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3D assembled carbon materials, featuring unique hierarchical porosity and interconnected channels, are essential for the advancement of emerging zinc-air batteries (ZABs). In this study, nitrogen (N) and sulfur (S) co-doped 3D carbon nanoholes (N/S-CNHs) are synthesized through a straightforward procedure involving self-assembly followed by carbonization. This process utilizes a hybrid of self-assembled covalent triazine framework and sodium lignosulphonate (CTF@LS) as a multifunctional precursor. The resulting N/S-CNHs exhibit a distinctive nanoholes microstructure composed of interwoven carbon nanoclusters, which facilitates efficient ion and electron transport during the electrocatalytic process. The incorporation of N and S atoms intriguingly alters the wetting properties of the catalyst microenvironment, thereby significantly facilitating the transfer of key intermediates and their interaction with the electrolyte. Consequently, the optimized N/S-CNH-900 demonstrates remarkable electrocatalytic activity for the ORR (E 1/2 = 0.86 V vs RHE), surpassing the performance of state-of-the-art Pt/C electrocatalyst. Theoretical calculations reveal that the synergistic effect of N and S heteroatom doping significantly enhances *OOH desorption and its transformation to O*, thereby markedly accelerating the ORR process. Furthermore, both liquid and quasi-solid ZABs equipped with the N/S-CNH-900 cathode exhibit improved peak power density and specific capacity relative to those employing commercial Pt/C catalysts., (© 2024 Wiley‐VCH GmbH.)

Aqueous Zinc-iodine batteries (ZIBs) are widely viewed as promising energy storage devices due to their high energy density and intrinsic safety. However, they encounter great challenges such as grievous polyiodides shuttle and sluggish iodine (I 2 ) redox reaction kinetics, thus undesirable cycling performance. Here a high-performance ZIB with an ultra-long lifespan is reported through the rational I 2 cathode catalyst design. Specifically, a covalent triazine framework with defect-rich sites and micro-mesoporous structure (i.e., CTF500) is developed as an effective I 2 cathode catalyst. Benefiting from the synergistic effect of micro-mesoporous structure and defect-rich sites for the confinement and conversion of I 2 species, the resulting ZIBs with I 2 loaded CTF500 (I 2 @CTF500) cathode show an ultra-long lifespan over 75,000 cycles at 5 A g -1 , and an impressive cyclic performance over 15,000 cycles at high I 2 loading of 3.59 mg cm -2 , highlighting its commercial application prospect. In/ex situ spectral characterizations combined with theoretical calculations clearly reveal the reversible reaction mechanism of I 2 species in I 2 @CTF500 cathode and the essential role of defect-rich sites in boosting the performance of ZIBs. This work not only guides the design of advanced I 2 cathodes for metal-iodine batteries but also expands the range of possible applications for defect-rich CTFs., (© 2024 Wiley‐VCH GmbH.)

Carbon nanotubes (CNTs) are nanoscale tubular materials with superior mechanical strength and electronic properties. However, the conventional CNTs are inherently non-piezoelectric, mainly due to the lack of polar structures with pure carbon elements. The direct synthesis of fully conjugated and polarized organic nanotubes with desired piezoelectric properties remains a challenge. Herein, we report the bottom-up synthesis of a new type of covalent triazine-based nanotube (CTN-1) as a novel piezoelectric material. The CTN-1 comprises of high surface area, nitrogen-rich and fully conjugated structure, which provides a series of merits for piezoelectric catalytic processes. These structural features combined with one-dimensional tubular morphology endow CTN-1 with excellent mechanical stimuli response and thus displaying prominent piezoelectric properties via pronounced nanocurvature effect. We further show that the CTN-1 enables the efficient synthesis of H 2 O 2 from water in the air via mechanical energy conversion, with an excellent piezocatalytic H 2 O 2 evolution rate of 4115 μmol g -1  h -1 , which exceeds other reported piezoelectric materials. The piezocatalysis by the CTN-1 can be practically integrated into a self-Fenton system, which exhibits excellent pollutant degradation capability. This work demonstrates the enormous potential of a new type of piezoelectric synthetic nanotube from organic frameworks for the in situ synthesis valuable chemicals., (© 2024 Wiley-VCH GmbH.)

As a high-performance energy storage device consisting of a battery-type anode and a capacitor-type cathode, hybrid lithium-ion capacitors (HLICs) combine the advantages of high energy density of batteries and high power density of capacitors. However, the imbalance in electrochemical kinetics between the battery-type anode and the capacitor-type cathode hinders the further development of HLICs. Fully conjugated covalent organic frameworks have great potential as electrode materials for HLICs due to the designability of their structure. Herein, a fully conjugated covalent triazine framework (PT-CTF) integrating the hexaazatrinaphthylene unit was constructed, which provides abundant active sites (C═N and C═C groups) as the pseudocapacitive anode material for HLICs. And the connection of the triazine unit of PT-CTF improves the molecular conjugate degree, facilitating the transport of electrons. The fabricated PT-CTF||AC HLICs exhibit a high energy density (164.9 Wh kg -1 at 100 mA g -1 ), large power density (13.1 kW kg -1 at 4 A g -1 ), and excellent cycling capability (72% after 10 000 cycles at 2 A g -1 ).

The appearance of disordered lithium dendrites and fragile solid electrolyte interfaces (SEI) significantly hinder the serviceability of lithium metal batteries. Herein, guided by theoretical predictions, a multi-component covalent triazine framework with partially electronegative channels (4C-TA 0.5 TF 0.5 -CTF) is incorporated as a protective layer to modulate the interface stability of the lithium metal batteries. Notably, the 4C-TA 0.5 TF 0.5 -CTF with optimized electronic structure at the molecular level by fine-tuning the local acceptor-donor functionalities not only enhances the intermolecular interaction thereby providing larger dipole moment and improved crystallinity and mechanical stress, but also facilitates the beneficial effect of lithiophilic sites (C-F bonds, triazine cores, C=N linkages and aromatic rings) to further regulate the migration of Li + and achieve a uniform lithium deposition behavior as determined by various in-depth in/ex situ characterizations. Due to the synergistic effect of multi-component organic functionalities, the 4C-TA 0.5 TF 0.5 -CTF modified full cells perform significantly better than the common two/three-component 2C-TA-CTF and 3C-TF-CTF electrodes, delivering an excellent capacity of 116.3 mAh g -1 (capacity retention ratio: 86.8 %) after 1000 cycles at 5 C and improved rate capability. This work lays a platform for the prospective molecular design of improved organic framework relative artificial SEI for highly stable lithium metal batteries., (© 2024 Wiley-VCH GmbH.)

The development of a low-cost, highly active, and non-precious metal catalyst for oxygen evolution reaction (OER) is of great significance. Multi-metallic catalysts containing Fe, Co, and Ni exhibit remarkable OER activity, while the specific contributions of each component and the synergistic effects in the ternary metal catalyst has remained elusive. In this work, we synthesized a series of S and N-doped mono-metallic, bi-metallic, and tri-metallic hollow carbon sphere electrocatalysts (M-SNC) with the goal of enhancing the catalysts OER activity and shedding light on the unique roles and synergistic effects of the various metals in the FeCoNi ternary metal catalyst. Our systematic analyses demonstrated the introduction of Fe effectively reduces the overpotential, Co accelerates the kinetics of OER, and the addition of Ni further improves the OER performance. Benefiting from the synergistic effects, the FeCoNi-SNC exhibits a low overpotential of 270 mV, with no morphological or structural changes after reaction, maintaining high activity for 72 h at 10 mA cm -2 . Moreover, the assembled FeCoNi-SNC || Pt/C water electrolysis device operates for 65,000 s with minimal degradation, demonstrating its potential for practical application. This work presents a synergy strategy for the preparation of low-cost and highly efficient OER catalysts and further provides insights into the rational design and preparation of multicomponent catalysts., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

Porphyrins-based porous organic polymers (POP) were widely used in photocatalytic oxidation under visible light owing to their superiority in the activation of oxygen. In contrast, the efficiency is usually limited due to the fast recombination and slow electron transfer. Herein, we report the use of a trioporphyrins-based covalent triazine framework (Por-CTF) as visible-light-active photocatalyst for the coupling oxidative of amines to imines at room temperature. By incorporating the π-conjugated porphyrin building block led to the enhanced electron transport between molecules, and the extended recombination time of excited electrons. The photocatalytic efficiency of Por-CTF is superior to that of polymer in absence of triazine framework (POP-TSP), which was prepared by radical polymerization using tetra-(4-vinylphenyl) porphyrin (TSP) as monomer. Por-CTF catalyst presented excellent efficiency for various primary amines and stability. This work provides a reasonable guidance of catalyst molecular structure design for enhancing efficiency in the photocatalytic oxidation., (© 2024 Wiley-VCH GmbH.)

The high crystalline covalent triazine framework-1 (CTF-1), composed of alternating triazine and phenylene, has emerged as an efficient photocatalyst for solar-driven hydrogen evolution reaction (HER). However, it is of great challenge to further improve photocatalytic HER performance via increasing crystallinity due to its near-perfect crystallization. Herein, an alternative strategy of scaffold functionalization is employed to optimize the energy band structure of crystalline CTF-1 for boosting hydrogen-evolving activity. Guided by the computational predictions, versatile CTF-based polymer photocatalysts are prepared with different functional groups (OH, NH 2 , COOH) using binary polymerization for practical hydrogen production. Experiment evidence verifies that the introduction of a limited number of electron-donating groups is sufficient to maintain high crystallinity in CTF, modulate the band structure, broaden visible light absorption, and consequently enhance its photophysical properties. Notably, the functionalization with OH exhibits the most positive effect on CTF-1, delivering a photocatalytic activity with a hydrogen-producing rate exceeding 100 µmol h -1 ., (© 2024 Wiley‐VCH GmbH.)

We introduce the first mechanochemical cyclotrimerization of nitriles, a facile strategy for synthesizing triazine-containing molecules and materials, overcoming challenges related to carbonization and solubility. Conducting this solid-state approach in a mixer ball mill with 4-Methylbenzonitrile, we synthesize Tris(4-methylphenyl)-1,3,5-triazine quantitatively in as little as 90 minutes. Just as fast, this mechanochemical method facilitates the synthesis of the covalent triazine framework CTF-1 using 1,4 Dicyanobenzene. Material characterization confirms its porous (650 m 2  g -1 ) and crystalline nature. Adjusting the induced mechanical energy allows control over the obtained stacking conformation of the resulting CTFs - from a staggered AB arrangement to an eclipsed AA stacking conformation. Finally, a substrate scope demonstrates the versatility of this approach, successfully yielding various CTFs., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

The catalytic oxidation of alcohols is an important transformation in the chemical industry. Carbon materials with a large surface area and N doping show great promise as metal-free catalysts for the reaction. In this study, a rich N-containing covalent triazine framework polymerized by cyanuric chloride and p-phenylenediamine was used to synthesize N-doped porous carbon with the assistance of a pore-forming agent-NaCl. First, the mass ratio of the polymer/NaCl was optimized to 1:9. Then, the influence of the pyrolysis temperatures (700-1000 °C) on the materials was studied in detail. It was found that the carbon materials were gradually exfoliated by molten salt at high temperatures. XRD and Raman characterizations showed them with a certain graphitization. The optimal doped carbon CNN-1-9-900 achieved the highest surface area of 199.03 m 2 g -1 with the largest pore volume of 0.29 cm 3 g -1 . Furthermore, it had a high N content of 9.9 at% with the highest relative proportion of pyridinic/graphitic N. Due to the synergistic effect between the surface area and pyridinic/graphitic N, CNN-1-9-900 showed the best performance for benzyl alcohol oxidation with TBHP at moderate conditions, and the process also worked for its derivatives.

Investigations into the selective oxidation of inert sp 3 C-H bonds using polymer photocatalysts under mild conditions have been limited. Additionally, the structure-activity relationship of photocatalysts often remains insufficiently explored. Here, a series of thiophene-based covalent triazine frameworks (CTFs) are used for the efficient and selective oxidation of hydrocarbons to aldehydes or ketones under ambient aerobic conditions. Spectroscopic methods conducted in situ and density functional theory (DFT) calculations revealed that the sulfur atoms within the thiophene units play a pivotal role as oxidation sites due to the generation of photogenerated holes. The effect of photogenerated holes on photocatalytic toluene oxidation was investigated by varying the length of the spacer in a CTF donor-acceptor based photocatalyst. Furthermore, the manipulation of reactive oxygen species was employed to enhance selectivity by weakening the peroxidative capacity. As an illustrative example, this study successfully demonstrated the synthesis of a precursor of the neurological drug AMG-579 using a photocatalytic protocol., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Membrane separation of aromatics and aliphatics is a crucial requirement in chemical and petroleum industries. However, this task presents a significant challenge due to the lack of membrane materials that can endure harsh solvents, exhibit molecular specificity, and facilitate easy processing. Herein, we present a novel approach to fabricate a covalent triazine framework (CTF) membrane by employing a mix-monomer strategy. By incorporating a spatial monomer alongside a planar monomer, we were able to subtly modulate both the pore aperture and membrane affinity, enabling preferential permeation of aromatics over aliphatics with molecular weight below 200 Dalton (Da). Consequently, we achieved successful all-liquid phase separation of aromatic/aliphatic mixtures. Our investigation revealed that the synergistic effects of size sieving and the affinity between the permeating molecules and the membrane played a pivotal role in separating these closely resembling species. Furthermore, the membrane exhibited remarkable robustness under practical operating conditions, including prolonged operation time, various feed compositions, different applied pressure, and multiple feed components. This versatile strategy offers a feasible approach to fabricate membranes with molecule selectivity toward aromatic/aliphatic mixtures, taking a significant step forward in addressing the grand challenge of separating small organic molecules through membrane technology., (© 2024 Wiley‐VCH GmbH.)

We have synthesized low-cost high performance covalent triazine framework (CTF) through Schiff base reaction of melamine and terephthalaldehyde with different proportions of the reactants. The synthesized adsorbents showed excellent capacity for adsorption of Cr (VI) at acidic pH while almost negligible adsorption at higher pH. The adsorbent displays excellent reusability, with a little decrease in adsorption capacity with the increasing number of cycles. Moreover, Cr (VI) the adsorption is unaffected by the presence of 50-500 times higher concentration of alkali metal and halide ions in solution, while sulphate ions demonstrate shielding behavior decreasing the adsorption capacity. Mechanistic studies indicate electrostatic attractions, ion exchange and reduction being responsible for the adsorption mediated by abundant nitrogen sites that also imbibes the adsorbent with high capacity. The adsorbent was also utilized to recover chromium from an industrial electroplating effluent, which demonstrates applicability of material for practical applications., Competing Interests: Declaration of competing interest We declare that we have no known competing financial interests or personal relationships that could influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

It is highly desirable to fabricate transition bimetallic alloy-embedded porous nanocarbons with a unique nanoarchitecture for the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) in rechargeable zinc-air batteries. In this work, we introduce a template-assisted in situ alloying synthesis of FeNi alloy nanoparticle-decorated coral-like nanocarbons (FeNi-CNCs) as efficient OER/ORR dual-functional electrocatalysts. The present materials are produced through polycondensation of a covalent triazine framework (CTF), the coordination of Ni and Fe ions, and sequential pyrolytic treatment. Through the pyrolysis process, the nanolamellar FeNi-CTF precursors can be facilely converted into FeNi alloy nanoparticle-decorated nanocarbons. These nanocarbons possess a distinctive three-dimensional (3D) coral-like nanostructure, which is favorable for the transport of oxygen and the diffusion of electrolyte. As a result, FeNi-CNC-800 with the highest efficiency exhibited remarkable electrocatalytic performance and great durability. Additionally, it also can be assembled into rechargeable zinc-air batteries that can be assembled in both liquid and solid forms, offering a superior peak power density, large specific capacity, and outstanding reusability during charging/discharging cycles (e.g., 5160 charging-and-discharging cycles at 10 mA cm -2 for the liquid forms). These traits make it a highly promising option in the burgeoning field of wearable energy conversion.

An in vivo solid-phase microextraction (SPME) fiber with high-coverage capture capacity of plant endogenous substances based on the porous covalent triazine framework (CTF) material was developed. The CTF fiber coupled with gas chromatographic quadrupole time-of-flight mass spectrometer (GC-QTOF-MS) analysis was used for monitoring untargeted endogenous metabolites in living Chinese cabbage plants (Brassica campestris L. ssp. chinensis Makino (var. communis Tsen et Lee)). A total of 100 endogenous substances were identified, mainly including aldehydes, ketones, acids, alcohols, phenols, alkanes, alkenes, esters, isorhodanates, nitriles, as well as indole and its derivatives. Using the in vivo metabolites analysis method, Chinese cabbage plants at different growing stages demonstrated significantly statistical differences in plant metabolism. In addition, metabolic dysregulation of Chinese cabbage plants under fipronil pesticide contamination was observed. To summarize, the proposed approach provides a feasible method to capture metabolic information in living vegetables and for risk assessment of pesticide use during agricultural production., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Electrochemical two-electron water oxidation (2e WOR) is gaining surging research traction for sustainable hydrogen peroxide production. However, the strong oxidizing environment and thermodynamically competitive side-reaction (4e WOR) posit as thresholds for the 2e WOR. We herein report a custom-crafted covalent triazine network possessing strong oxidizing properties as a proof-of-concept metal-free functional organic network electrocatalyst for catalyzing 2e WOR. As the first-of-its-kind, the material shows a maximum of 89.9 % Faradaic Efficiency and 1428 μmol/h/cm 2 H 2 O 2 production rate at 3.0 V bias potential (vs reversible hydrogen electrode, RHE), which are either better or comparable to the state-of-the-art electrocatalysts. We have experimentally confirmed a stepwise 2e WOR mechanism which was further computationally endorsed by density functional theory studies., (© 2023 Wiley-VCH GmbH.)

Two-dimensional (2D) polymeric semiconductors, especially covalent triazine framework (CTF) nanosheets with aromatic triazine linkages are emerging as attractive metal-free photocatalysts owing to their predictable structures, good semiconducting properties, and high stability. However, the quantum size effect and ineffective electron screening of 2D CTF nanosheets cause an enlargement of electronic band gap and high excited electron-hole binding energies, which lead to low-level enhancements in photocatalytic performance. Herein, we present a novel triazole groups functionalized CTF nanosheet (CTF-LTZ) synthesized by facile combination of ionothermal polymerization and freeze-drying strategy from the unique letrozole precursor. The incorporation of the high-nitrogen-containing triazole group effectively modulates the optical and electronic properties, resulting in narrowed bandgap from 2.92 eV for unfunctionalized CTF to 2.22 eV for CTF-LTZ and dramatically improved charge separation, as well as highly-active sites for O 2 adsorption. As a result, CTF-LTZ photocatalyst exhibits excellent performance and superior stability in H 2 O 2 photosynthesis, with a high H 2 O 2 production rate of 4068 μmol h -1 g -1 and a remarkable apparent quantum efficiency of 4.5 % at 400 nm. This work provides a simple and effective approach for rational design highly-efficient polymeric photocatalysts for H 2 O 2 production., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Inc. All rights reserved.)

Using photocatalytic oxidation to convert basic chemicals into high value compounds in environmentally benign reaction media is a current focus in catalytic research. The challenge lies in gaining controllability over product formation selectivity. We design covalent triazine frameworks as heterogeneous, metal-free, and recyclable photocatalysts for visible-light-driven switchable selective oxidation of styrene in pure water. Selectivity in product formation was achieved by activation or deactivation of the specific photogenerated oxygen species. Using the same photocatalyst, by deactivation of photogenerated H 2 O 2 , benzaldehyde was obtained with over 99 % conversion and over 99 % selectivity as a single product. The highly challenging and sensitive epoxidation of styrene was carried out by creating peroxymonocarbonate as an initial epoxidation agent in the presence of bicarbonate, which led to formation of styrene oxide with a selectivity up to 76 % with near quantitative conversion. This study demonstrates a preliminary yet interesting example for simple control over switchable product formation selectivity for challenging oxidation reactions of organic compounds in pure water., (© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

The tunability of porous covalent triazine frameworks (CTFs) can mitigate poor photostability and rapid hole-electron recombination. Herein, an excellent improvement of visible light-driven photocatalytic pollutant degradation was achieved using a hybrid semiconductor of covalent triazine framework-zinc ferrite spinel catalysts (CTF-ZnFe 2 O 4 ). The as-prepared CTF-ZnFe 2 O 4 composites were fabricated using a facile one-pot ionothermal method. The hybrid photocatalysts were identified using X-ray diffraction (XRD), scanning electron microscopy/energy-dispersive X-ray (SEM-EDX), X-ray photoelectron spectrometer (XPS), Brunauer-Emmett-Teller (BET), Fourier transform infrared (FTIR), and UV-visible diffuse reflection spectroscopy (UV-vis DRS) characterizations. The analysis reveals that hybridization successfully ensued and altered the crystallinity structure, morphology, surface area, and bandgap energy of hybrid material. It was found that CTF-ZnFe 2 O 4 90:10 is very effective for the degradation of MB in a UV-vis light photocatalytic process with the efficiency of 95.4% and k obs of 0.421 min -1 for degradation of 50 mg/L MB with 0.5 g/L dosages for 120 min. Additionally, the scavenger study, effect of additional oxidants, and stability were performed for the practical application of a hybrid photocatalyst. CTF-ZnFe 2 O 4 90:10 shows outstanding pollutant degradation in sunlight irradiation and high stability with only a 5.2% reduction after a five-times sequential recycling process. Moreover, the photocatalytic mechanism of as-prepared CTF-ZnFe 2 O 4 was mainly influenced by [Formula: see text] radical compared to [Formula: see text] and [Formula: see text] radicals. Overall, The as-prepared CTF-ZnFe 2 O 4 shows significant potential to be utilized for photocatalytic wastewater treatment., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Herein, a series of covalent triazine framework/bismuth vanadate (CTF/BiVO 4 ) heterojunction catalysts were prepared using the hydrothermal method. The mechanism of the CTF/BiVO 4 heterojunction photocatalyst in the system was examined to provide a theoretical basis for constructing a high-efficiency photocatalysis composite system for removing organic pollutants from water. Compared with CTF and BiVO 4 catalysts alone, composite materials have been shown to have significantly higher degradation efficiencies against organic pollutants in water. Moreover, the degradation effect was found to be optimal when the mass ratio of CTF to BiVO 4 was 1:1 (1-CTF/BiVO 4 ). On the basis of physicochemical characterization results, it was concluded that the effective construction of CTF/BiVO 4 composite photocatalyst material systems and the formation of type II heterojunction structures between CTF and BiVO 4 effectively promote the separation of photogenerated carriers and increase the interface charge transfer efficiency., (© 2022. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Selenium (Se) removal from contaminated water has become a major environmental problem in recent years. Designing efficient and selective materials for selenium adsorption is urgent and still represents a great challenge. Herein, two novel cationic covalent triazine frameworks (CTFS-Cl and CTFL-Cl) are developed for the first time and employed as a new class of Se adsorbents. The results from systematic adsorption experiments indicate that these materials can adsorb SeO 4 2- in a wide range of pH values (2-11) with fast kinetics (5 min), outstanding adsorption capacity, and excellent selectivity over other competing anions. The maximum adsorption capacity achieved (149.3 mg/g by CTFS-Cl) constitutes one of the highest values among the organic polymeric materials. More importantly, after a single step adsorption, these materials can reduce the Se concentrations to lower than 10 μg/L, the lowest drinking water standard in the world. The adsorption mechanism was probed by XPS technique, EDS analysis, adsorption experiments, and DFT calculations, which reveals that anion exchange between Cl - and SeO 4 2- is the main driving force for Se adsorption. Additionally, CTFS-Cl and CTFL-Cl perform well toward real contaminated river water sample with the residual Se being less than 8.49 μg/L. This work demonstrates the excellent performance of CTFs-based materials with great application prospect for Se removal in contaminated water treatment., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Iridium oxide (IrO x -NP) and palladium nanoparticles (Pd-NP) were supported on a 2,6-dicyanopyridine-based covalent-triazine framework (DCP-CTF) by energy-saving and sustainable microwave-assisted thermal decomposition reactions in propylene carbonate and in the ionic liquid [BMIm][NTf 2 ]. Transmission electron microscopy (TEM), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS) confirm well-distributed NPs with sizes from 2 to 13 nm stabilized on the CTF particles. Metal contents between 10 and 41 wt% were determined by flame atomic absorption spectroscopy (AAS). Nitrogen sorption measurements of the metal-loaded CTFs revealed Brunauer-Emmett-Teller (BET) surface areas between 904 and 1353 m 2  g -1 . The composites show superior performance toward the hydrogen evolution reaction (HER) with low overpotentials from 47 to 325 mV and toward the oxygen reduction reaction (ORR) with high half-wave potentials between 810 and 872 mV. IrO x samples in particular show high performances toward HER while the Pd samples show better performance toward ORR. In both reactions, electrocatalysts can compete with the high performance of Pt/C. Exemplary cyclic voltammetry durability tests with 1000 cycles and subsequent TEM analyses show good long-term stability of the materials. The results demonstrate the promising synergistic effects of NP-decorated CTF materials, resulting in a high electrocatalytic activity and stability., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2022 Rademacher, Beglau, Heinen, Barthel and Janiak.)

Scalable and eco-friendly synthesis of crystalline porous covalent triazine frameworks (CTFs) is essential to realize their broad industrial applications but remains a great challenge, which requires the fundamental understanding of the two-dimensional polymerization mechanism. Herein, we report a universal polyphosphoric acid (H 6 P 4 O 13 )-catalyzed nitrile trimerization route to synthesize a series of highly crystalline CTFs with high specific surface areas. This new strategy enables the cost-effective large-scale fabrication of crystalline CTFs at kilogram level for the first time. Through density functional theory calculation and detailed controlled experiments, we reveal that the polyphosphate acid show much higher catalytic activity for trimerization reaction than its analogues such as P 2 O 5 and H 3 PO 4 . Furthermore, the crystalline CTFs with regular porosity and abundant triazine groups exhibit ultrahigh removal efficiency of micropollutants, indicating its great potential in environment remediation., (© 2022 Wiley-VCH GmbH.)

Recently, triazine-based two dimensional (2D) porous materials have received increasing attention in photocatalysis. Herein, CTF-1, a covalent triazine framework, was adopted as the blueprint for designing a 2D bespoke photocatalyst. The thiazolo[5,4-d]thiazole (TzTz) linkage was inserted into the framework of CTF-1, affording TzTz-TA, which belongs to conjugated microporous polymers (CMPs). Rather than the direct insertion via the challenging CH activation, TzTz-TA was assembled from 2,4,6-tris(4-formylphenyl)-1,3,5-triazine and dithiooxamide, in which TzTz was formed in situ by a process of catalyst-free solvothermal condensation. Both CTF-1 and TzTz-TA had similar energy gaps (E g ), photocurrents, and charge carrier lifetimes, in line with the similar molecular underpinnings. However, the reduction potential of TzTz-TA is less negative than that of CTF-1 due to the insertion of TzTz linkage, in a more appropriate position for activating O 2 to superoxide (O 2 •- ). In return, blue light-mediated oxidation of sulfides to sulfoxides with O 2 over TzTz-TA was accomplished with significantly superior conversions to those over CTF-1. Intriguingly, extensive sulfides could be oxidized to corresponding sulfoxides with outstanding recycling stability of TzTz-TA. Notably, attendance of an induction period was observed during TzTz-TA photocatalysis. This work highlights the vast potential of designing triazine-based porous materials to meet the tailor-made demands, such as the oxidative transformation of organic molecules with O 2 ., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Inc. All rights reserved.)

Covalent triazine frameworks (CTFs) are a class of porous organic polymers that continuously attract growing interest because of their outstanding chemical and physical properties. However, the control of extended porous organic framework structures at the molecular scale for a precise adjustment of their properties has hardly been achieved so far. Here, we present a series of bipyridine-based CTFs synthesized through polycondensation, in which the sequence of specific building blocks is well controlled. The reported synthetic strategy allows us to tailor the physicochemical features of the CTF materials, including the nitrogen content, the apparent specific surface area, and optoelectronic properties. Based on a comprehensive analytical investigation, we demonstrate a direct correlation of the CTF bipyridine content with the material features such as the specific surface area, band gap, charge separation, and surface wettability with water. The entirety of these parameters dictates the catalytic activity as demonstrated for the photocatalytic hydrogen evolution reaction (HER). The material with the optimal balance between optoelectronic properties and highest hydrophilicity enables HER production rates of up to 7.2 mmol/(h·g) under visible light irradiation and in the presence of a platinum cocatalyst.

The construction of hollow mesoporous carbon nanospheres (HMCS) avoiding the use of traditional soft/hard templates is highly desired for nanoscience yet challenging. Herein, we report a simple and straightforward template-free strategy for preparing nitrogen, sulfur dual-doped HMCSs (N/S-HMCSs) as oxygen reduction reaction (ORR) electrocatalysts. The unique hollow spherical and mesoporous structure was in-situ formed via a thermally initiated hollowing pathway from an elaborately engineered covalent triazine framework. Regulation of pyrolysis temperatures contributed to precisely tailoring of the shell thickness of HMCSs. The resulting N/S-HMCS 900 (pyrolyzed at 900 °C) possessed high N and S contents, large specific surface areas, rich and uniform mesopores distribution. Consequently, as a metal-free ORR electrocatalyst, N/S-HMCS 900 exhibits a high half-wave potential, excellent methanol tolerance and great long-term durability. Additionally, density functional theory calculations demonstrate that N, S-dual dopant can create extra active sites with higher catalytic activity than the isolated N-dopant. This strategy provides new insights into the construction of hollow and mesoporous multi-heteroatom-doped carbon materials with tunable nanoarchitecture for various electrochemical applications., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier Inc. All rights reserved.)

The shuttling effect of polysulfides is one of the major problems of lithium-sulfur (Li-S) batteries, which causes rapid capacity fading during cycling. Modification of the commercial separator with a functional interlayer is an effective strategy to address this issue. Herein, we modified the commercial Celgard separator of Li-S batteries with one-dimensional (1D) covalent triazine framework (CTF) and a carbon nanotube (CNT) composite as a functional interlayer. The intertwined CTF/CNT can provide a fast lithium ionic/electronic transport pathway and strong adsorption capability towards polysulfides. The Li-S batteries with the CTF/CNT/Celgard separator delivered a high initial capacity of 1314 mAh g -1 at 0.1 C and remained at 684 mAh g -1 after 400 cycles -1 at 1 C. Theoretical calculation and static-adsorption experiments indicated that the triazine ring in the CTF skeleton possessed strong adsorption capability towards polysulfides. The work described here demonstrates the potential for CTF-based permselective membranes as separators in Li-S batteries.

Perfluorinated covalent triazine frameworks (F-CTFs) have shown unique features and attractive performance in separation and catalysis. However, state-of-the-art F-CTFs synthesized via the ZnCl 2 -promoted procedure have quite low fluorine contents due to C-F bond cleavage induced by chloride (a Lewis base) and the harsh conditions deployed (400-700 °C). Fabricating F-CTFs with high fluorine contents (>30 wt %) remains challenging. Herein, we present a low-temperature ionothermal approach (275 °C) to prepare F-CTFs, which is achieved via polymerization of tetrafluoroterephthalonitrile (TFPN) over the Lewis superacids, e.g., zinc triflimide [Zn(NTf 2 ) 2 ] without side reactions. With low catalyst loading (equimolar), F-CTFs are afforded with high fluorine content (31 wt %), surface area up to 367 m 2  g -1 , and micropores around 1.1 nm. The highly hydrophobic F-CTF-1 exhibits good capability to boost electroreduction of CO 2 to CO, with faradaic efficiency of 95.7 % at -0.8 V and high current density (-141 mA cm -2 ) surpassing most of the metal-free electrocatalysts., (© 2021 Wiley-VCH GmbH.)

Ultrathin nanosheets have great potential for photocatalytic applications, however, suffer from enlarged band gap and narrowed visible-light-responsive range due to the quantum confinement effect. Herein, we report a novel redox strategy for efficient preparation of ultrathin crystalline amide-functionalized covalent-triazine-framework nanosheets (CTF NSs) with enhanced visible light absorption. The CTF NSs exhibited photocatalytic hydrogen (512.3 μmol h -1 ) and oxygen (12.37 μmol h -1 ) evolution rates much higher than that of pristine bulk CTF. Photocatalytic overall water splitting could be achieved with efficient stoichiometric H 2 (5.13 μmol h -1 ) and O 2 (2.53 μmol h -1 ) evolution rates under visible light irradiation. Experimental and theoretical analysis revealed that introduction of amide groups as electron donor optimized the band structure and improve its visible-light absorption, hydrophilicity and carrier separation efficiency, thus resulting in the enhanced photocatalytic performance. The well-dispersed CTF NSs could be easily cast onto a support as a thin film device and demonstrate excellent photocatalytic activity (25.7 mmol h -1  m -2 for hydrogen evolution)., (© 2021 Wiley-VCH GmbH.)

Lithium-sulfur (Li-S) batteries have been widely considered as the next-generation energy storage system but hindered by the soluble polysulfide intermediate-induced shuttle effect. Doping heteroatoms was confirmed to enhance the affinity of polysulfide and the carbon host, release the shuttle effect, and improve the battery performance. To enhance the Lewis acidity and reinforce the interaction between polysulfide and the carbon skeleton, a novel covalent triazine framework (CTFO) was designed and fabricated by copolymerizing 2,4,6-triphenoxy- s -triazine and 2,4,6-trichloro-1,3,5-triazine through Friedel-Crafts alkylation. Polymerization led to triazine substitution on the para-position of the phenoxy groups of 2,4,6-triphenoxy-triazine and produced two-dimensional three-connected honeycomb nanosheets. These nanosheets were confirmed to exhibit packing in the AB style through the intralayer π-π interaction to form a three-dimensional layered network with micropores of 0.5 nm. The practical and simulated results manifested the enhanced polysulfide capture capability due to the abundant N and O heteroatoms in CTFO. The unique porous polar network endowed CTFO with improved Li-S battery performance with high Coulombic efficiency, rate capability, and cycling stability. The S@CTFO cathode delivered an initial discharge capacity of 791 mAh g -1 at 1C and retained a residual capacity of 512 mAh g -1 after 300 charge-discharge cycles with an attenuation rate of 0.117%. The present results confirmed that multiple heteroatom doping enhances the interaction between the porous polar CTF skeleton and polysulfide intermediates to improve the Li-S battery performance.

Rapid and high-flux enantiomer separation is significant for drug development. Membrane separation technology provides promising approaches for enantiomer separations. Porous membrane with good selectivity and high permeability is an ideal choice for enantiomer separations. Herein, we demonstrate the preparation of a novel two-dimensional chiral covalent triazine frameworks (CCTF) membrane by "in situ growth" method. Inheriting the strong chirality and specific interactions from CCTF, the CCTF membranes exhibited good enantioselectivity for drug intermediates and drug, including (R)/(S)-1-phenylethanol, (R)/(S)-1,1'-binaphthol and (R)/(S)-ibuprofen. Under optimal separation conditions, the enantiomeric excess value (e.e %) was above 21.7 % for (R)/(S)-1-phenylethanol, 12.0% for (R)/(S)-1,1'-binaphthol and 9.7 % for (R)/(S)-ibuprofen. The mechanism of the CCTF recognizing enantiomers were simulated by quantum mechanical calculations. In addition, the mechanism was also proved by the separation of enantiomers using this CCTF-modified silica column in liquid chromatography. The CCTF membrane may bring about the potentially application for large-scale production of chiral compounds. Meanwhile, this work provides a theoretical guidance for the application of CCOFs in enantiomer separation., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.The authors declare the following financial interests/personal relationships which may be considered as potential competing interests:, (Copyright © 2021 Elsevier B.V. All rights reserved.)

A solid-phase extraction (SPE) method was established for fipronil and its metabolite residues (fipronil desulfinyl, fipronil sulphone and fipronil sulphide) in eggs with a covalent triazine framework (CTF) porous material as the adsorbent followed by ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) detection. Multiple probes and quantum chemistry theory calculations were conducted to describe the versatile adsorption property directly and quantifiably. The conjugated structure of CTF and N-containing triazine generated π-π interactions and hydrogen bonds between the CTF and the targets, which led to high extraction efficiency and recoveries. The solid-phase extraction parameters, including amount of the adsorbent, type of eluent, amount of eluent and loading rate were investigated. Under the optimal experimental conditions, the recoveries of the analytes were between 85.5% and 103.2%, and the RSD (n = 5) was between 1.8% and 3.6%. The LODs and LOQs were 0.13-0.2 ng g -1 and 0.5-0.8 ng g -1 , respectively. The sorbent can effectively reduce the interference of the matrix and meet the detection requirements of fipronil and its metabolites in eggs. These results imply that the CTF as adsorbents have great potential in the analysis of trace targets in samples with complex matrices.

Synthesis of solid-state proton-conducting membranes with low activation energy and high proton conductivity under anhydrous conditions is a great challenge. Here, we show a simple and convenient way to prepare covalent triazine framework membranes (CTF-Mx) with acid in situ doping for anhydrous proton conduction in a wide temperature range from subzero to elevated temperature (160 °C). The low proton dissociation energy and continuous hydrogen bond network in CTF-Mx make the membrane achieve high proton conductivity from 1.21×10 -3 S cm -1 (-40 °C) to 2.08×10 -2 S cm -1 (160 °C) under anhydrous conditions. Molecular dynamics and proton relaxation time analyses reveal proton hopping at low activation energies with greatly enhanced mobility in the CTF membranes.

The construction of multiple heteroatom-doped porous carbon with unique nanoarchitectures and abundant heteroatom active sites is promising for reversible oxygen-involving electrocatalysis. However, most of the synthetic methods required the use of templates to construct precisely designed nanostructured carbon. Herein, we introduced an ultrasound-triggered route for the synthesis of a piperazine-containing covalent triazine framework (P-CTF). The ultrasonic energy triggered both the polycondensation of monomers and the assembly into a nanoflower-shaped morphology without utilizing any templates. Subsequent carbonization of P-CTF led to the formation of nitrogen, phosphorus, and fluorine tri-doped porous carbon (NPF@CNFs) with a well-maintained nanoflower morphology. The resultant NPF@CNFs showed high electrocatalytic activity and stability toward bifunctional electrolysis, which was better than the commercial Pt/C and IrO 2 electrocatalysts toward oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), respectively. As a further demonstration, employing NPF@CNFs as air electrode materials resulted in an excellent performance of liquid-state and solid-state Zn-air batteries, showing great potentials of the obtained multiple heteroatom-doped porous carbon electrocatalysts for wearable electronics.

Covalent triazine frameworks (CTFs) as a kind of covalent organic framework (COF) materials show great potential for practical application by virtue of their high stability and facile large-scale synthesis. In this work, we developed three CTFs (MSCTF-1, MSCTF-2, and xSCTF-2) of different pore size decorated with S-groups using different functionalization methods for achieving selective Hg 2+ removal from aqueous solutions. The material structures were comprehensively studied by gas adsorption, IR and XPS, etc. Among them, the MSCTF-2 with 24.45% S content showed the highest Hg 2+ adsorption capacity of 840.5 mg g ‒1 , while MSCTF-1 exhibiting much larger distribution coefficient of 1.67 × 10 8 mL g ‒1 renders an exceptionally high efficiency for reducing the concentration of Hg 2+ contaminated water to less than 0.03 μg L ‒1 . Moreover, the MSCTFs show distinct features of: (i) high selectivity toward Hg 2+ over various transition metal ions; (ii) high stability over a wide pH range from pH 1 to 12; and (iii) good recyclability with 94% of Hg 2+ removal over five consecutive cycles. The Hg 2+ adsorption on functionalized CTFs followed pseudo-second-order kinetics and Langmuir isotherm. Our results revealed the material structure-performance relationship that the adsorption capacities depend on the binding site density whereas the distribution coefficient is essential to the removal efficiency., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Carbon dioxide catalytic conversion (i. e., CO 2 catalysis) is considered as one of the most promising technologies to control CO 2 emissions, which is of great significance to build a sustainable society with green low-carbon cycle. In view of its thermodynamic stability and kinetic inertness, CO 2 selective activation is still desired. Nowadays, the traditional strategy is to selectively capture and efficiently convert atmospheric CO 2 into high value-added chemicals and fuels. Covalent triazine frameworks (CTFs) as a newly emerging and attractive kind of porous organic polymer (POP) have drawn worldwide attention among heterogeneous catalysis because of their nitrogen-rich porous structures and exceptional physicochemical stabilities. In this Minireview, the focus was mainly placed on the structural design and synthesis of CTFs and their applications in CO 2 catalysis including CO 2 cycloaddition, CO 2 carboxylation, CO 2 hydrogenation, CO 2 photoreduction, and CO 2 electroreduction. By discussing the structure-property relationship, valuable guidance from a sustainable perspective may be provided for developing precisely designed CTFs with high performance and excellent industrial application prospects in sustainable CO 2 catalysis., (© 2020 Wiley-VCH GmbH.)

Covalent triazine frameworks (CTFs) with polypyridyl ligands are very promising supports to anchor photocatalytic complexes. Herein, we investigate the photophysical properties of a series of ligands which vary by the extent of the aromatic system, the nitrogen content and their topologies to aid in selecting interesting building blocks for CTFs. Interestingly, some linkers have a rotational degree of freedom, allowing both a trans and cis structure, where only the latter allows anchoring. Therefore, the influence of the dihedral angle on the UV-Vis spectrum is studied. The photophysical properties are investigated by a combined computational and experimental study. Theoretically, both static and molecular dynamics simulations are performed to deduce ground- and excited state properties based on density functional theory (DFT) and time-dependent DFT. The position of the main absorption peak shifts towards higher wavelengths for an increased size of the π-system and a higher π-electron deficiency. We found that the position of the main absorption peak among the different ligands studied in this work can amount to 271 nm; which has a significant impact on the photophysical properties of the ligands. This broad range of shifts allows modulation of the electronic structure by varying the ligands and may help in a rational design of efficient photocatalysts., (© 2020 The Authors. Published by Wiley-VCH GmbH.)

Defective nitrogen-doped carbon materials have shown a promising application as metal-free electrocatalysts in the oxygen reduction reaction (ORR) and the hydrogen evolution reaction (HER). However, there are still some challenges in the tuning of metal-free electrocatalysts and in understanding the roles of various nitrogen species in their electrocatalytic performance. Herein, we design a covalent triazine framework (CTF)-based material as an effective metal-free bifunctional electrocatalyst. We chose BINOL-CN (2,2'-dihydroxy-[1,1'-binaphthalene]-6,6'-dicarbonitrile) as both a carbon and a nitrogen source for the fabrication of N-containing CTF-based materials. Four BINOL-CTFs with varying N-functionalities (pyridinic-N/triazine-N, pyrrolic-N, quaternary-N, and pyridine-N-oxide) were successfully obtained. These materials were evaluated in the ORR and the HER in basic and acidic conditions, respectively. The best material has an onset potential of 0.793 V and a half-wave potential of 0.737 V, and it follows first-order kinetics in a 4e - pathway in the ORR reaction. The same material shows an impressive HER activity with an overpotential of 0.31 V to achieve 10 mA/cm 2 and a small Tafel slope of 41 mV/dec, which is comparable to 31 mV/dec for Pt/C, making it a potential bifunctional electrocatalyst. We showed that the ORR and HER reactivity of CTF-based materials depends exclusively on the amount of quaternary-N species and on the available surface area and pore volume. This work highlights the engineering of CTF materials with varying amounts of N species as high-performance bifunctional electrocatalysts.

Gas sensors with high sensitivity, fast response/recovery, good selectivity, and room-temperature operation are highly desirable for practical use. However, most of the existing gas sensing materials, either conventional metal oxide semiconductors or advanced inorganic two-dimensional (2D) polymers, can hardly satisfy the above requirements. Herein, we demonstrate an organic 2D polymer derived from a covalent triazine framework (CTF), which possesses nanoscale thickness, intrinsic and periodic pore structures, and abundant functional groups with excellent gas sensing performance. The as-prepared triazine-based 2D polymer (T-2DP) exhibits selective recognition to NO 2 with an ultrahigh sensitivity of 452.6 ppm -1 , which outperforms most other 2D nanomaterials and its CTF matrix. The sensing effect is superfast (35-47 s) and fully reversible operated at room temperature. The superior comprehensive gas sensing performance of T-2DP and the underlying mechanism was experimentally studied and further discussed by comparison with that of CTF and widely investigated inorganic 2D polymers including graphene and MXene. As a proof of concept, a flexible NO 2 chemiresistor based on T-2DP was fabricated to demonstrate its potential for integration into wearable electronics. The scientific findings in this work may propose a new route for the design of high-performance gas sensing materials on the basis of organic 2D polymers in next-generation wearable electronic devices.

It is found that a covalent triazine framework (CTF-1) (that was prepared from 1,4-dicyanobenzene) exhibits oxidase-like activity toward the oxidation of luminol with dissolved oxygen in alkaline condition to produce intense blue chemiluminescence (CL). The reaction follows Michaelis-Menten kinetics and shows strong specificity for luminol. Reactive oxygen species including 1 O 2 , • OH and O 2 •- are testified to be involved in the reaction and responsible for the CL. The reaction was applied to the determination of the radical-scavenging activity of antioxidants, with rutin, kaempferol and ferulic acid serving as model scavengers. A sensitive CL method was developed for the determination of rutin based on its inhibitory effect on the reaction. The CL system gave a linear response to the concentration of rutin in the range of 0.03-0.25 μmol·L -1 with a limit of detection of 0.015 μmol·L -1 . The practicability of the method was demonstrated by successful determination of rutin in tablets and in Flos Sophorae Immaturus. Graphical Abstract.

The production of multifunctional pure organic materials that combine different sizes of pores and a large number of electron spins is highly desirable due to their potential applications as polarizers for dynamic nuclear polarization-nuclear magnetic resonance and as catalysts and magnetic separation media. Here, we report a polychlorotriphenylmethyl radical-linked covalent triazine framework (PTMR-CTF). Two different sizes of micropores were established by N 2 sorption and the presence of unpaired electrons (carbon radicals) by electron spin resonance and superconducting quantum interference device-vibrating sample magnetometer analyses. Magnetization measurements demonstrate that this material exhibits spin-half paramagnetism with a spin concentration of ∼2.63 × 10 23 spins/mol. We also determined the microscopic origin of the magnetic moments in PTMR-CTF by investigating its spin density and electronic structure using density functional theory calculations.

The structural features of adsorbents and the interactions between adsorbents and adsorbates dominate the removal capacity of porous materials to a certain degree. In this work, we used a bottom-up strategy to select a high-performance catalytic adsorbent with appropriate pore structure characteristics by integrating adsorption and catalytic degradation to wipe off Safranin T (ST) dye. That is, a covalent triazine framework based on tetra(4-cyanophenyl)-ethylene (CTF-TCPE) was synthesized to wipe out ST dye from aqueous solution. Systematic researches including kinetics, equilibrium adsorption and photo-catalysis studies were performed. The micro-layer and hierarchical pore structure, high surface area, large pore volume, high negative Zeta potential and the catalytic degradation of CTF-TCPE play key roles in the removal process of ST. The removal amount reaches 6743 mg g -1 in experiment, which is much higher than most experimental values of the other porous materials reported so far, as far as we know. The removal efficiency can reach as high as 99% even above 1000 ppm ST concentration. Removal process and mechanism analyses show that there are strong electrostatic interactions and π-π interactions between CTF-TCPE and ST. The desorption and kinetics experiments show that there exists catalytic degradation during the adsorption process. In high initial concentration of the dye system, partly multilayer adsorption phenomenon occurs between CTF-TCPE and ST dye. The catalytic degradation and multilayer adsorption combine to result in high removal capacity of CTF-TCPE for ST. The effects of pH and ionic strength on ST removal show that CTF-TCPE can work at wide pH and ionic strength ranges. These results indicate that CTF-TCPE is high-efficiency for removal of ST from aqueous solution. Therefore, the strategy of selecting adsorbents based on the structural characters integrating adsorption and catalytic degradation is efficient for designing and synthesizing high-performance removal materials., (Copyright © 2018 Elsevier Inc. All rights reserved.)

The exposures of pharmaceutical antibiotics in water solution caused potential risks for ecological environment and human health. In the present study, porous covalent triazine frameworks (CTFs) were synthesized and the adsorption behavior of sulfamethoxazole (SMX) and tylosin (TL) was investigated. The CTFs were characterized by X-ray diffraction, transform infrared and N 2 adsorption/desorption. Sulfamethoxazole displayed much stronger adsorption than tylosin on microporous CTF-1 adsorbent due to the pore-filling effect. While the adsorption of bulky tylosin on microporous CTF-1 was suppressed because of the size exclusion effect. Additionally, the porous CTF DCBP showed stronger adsorption affinity and faster adsorption kinetics than other porous adsorbents, which was attributed to wide pore size distribution and open pore structure. Findings in this study highlight the potential of using porous CTFs as a potential adsorbent to eliminate antibiotics from water, especially for selective adsorption of bulky molecular pollutant., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Five porous ether-linked phthalazinone-based covalent triazine frameworks (PHCTFs) were successfully constructed via ionothermal polymerizations from flexible dicyano monomers containing asymmetric, twisted, and N-heterocyclic phthalazinone structure. All the building blocks could be easily prepared by simple and low-cost aromatic nucleophilic substitution reactions, showing the large-scale application potential of thermal stable phthalazinone structure in constructing porous materials. Generally, the flexible building blocks are avoided to prevent the networks from collapsing in constructing high surface area porous materials. Our experimental results revealed that the introduction of the substituents can effectively decrease the probability of the network interpenetration from the longer struts and the intermolecular/intramolecular intercalation from the increased degree of conformation freedom in the flexible ether-linkage, the BET surface areas of PHCTFs increasing from 676 to 1270 m 2 g -1 . Meanwhile, the effects of introducing different sizes (methyl or phenyl group) and amounts (one or two) of substituents on the porosities of the target polymer networks were also investigated in detail. The high CO 2 adsorption capacity of 10.3 wt % (273 K, 1 bar) can be ascribed to the strong affinity of the electron-rich N,O-containing networks with CO 2 . Excitingly, PHCTF-5 demonstrates the high CO 2 /N 2 selectivity up to 138 (273 K, 1 bar), according to the ideal adsorbed solution theory (IAST) for the higher proportion of V micro accompanied the electron-rich heteroatoms characteristic. Such high CO 2 adsorption capacity and good separation properties are superior to those of many other microporous organic polymers. These properties along with easily up-scalable synthesis make porous PHCTFs promising candidates applied in gas sorption and separation field.

Significant progress has been made on the synthesis and application of mesoporous γ-alumina. To date, little attention has been paid to the synthesis of microporous crystalline alumina. Here, fabrication of microporous crystalline γ-alumina using a microporous covalent triazine framework (CTF-1) as a template is described. Microporous crystalline γ-alumina with a micro-meso binary pore system was replicated by infiltration of aluminum nitrate into the micropores of the CTF-1 template through a NH 3 /water-vapor-induced internal hydrolysis method, followed by thermal treatment, and subsequent removal of the CTF-1 template with a 30 % H 2 O 2 aqueous solution. The obtained crystalline γ-alumina material exhibits a large surface area (349 m 2  g -1 ) with micropore distribution centered at about 1.27 nm. Ru supported on microporous γ-Al 2 O 3 can be employed as catalyst for hydrolytic dehydrogenation of ammonia borane, and it exhibits high catalytic activity and good durability. This finding provides a new benchmark for preparing well-defined crystalline microporous alumina materials by a template method, which can be applied in a wide range of fields., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Ultrathin membranes with intrinsic pores are highly desirable for gas separation applications, because of their controllable pore sizes and homogeneous pore distribution and their intrinsic capacity for high flux. Two-dimensional (2D) covalent organic frameworks (COFs) with layered structures have periodically distributed uniform pores and can be exfoliated into ultrathin nanosheets. As a representative of 2D COFs, a monolayer triazine-based CTF-0 membrane is proposed in this work for effective separation of helium and purification of hydrogen on the basis of first-principles calculations. With the aid of diffusion barrier calculations, it was found that a monolayer CTF-0 membrane can exhibit exceptionally high He and H2 selectivities over Ne, CO2, Ar, N2, CO, and CH4, and the He and H2 permeances are excellent at appropriate temperatures, superior to those of conventional carbon and silica membranes. These observations demonstrate that a monolayer CTF-0 membrane may be potentially useful for helium separation and hydrogen purification.

A heterogenized catalyst on a highly porous covalent triazine framework was synthesized and characterized to have a coordination environment similar to that of its homogeneous counterpart. The catalyst efficiently converted CO2 into formate through hydrogenation with a turnover number of 5000 after 2 h and an initial turnover frequency of up to 5300 h(-1) ; both of these values are the highest reported to date for a heterogeneous catalyst, which makes it attractive toward industrial application. Furthermore, the synthesized catalyst was found to be stable in air and was recycled by simple filtration without significant loss of catalytic activity., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The microstructural evolution of a series of triazine framework-based microporous (TFM) membranes under different conditions has been explored in this work. The pristine TFM membrane is in situ fabricated in the course of polymer synthesis via a facile Brønsted-acid-catalyzed cyclotrimerizaiton reaction. The as-synthesized polymer exhibits a microporous network with high thermal stability. The free volume size of the TFM membranes gradually evolved from a unimodal distribution to a bimodal distribution under annealing, as analyzed by positron annihilation lifetime spectroscopy (PALS). The emergence of the bimodal distribution is probably ascribed to the synergetic effect of quenching and thermal cyclization reaction. In addition, the fractional free volume (FFV) of the membranes presents a concave trend with increasing annealing temperature. Vapor sorption tests reveal that the mass transport properties are closely associated with the free volume evolution, which provides an optimal condition for dehydration of biofuels. A promising separation performance with extremely high water permeability has been attained for dehydration of an 85 wt % ethanol aqueous solution at 45 °C. The study on the free volume evolution of the TFM membranes may provide useful insights about the microstructure and mass transport behavior of the microporous polymeric materials., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)