting with a long lifespan. Herein, a 2D fully conjugated covalent organic framework featuring abundant C═O and C═N groups (HTPT-COF) was strategically synthesized by coupling 2,3,7,8-tetraamino-1,4,6,9-tetraketone with hexaketocyclohexane octahydrate. It stabilizes the enriched active centers by an extended π-conjugated skeleton, thereby affording a high theoretical capacity in conjunction with potential structure stability. To further unlock the barriers of fast charge, the HTPT-COF was interwoven around highly conductive carbon nanotubes, creating a robust core-sheath heterostructure (HTPT-COF@CNT). Consequently, the crafted HTPT-COF@CNT achieves large reversible capacities of 507.7 mA h g -1 , high-rate performance (247.8 mA h g -1 at 20.0 A g -1 ), and long-term durability (1000 cycles). Aiming to streamline the process and cut the cost of battery manufacturing, all-organic symmetric batteries were well fabricated using HTPT-COF@CNT as both cathode and anode, demonstrating high energy/power density (up to 191.7 W h kg -1 and 3800.3 W kg -1 , respectively) and long-term stability over 1000 cycles. Such HTPT-COF@CNT represents a promising sustainable electrode that effectively addresses irreconcilable contradictions encountered by OEMs, boosting the development of advanced organic batteries with high capacity and cycling stability.

Since radioactive iodine can be harmful to both environmental protection and human health, it is of great significance to design and develop efficient iodine adsorption materials. In this paper, two Covalent Organic Polymers (BPLOH and BPLDA) were synthesized via a Schiff base condensation reaction, utilizing an elaborate bipyridine-containing π-electron-rich tetraaldolyl linker unit, BPDDP, in conjunction with 3,3′-dihydroxybenzidine (LOH) and 3,3′-Dimethoxybiphenyl-4,4′-diamine (LDA) as the amino linker units. Owing to the abundant N/O atoms and π-electron-rich conjugated groups, the prepared COPs exhibit a fast and strong iodine adsorption capacity for volatile iodine. Under atmospheric pressure at 75 °C, the iodine vapor adsorption capacity of two COPs exceeded 2.3 g g−1 within 1 hour. Specifically, BPLOH and BPLDA exhibited optimal iodine vapor capture capacities of 5.99 g g−1 and 5.39 g g−1, respectively, surpassing the performance of most iodine adsorbents reported thus far. This work introduces new ideas and avenues for the rational design of abundant N/O atoms containing electron rich covalent organic polymers for the efficient capture of iodine related applications. [Display omitted] [ABSTRACT FROM AUTHOR]

The non-covalent interaction that appears along with electronic tuning is often overlooked in interpreting the oxygen reduction reaction (ORR) dynamics, resulting in a limited understanding of the governing principles. Herein, through intricately engineering pedant substituents on porphyrins backbones, Co-N 4 moieties featuring varied electronic configurations served as an exemplary model to elucidate the role of hydrogen bonding interaction appears along with electronic tuning in determining 2e- ORR performance. Co-TEPP with an electron-deficient Co-N 4 moiety emerges as a standout performer for O 2 -to-H 2 O 2 conversion. Upon covalently linking the Co-TEPP monomer on rGO to form robust organic polymer structures (Co-TEPP-COP/rGO), superior H 2 O 2 selectivity (> 95 %), remarkable H 2 O 2 production rate (∼18.8 mol g cat −1 h−1), and excellent performance durability are identified. Such optimized H 2 O 2 electrosynthesis could be attributed to the suppressed hydrogen bonding interaction between *OOH and electron-deficient Co-N 4 moiety, which consequently weakens *OOH binding strength to favor H 2 O 2 electrosynthesis. [Display omitted] • A remote electronic tuning strategy was reported to accelerate the intrinsic 2e- ORR kinetics of Co porphyrins. • The Co-TEPP-COP/rGO presented superior H 2 O 2 selectivity (> 95 %) and remarkable H 2 O 2 production rate (∼18.8 mol g cat −1 h−1). • A cumulative H 2 O 2 concentration ∼1.18 wt% was observed on the Co-TEPP-COP/rGO. • This study revealed electron-deficient Co-N 4 could suppress its interaction with *OOH and accelerate H 2 O 2 electrosynthesis. [ABSTRACT FROM AUTHOR]

Uranium is the main actinide highly related with recycling fission fuel. In this study, we controllably construct a lignin-based covalent organic polymers (AO-EHL), for uranium extraction with high adsorption capacity (94.70 mg/g). The balanced adsorption efficiency for uranium is remarkably high under highly acidic conditions, and even maintains 99.99 % in pH = 1.0. Moreover, the high adaptability, excellent reusability, and extremely low operating costs further indicated the high feasibility of AO-EHL for uranium extraction in industrial scale. The excellent adsorption performance of AO-EHL for uranium is reasonably attributed to synthetic effects of amidoxime groups and the covalent structure of lignin, which can highly prevent the protonation of amidoxime groups, and thus showing strong complexation with uranium at high acidities. This study suggests a promising method to construct advanced functional materials by using cheap and green natural materials and realizing the efficient uranium extraction under highly acidic conditions. [Display omitted] • AO-EHL was synthesized by the resource utilization of lignin. • The adsorption efficiency of AO-EHL for U(VI) maintains 99.99 % in pH = 1.0. • The covalent structure of lignin restrains the protonation of amidoxime. • AO-EHL exhibits large practical potential for U(VI) extraction. [ABSTRACT FROM AUTHOR]

Covalent organic polymers and frameworks have excellent potential to degrade and eliminate organic pollutants in industrial wastewater. Herein, a family of donor–acceptor covalent organic polymers (D–A COPs) that contain thiazole units and varying amounts of hydroxyl groups from 0 to 100 %, have been designed and synthesized for improved adsorption and photocatalytic performance. Compared with COPs containing hydroxyl groups, NXCOP-3000 without a hydroxyl group is more effective in the adsorption of organic dye pollutants, and the maximum adsorption capacity was 122.5 mg g−1, which is also supported by the theoretical simulation. The more the hydroxyl group content is, the narrower the band gap is in this case. Interestingly, NXCOP-3075 with a 75 % hydroxyl group has demonstrated superior photocatalytic activity, where the dye removal efficiency reaches 98.87 %, which suggests that these COPs create efficient carrier pathways to separate photogenerated holes and electrons efficiently. Therefore, introducing hydroxyl groups into COP can be used as a strategy to enhance photocatalytic activity. A family of covalent organic polymers constructed from bithiazole units and varying amounts of hydroxyl groups from 0 to 100 % bears donor–acceptor features, showing high adsorptive and photocatalytic activity. [Display omitted] • ➢Five bithiazole-based COPs with varying hydroxyl content have been synthesized. • ➢These COPs have been investigated for the removal of organic dye pollutants. • ➢ NXCOP-3075 has better carrier separation and transport than NXCOP-3000. • ➢When passes the adsorbent after five times, the removal efficiency reaches 97.34 %. [ABSTRACT FROM AUTHOR]

Water electrolysis is considered to be one of the most promising approaches for developing sustainable energy technologies, however, the high cost and lack of stability of traditional precious metal electrocatalysts have hindered the development of the field of water electrolysis. Covalent organic polymers have greater potential for the preparation of low-cost electrocatalysts with high efficiency and long-term stability due to their low cost, controllable chemical composition, and rich pore structure. Cobalt phthalocyanine-based covalent organic polymers were loaded onto few-layer graphene by a hydrothermal method and then pyrolyzed to produce Co, N, and P co-doped few-layer graphene (Co–N/P-FG-700). Co–N/P-FG-700 demonstrates superior performance for oxygen evolution reaction (OER) due to the synergistic effect of abundant active sites and conductive carriers, with an overpotential of 358 mV at a current density of 10 mA cm−2 and 90% of the current density after 50,000 s of stability testing. Co–N/P-FG-700 exhibits excellent results for hydrogen evolution reaction (HER) with an overpotential of −275 mV at a current density of −10 mA cm−2 and a current density retention of 93% after a 50,000 s stability test. This study provides a rational pathway for the design of low-cost, high-performance, stable bifunctional OER/HER electrocatalysts. Covalent organic polymers are loaded onto few-layer graphene for pyrolysis to obtain Co, N, and P co-doped few-layer graphene. Due to the component tunability of the covalent organic polymer and the efficient and low-cost graphene preparation method, OER/HER bifunctional catalysts with abundant active sites and good stability are prepared. [Display omitted] • Cobalt phthalocyanine-based covalent organic polymer anchored as a sacrificial body on few-layer graphene for fixed doping by pyrolysis. • Covalent organic polymers provide a wealth of active sites for materials. • Few-layer graphene gives the material good stability and conductivity. [ABSTRACT FROM AUTHOR]

A novel imidazole-Linked Covalent Organic Polymer PMTP cathode was designed and synthesized for aqueous zinc-organic batteries. To facilitate mass/charge transfer, integrating PMTP with carbon nanotubes highly improved the utilization of multiple redox centres, thus showing ultra-fast kinetics and long lifespan. [Display omitted] • A imidazole-linked covalent organic polymer (COP, PMTP) was successfully designed and prepared. • The six-electrons reaction process of PMTP materials in aqueous zinc ion batteries (AZIBs) have been systematically explored. • The combination of PMTP and carbon nanotubes further improved charge/charge transfer and specific capacity. • The PMTP@CNT-40 composite delivers high capacity and long lifespan (230 mA h g−1, 4000 cycles at 3 A/g). Organic polymer cathodes are of long-standing interest for aqueous zinc-ion batteries (AZIBs) due to their specific redox-sites and stable structural frameworks. However, the high redox potential of Zn anode and poor electrical conductivity as well as sluggish mass/charge transfer of organic polymers prevent most of organic cathodes from effectively participating in the redox reaction. Therefore, designing and applying suitable cathodes through molecular engineering for high-performances AZIBs still remains a challenging task. Herein, we design an imidazole-linked polymer PMTP used as cathode for AZIBs by the condensation of benzene-1,3,5-tricarbaldehyde (BT) linker and 2,3,7,8-Tetraaminophenazine-1,4,6,9-tetraone (TAPT) redox-ligand, which exhibits six-electrons reaction process of each structural unit. In addition, the PMTP@CNT-X composite (X denotes the mass percent of CNTs in composite) is fabricated by in-situ polymerization of PMTP on the surface of carbon nanotubes (CNTs) to promote the charge/mass transfer. Benefiting from the integration strategy, PMTP@CNT-40 delivers high redox-active site utilization, thus achieving high capability of 230 mA h g−1 and long lifespan up to 4000 cycles at 3 A g-1. This work may shed light on designing and developing novel organic cathodes for advanced AZIBs. [ABSTRACT FROM AUTHOR]

Abstract The integration of multiple functions with organic polymers-based nanoagent holds great potential to potentiate its therapeutic efficacy, but still remains challenges. In the present study, we design and prepare an organic nanoagent with oxygen-evolved and targeted ability for improved phototherapeutic efficacy. The iron ions doped poly diaminopyridine (FeD) is prepared by oxidize polymerization and modified with hyaluronic acid (HA). The obtained FeDH appears uniform morphology and size. Its excellent colloidal stability and biocompatibility are demonstrated. Specifically, the FeDH exhibits catalase-like activity in the presence of hydrogen peroxide. After loading of photosensitizer indocyanine green (ICG), the ICG@FeDH not only demonstrates favorable photothermal effect, but also shows improved generation ability of reactive oxygen species (ROS) under near-infrared laser irradiation. Moreover, the targeted uptake of ICG@FeDH in tumor cells is directly observed. As consequence, the superior phototherapeutic efficacy of the targeted ICG@FeDH over non-targeted counterparts is also confirmed in vitro and in vivo. Hence, the results demonstrate that the developed nanoagent rationally integrates the targeted ability, oxygen-evolved capacity and combined therapy in one system, offering a new paradigm of polymer-based nanomedicine for tumor therapy.

Microcapsules have been widely used in drug carriers, nano/microreactors, artificial organelles for their empty space and functional shell. Microcapsules synthesized from spherical liquid-liquid interface show ultrathin shell and large cavities. However, spherical liquid-liquid interfaces generated by stirring or sonicating are difficult in controlling the droplet size and preventing their coalescence, which results in inhomogeneous capsules. Here, we demonstrate a microfluidic interfacial synthetic method to produce microcapsules using the hot covalent organic polymers (COPs) coupled with Schiff-base reaction. A very high throughput of uniform and individual microdroplets about ~1400 min−1 was generated under high flow rate for COP capsules fabrication. Acidic catalyst promoted amine and aldehyde condensation that reacted less than 1 ​s assured the polymerization occurred at the liquid-liquid interface regardless of the diffusion intensification in microfluidic system. COP capsules with shell thickness around 50 ​nm were flexible enough to response to slight interior capillary force and exterior filtration force to form origami structure and sealed flat membrane, respectively. Each of the interfacial synthesized capsule expressed large capacity by encapsulating 1.41 ​× ​10−2 ​μg SiO2 nanoparticles as theoretically calculated. Thus, these properties make the COP capsules promising in, but not limited to, fast drug delivery and microreactors.

Cu(II)-modified nitrogen-rich covalent organic polymer (Cu/N-COP-1) was fabricated and employed to catalyze the cross-dehydrogenative ortho-aminomethylation of phenols. The Cu/N-COP-1 catalyst displayed excellent catalytic activity under mild conditions without any ligand. Various substituted phenols and N,N-dimethylanilines were successfully converted to the corresponding products. Moreover, the catalyst can be readily reused for at least five consecutive runs without obvious loss of catalytic activity. This can be attributed to the interaction between the nitrogen-containing group of the covalent organic polymer and Cu species, which makes Cu species steadily immobilized on the surface of polymer.

The combination of micron-scale macropores with meso-/micropores into three-dimensional (3D) macroscopic architectures could give increasing attention to both fast diffusion and mass transfer and exposure of the intrinsic micropores, thereby improving the performance and realizing the real-world applicability of nanoscale functionalized materials. In this report, the emulsion-droplet-templated method was used for the preparation of a hierarchically porous macroscopic covalent organic polymer (COP) monolithic foam, showing compressibility, high mass transfer, and excellent chromatographic separation capacity. The as-synthesized COP nanoparticles with the size of about 40 nm possessed good crystallization and high chemical and thermal stability. More importantly, the resulting COP nanoparticles showed interfacial activity, absorbing and accumulating the water/mesitylene interface, thus producing the COP nanoparticle film. As a result, a series of Pickering emulsions stabilized by COP nanoparticles were formed. Emulsion droplets of approximately 4.90 μm could serve as templates, producing hierarchically porous COP monolithic foams via freeze-drying of the starting Pickering emulsions. In view of the effective merging of macropores with meso-/micropores, the very thin disklike COP monolith (1 mm height × 10 mm i.d.) can serve as a separation column, which is highly efficient in differentiating the isomers of p- < o- < m-nitrotoluenes and chloronitrobenzenes. Clearly, the macropores guarantee high mass transfer, while the micropores provide many active sites. Therefore, the resulting COP foam shows excellent chromatographic separation capacity. Finally, the as-prepared COP monolithic foam has great potential as a prospective chromatographic column for highly efficient separation of isomers. [ABSTRACT FROM AUTHOR]

Advancement of novel coating materials for solid‐phase microextraction is highly needed for sample pretreatment. Herein, a triazine‐based covalent organic polymer was constructed from the monomers of cyanuric chloride and trans‐stilbene via the Friedel‐Crafts reaction and thereafter used as a solid‐phase microextraction fiber coating for the extraction of polycyclic aromatic hydrocarbons and their nitrated and oxygenated derivatives. The newly‐developed solid‐phase microextraction method coupled with gas chromatography/flame ionization detection gives enhancement factors of 548–1236 and limits of detection of 0.40–2.81 ng/L for the determination of polycyclic aromatic hydrocarbons and their derivatives. The one fiber precision for five replicate determinations of the analytes and the fiber‐to‐fiber precision with three parallel prepared fibers, expressed as relative standard deviations, was in the range of 4.6–9.4% and 6.2–10.9%, respectively. The relative recoveries of the analytes for environmental water samples were in the range of 88.6–106.4% with the relative standard deviations ranging from 4.0 to 11.7% (n = 5). [ABSTRACT FROM AUTHOR]

Developing high-performance non-precious metal-based electrocatalysts for oxygen reduction reaction (ORR) is an urgent demand. In this study, we prepared highly efficient Fe 3 O 4 -nanoparticles-decorated Fe–N–C nanosheets (Fe 3 O 4 /CCOP HM -F127) from 2D covalent organic polymer (COP) for ORR via a facile impregnation method. The introduced anionic surfactant, i.e. F127, can effectively improve the distribution and size uniformity of Fe 3 O 4 nanoparticles. The onset potential of Fe 3 O 4 /COP HM -F127 is 1.0 V, which is equivalent to that of commercial Pt/C. Moreover, the half-wave potential of Fe 3 O 4 /COP HM -F127 can reach up to 0.87 V, which is better than that of commercial Pt/C. Fe 3 O 4 /COP HM -F127 also exhibits excellent durability and methanol tolerance during the electrocatalytic process. • Fe 3 O 4 nanoparticles decorated Fe–N–C nanosheets is prepared by a impregnation method. • F127 is used for improving the distribution and size uniformity of Fe 3 O 4 nanoparticles. • Fe 3 O 4 /COP HM -F127 exhibits enhanced performances for oxygen reduction reaction. [ABSTRACT FROM AUTHOR]

A novel covalent organic polymer was prepared using 1,5‐diaminonaphthalene as a linker and cyanuric chloride as a node. A thin‐film nanocomposite of 1,5‐diaminonaphthalene covalent organic polymer and cellulose nanocrystalline was then fabricated via filtering and casting method. The effect of incorporation of various amounts of 1,5‐diaminonaphthalene covalent organic polymer and cellulose nanocrystalline was studied to obtain an efficient nanocomposite thin‐film with a large number of polar functional groups and high mechanical stability. Field emission scanning electron microscopy, X‐ray diffraction, Fourier transform infrared spectrometry, and thermogravimetric analysis techniques were applied for the characterization of physicochemical properties of the prepared materials. Imipramine was determined in the biological samples using thin‐film microextraction followed by gas chromatography flame ionization detection. Parameters affecting the extraction efficiency of imipramine were investigated. Under the optimized conditions, the limit of detection was 0.5 ng/mL. Film‐to‐film reproducibility for three different films fabricated under the same conditions (at three concentration levels) varied between 8.9 and 9.7%. The linear dynamic range covered more than three orders of magnitude (2–5000 ng/mL) with a determination coefficient of 0.9985. The method was successfully applied for preconcentration and determination of imipramine in biological samples with spiking recoveries between 78 and 93%. [ABSTRACT FROM AUTHOR]

[Display omitted] • A shapeable three-component SLEL-3 with sulfonic acid was well-fabricated. • The adsorption behaviors and mechanisms of FQs were explored. • SLEL-3 showed self-moldability, chemical resistance and felicitous hydraulic conductivity. • The long-term effectiveness of LVF decontamination was realized through 1-D column and 2-D tank PRB systems. Fluoroquinolones (FQs) antibiotics found in groundwater pose hazardous impacts to organisms and humans. Moreover, permeable reactive barrier (PRB) is reckoned as an effective in-situ remediation technique for FQ-contaminated groundwater, in which PRB materials with high adsorption capacity and moldability are severely desired. Herein, a shapeable three-component hydrogen-bonded covalent-organic aerogel with sulfonic acid (SLEL-3) was fabricated based on a multiple-component method. The appraisal of SLEL-3 for the capture of levofloxacin (LVF) and ciprofloxacin (CIP) was evaluated systematically through kinetics and isotherms, which exhibited satisfactory adsorption performance in the following aspects: amended adsorption capacity, acceptable removal depth and resistance to ions and acidity/alkalinity. The proposed adsorption mechanisms involved a combination of pore filling effect, electrostatic effect, hydrogen bonding, π-π/n-π electron-donor–acceptor (π-π/n-π EDA), Lewis acid-base and hydrophobic/hydrophilic interaction. More importantly, in view of self-shaping ability, adaptability to harsh conditions, high swellability as well as felicitous hydraulic conductivity, novel PRB systems integrating SLEL-3 into 1-D column and 2-D tank in lab-scale study were developed for the capture of LVF, achieving impressive removal efficiencies of 86% and 92.65% over a 72-h period, respectively. Thus, this study provides a new notion of contriving a shapeable, eco-friendly and practicable covalent-organic polymer for potentially efficient in-situ remediation of FQ contaminated groundwater with a large area. [ABSTRACT FROM AUTHOR]