Aqueous Sol-Gel Synthesis and Shaping of Covalent Organic Frameworks.

The intrinsic fragility and insoluble nature of covalent organic frameworks (COFs) have strongly impeded their processability for practical applications. Herein, an aqueous-based sol-gel synthetic strategy is reported for the synthesis and shaping of COFs with task-specific applications that satisfy the principles of green chemistry for gram-scale production of crystalline materials. Our successful approach involves three pivotal aspects: the "prodrug mimic" design of water-soluble monomers, the utilization of hydrolyzable bonds, and the manipulation of reaction kinetics. The generality of the method is demonstrated by the successful preparation of representative high-surface area two-dimensional (2D) COFs with several commonly used amines. By virtue of this strategy, a COF colloidal dispersion is achieved and can be formulated into processable fluids, structured films, and COF monoliths. Remarkably, the obtained lightweight (∼0.020 g cm-3) and robust aerogels displayed outstanding adsorption capacity (exceeding 57 times its own weight) toward a variety of organic solvents and exhibited superior thermal insulating properties compared to the widely used sponge and cotton. This work demonstrates a versatile strategy for the synthesis and shaping of processable COF materials in water that will contribute to the development of COF monoliths for advanced applications.

Porous Ionic Network/CNT Composite Separator as a Polysulfide Snaring Shield for High Performance Lithium-Sulfur Battery.

Lithium-sulfur (Li-S) battery features a high theoretical energy density, but the shuttle of soluble polysulfides between the two electrodes often results in a rapid capacity decay. Herein, a straightforward electrostatic adsorption strategy based on a cross-linked polyimidazolium separator as a snaring shield of polysulfides is reported, which suppresses the undesirable migration of polysulfides to the anode. The porous ionic network (PIN)-modified carbon nanotubes (CNTs) are successfully prepared and coated onto a commercial porous polypropylene membrane in a vacuum-filtration step. The favorable affinity of the imidazolium ring toward polysulfide via the polar interaction and the electrostatic effect of ions mitigates the undesirable shuttle of polysulfides in the electrolyte, improving the Li─S battery in terms of rate performance and cycling life. Compared to the reference PIN-free CNT-coated separator, the PIN/CNT-coated one has an increased initial capacity of 1.3 folds (up to 1394.8 mAh g-1 for PIN/CNT/PP-3) at 0.1 C.

Building Porous Ni(Salen)-Based Catalysts from Waste Styrofoam via Autocatalytic Coupling Chemistry for Heterogeneous Oxidation with Molecular Oxygen.

The development of robust and industrially viable catalysts from plastic waste is of great significance, and the facile construction of high performance heterogeneous catalyst systems for phenol-quinone conversions remains a grand challenge. Herein, a feasible strategy is demonstrated to reclaim Styrofoam into hierarchically porous nickel-salen-loaded hypercrosslinked polystyrene (PS@Ni-salen) catalysts with high activities through an unusual autocatalytic coupling route. The salen is immobilized onto PS chain by Friedel-Crafts alkylation of benzyl chloride derivatives, and the generated hydrogen chloride coordinately promotes the simultaneous crosslinking and bridge formation between aromatic rings via a Scholl coupling route, leading to hierarchically porous networks. After the metallization with Ni, the resultant networks exhibit high catalytic activity for the oxidation of 2,3,6-trimethylphenol to 2,3,5-trimethyl-1,4-benzoquinone under mild conditions (303 K, 1 bar of O2 ). This catalyst also demonstrates attractive recycling performance without an obvious loss of catalytic efficiency over five consecutive cycles. This methodology might provide a potential sustainable alternative to construct environmentally benign and cost-effective catalysts for specific organic transformation.

Reprocessible Triketoenamine-Based Vitrimers with Closed-Loop Recyclability.

Development of thermosets that can be repeatedly recycled via both chemical route (closed-loop) and thermo-mechanical process is attractive and remains an imperative task. In this work, we reported a triketoenamine based dynamic covalent network derived from 2,4,6-triformylphloroglucinol and secondary amines. The resulting triketoenamine based network does not have intramolecular hydrogen bonds, thus reducing its π-electron delocalization, lowering the stability of the tautomer structure, and enabling its dynamic feature. By virtue of the highly reversible bond exchange, this novel dynamic covalent bond enables the easy construction of highly crosslinked and chemically reprocessable networks from commercially available monomers. The as-made polymer monoliths exhibit high mechanical properties (tensile strength of 79.4 MPa and Young's modulus of 571.4 MPa) and can undergo a monomer-network-monomer (yields up to 90 %) recycling mediated by an aqueous solution, with the new-generation polymer capable of restoring the material strength to its original state. In addition, owing to its dynamic nature, a catalyst-free and low-temperature reprogrammable covalent adaptable network (vitrimer) was achieved. The design concept reported herein can be applied to the development of other novel vitrimers with high repressibility and recyclability, and sheds light on future design of sustainable polymers with minimal environmental impact.

Thiol-grafted covalent organic framework-based electrochemical platforms for sensitive detection of Hg(II) ions.

Triazine-based covalent organic frameworks functionalized by thiol and thioether (COFS-CH3/COFS-SH) were designed and served as a platform that could bind with mercury ions specifically based on Hard-Soft-Acid-Base theory. As such, when employing COFs as a modifier in a carbon paste electrode (CPE), the COFS-CH3-modified CPE revealed an extraordinary performance (detection limit of 0.01 ppb; linear range of 0.1 to 1.0 ppb) and repeatability for electrochemical detection of trace mercury, even in real samples collected from tap or lake water. This innovative approach leverages the inherent properties of covalent organic frameworks (COFs) to enable highly sensitive and selective detection of target analytes.

Water-dispersible and stable polydopamine coated cellulose nanocrystal-MXene composites for high transparent, adhesive and conductive hydrogels.

High conductive and transparent hydrogels with adhesion function are ideal candidates for soft electronic devices. However, it remains a challenge to design appropriate conductive nanofillers to endow hydrogels with all these characteristics. The 2D MXene sheets are promising conductive nanofillers for hydrogels due to excellent electricity and water-dispersibility. However, MXene is quite susceptible to oxidation. In this study, polydopamine (PDA) was employed to protect the MXene from oxidation and meanwhile endow hydrogels with adhesion. However, PDA coated MXene (PDA@MXene) were easily flocculated from dispersion. 1D cellulose nanocrystals (CNCs) were employed as steric stabilizers to prevent the agglomeration of MXene during the self-polymerization of dopamine. The obtained PDA coated CNC-MXene (PCM) sheets display outstanding water-dispersible and anti-oxidation stability and are promising conductive nanofillers for hydrogels. During the fabrication of polyacrylamide hydrogels, the PCM sheets were partially degraded into PCM nanoflakes with smaller size, leading to transparent PCM-PAM hydrogels. The PCM-PAM hydrogels can self-adhere to skin, and possess high transmittance of 75 % at 660 nm, superior electric conductivity of 4.7 S/m with MXene content as low as 0.1 % and excellent sensitivity. This study will facilitate the development of MXene based stable, water-dispersible conductive nanofillers and multi-functional hydrogels.

Interfacial Ti-S Bond Modulated S-Scheme MOF/Covalent Triazine Framework Nanosheet Heterojunctions for Photocatalytic C-H Functionalization.

Constructing photocatalyst systems to functionalize the inert C-H bonds has attracted extensive research interest. However, purposeful modulation of interfacial charge transfer in heterostructures remains a challenge, as it usually suffers from sluggish kinetics. Reported herein is an easy strategy to construct the heteroatom-induced interface for developing the titanium-organic frameworks (MOF-902) @ thiophene-based covalent triazine frameworks (CTF-Th) nanosheets S-scheme heterojunctions with controllable oxygen vacancies (OVs). Specifically, Ti atoms were first anchored onto the heteroatom site of CTF-Th nanosheets, and then grown into MOF-902 via an interfacial Ti-S linkage, generating OVs. Using in situ X-ray photoelectron spectroscopy (XPS), extended X-ray absorption fine structure (EXAFS) spectroscopy and density functional theory (DFT) calculations, the enhanced interfacial charge separation and transfer induced by moderate OVs in the pre-designed S-scheme nanosheets was validated. The heterostructures exhibited an improved efficiency in photocatalytic C3-acylation of indoles under mild conditions with a yield 8.2 times larger than pristine CTF-Th or MOF-902 and enabled an extended scope of substrates (15 examples). This performance is superior to state-of-the-art photocatalyst and can be retained, without significant loss, after 12 consecutive cycles.

Self-healing waterborne polyurethane coatings with high transparence and haze via cellulose nanocrystal stabilized linseed oil Pickering emulsion.

Protection coatings with self-healing ability can significantly enhance their anti-corrosion properties and service life. In this study, self-healing waterborne polyurethane (WPU) coatings with high transparence and haze were facile fabricated via cellulose nanocrystal (CNC) stabilized linseed oil (LO) Pickering emulsion. Sustainable CNCs displayed outstanding emulsifying ability and stability to stabilize LO Pickering emulsion. The size of LO Pickering emulsion droplets decreases with the CNC concentration, while the emulsion fraction and surface coverage by CNCs increase with CNC concentration, leading to a more stable Pickering emulsion. The self-healing rates of WPU coatings at varied time, temperature, CNC and catalyst concentration were investigated. Higher temperature, larger emulsion droplets, and with driers employed as catalysts generally lead to faster self-healing rate. The WPU self-healing coatings displayed much better abrasion resistance and mechanical properties than pristine WPU due to the incorporation of CNCs. Moreover, the WPU self-healing coatings show a high transparence and haze due to light scattering, and their applications as coatings of lamp covers and glass to achieve uniform light distribution and privacy protection with high light transmission were further demonstrated.

Coupling Ni-Cu atomic pair to promote CO2 electroreduction with near-unity CO selectivity.

The electrocatalytic reduction of CO2 towards CO is one of the most desirable routines to reduce atmospheric CO2 concentration and maintain a global carbon balance. In this work, a novel porous NiCu-embedded ZIF-derived N-doped carbon nanoparticle (NiCu@NCNPs) catalyst has been identified as an active, highly selective, stable, and cost-effective catalyst in CO2 reduction. A CO selectivity as high as 100% has been achieved on NiCu@NCNPs which is the highest reported to date. The particle current density of CO on NiCu@NCNPs is around 15 mA cm-2 under the optimized potential at -0.9 V vs. RHE. The NiCu@NCNPs electrode also exhibits excellent stability during the five sequential CO2 electroreduction experiments. The superior catalytic performance of NiCu@NCNPs in CO2RR can be related to its microstructure with high electrochemical surface area and low electron transfer resistance. Furthermore, a kinetic analysis has shown the formation of intermediate *COOH is the rate-determining step in CO2RR towards CO. According to the results of density functional theory (DFT) calculations, a low Gibbs-free energy change (∆G) for the rate-determining step leads to the enhanced catalytic performance of CO2RR on NiCu@NCNPs.

Synergistic removal of organic pollutants from water by CTF/BiVO4 heterojunction photocatalysts.

Herein, a series of covalent triazine framework/bismuth vanadate (CTF/BiVO4) heterojunction catalysts were prepared using the hydrothermal method. The mechanism of the CTF/BiVO4 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 BiVO4 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 BiVO4 was 1:1 (1-CTF/BiVO4). On the basis of physicochemical characterization results, it was concluded that the effective construction of CTF/BiVO4 composite photocatalyst material systems and the formation of type II heterojunction structures between CTF and BiVO4 effectively promote the separation of photogenerated carriers and increase the interface charge transfer efficiency.

Effects of residual pectin composition and content on the properties of cellulose nanofibrils from ramie fibers.

In this study, a series of pretreatment methods (pectin extraction) were employed to prepare cellulose nanofibrils (CNFs) with different pectin composition and contents from ramie fibers. The comprehensive effects of residual pectin on the final properties of CNFs were investigated. The residual pectin did not have a significant effect on the size distribution of the obtained CNFs. While the presence of pectin led to higher zeta potential value, improved dispersion stability and enhanced storage modulus of the CNF dispersion, with the sodium carbonate extraction method showing the greatest impact. The possible mechanism for enhanced dispersion stability of CNFs is the formation of self-assembled hierarchical pectin-hemicellulose/lignin-cellulose nanostructures, offering abundant electrostatic repulsion and steric hindrance between the nanoparticles. This work provides guidelines for the tailored production of CNFs to meet the requirements for different applications.

Structure and Properties of PVDF/PA6 Blends Compatibilized by Ionic Liquid-Grafted PA6.

Compatibilization of immiscible blends is critically important for developing high-performance polymer materials. In this work, an ionic liquid, 1-vinyl-3-butyl imidazole chloride, grafted polyamide 6 (PA6-g-IL(Cl)) with a quasi-block structure was used as a compatibilizer for an immiscible poly(vinylidene fluoride) (PVDF)/PA6 blend. The effects of two PA6-g-IL(Cl)s (E-2%-50K and E-8%-50K) on the morphology, crystallization behavior, mechanical properties, and surface resistance of the PVDF/PA6 blend were investigated systematically. It was found that the two types of PA6-g-IL(Cl)s had a favorable compatibilization effect on the PVDF/PA6 blend. Specifically, the morphology of the PVDF/PA6 = 60/40 blend transformed from a typical sea-island into a bicontinuous structure after incorporating E-8%-50K with a high degree of grafting (DG). In addition, the tensile strength of the PVDF/PA6/E-8%-50K blend reached 66 MPa, which is higher than that of PVDF, PA6 and the PVDF/PA6 blend. Moreover, the PVDF/PA6/E-8%-50K blend exhibited surface conductivity due to the conductive path offered by the bicontinuous structure and conductive ions offered by grafted IL(Cl). Differential scanning calorimetry (DSC) and wide-angle X-ray diffractometry (WAXD) results revealed that PA6-g-IL(Cl) exhibits different effects on the crystallization behavior of PVDF and PA6. The compatibilization mechanism was concluded to be based on the fact that the nongrafted PA6 blocks entangled with the PA6 chains, while the ionic liquid-grafted PA6 blocks interacted with the PVDF chains. This work offers a new strategy for the compatibilization of immiscible polymer blends.

A Knitting Copolymerization Strategy to Build Porous Polytriazolium Salts for Removal of Anionic Dyes and MnO4.

Although considerable efforts have been devoted to novel ionic porous networks (IPNs), the development of them in a scalable manner to tackle the issues in pollutant treatment by adsorption remains an imminent challenge. Herein, inspired by natural spider webs, a knitting copolymerization strategy is proposed to construct analogue triazolium salt-based porous networks (IPN-CSUs). It is not only convenient to incorporate the cationic motifs into the network, but easy to control over the contents of ionic pairs. The as-prepared IPN-CSUs displays a high surface area of 924 m2 g-1 , a large pore volume of 1.27 cm3 g-1 and abundant ionic sites, thereby exhibiting fast adsorption rate and high adsorption capacity towards organic and inorganic pollutants. The kinetics and thermodynamics study reveal that the adsorption followed a pseudo-second-order kinetic model and Langmuir isotherm model correspondingly. Specifically, the maximum adsorption capacity of the IPN-CSUs is as high as 1.82 mg mg- 1 for permanganate ions and up to 0.54 mg mg-1 for methyl orange, which stands out among the previously reported porous adsorbents so far. It is expected that the strategy reported herein can be extended to the development of other potential efficient adsorbents in water purifications.

Polarization-induced charge separation in conjugated microporous polymers for efficient visible light-driven C-3 selenocyanation of indoles.

Conjugated microporous polymers (CMPs) are cost-effective photocatalysts in organic transformations, while they are usually limited by the insufficient separation of photogenerated charges. Here we report a polarization strategy through molecular geometry optimization to promote the charge separation of CMPs. Three CMP photocatalysts with an alternative donor-acceptor skeleton and tunable symmetry were synthesized by the oxidative coupling of bis-carbazoles with electron-deficient bridges (benzene/pyridine/pyrimidine). Simply regulating the polarization of the starting monomers leads to tailorable porosity, photoelectric properties, and photocatalytic activity of the CMPs. They exhibited high efficiency in C-3 selenocyanation of indoles under visible-light and at room temperature, and pyridine-based CMPs with the largest dipole moment gave a yield of up to 94%, superior to their state-of-the-art photocatalyst counterparts. Photo-physical experiments combined with theoretical calculations further supported that the incorporation of the polarized linker introduced an internal electric field, benefitting efficient charge separation. This offered new insight into developing high-performance photocatalysts.

Visible-light-driven Cr(VI) reduction by ferrocene-integrated conjugated porous polymers via dual catalytic routes.

Conjugated porous polymers with rapid separation of photogenerated charges and multiple catalytic pathways remain a great challenge. Herein, two ferrocene-based polymers (Fc-CPPs) with high charge separation efficiency and unique dual catalytic routes for Cr(vi) reduction were developed. They exhibited an excellent efficiency, with almost 99% of Cr(vi) readily converted to Cr(iii) under 15 min of visible light illumination (λ > 420 nm).

Fe-based Fenton-like catalysts for water treatment: Preparation, characterization and modification.

Fenton reaction based on hydroxyl radicals () is effective for environment remediation. Nevertheless, the conventional Fenton reaction has several disadvantages, such as working at acidic pH, producing iron-containing sludge, and the difficulty in catalysts reuse. Fenton-like reaction using solid catalysts rather than Fe2+ has received increasing attention. To date, Fe-based catalysts have received increasing attention due to their earth abundance, good biocompatibility, comparatively low toxicity and ready availability, it is necessary to review the current status of Fenton-like catalysts. In this review, the recent advances in Fe-based Fenton-like catalysts were systematically analyzed and summarized. Firstly, the various preparation methods were introduced, including template-free methods (precipitation, sol gel, impregnation, hydrothermal, thermal, and others) and template-based methods (hard-templating method and soft-templating method); then, the characterization techniques for Fe-based catalysts were summarized, such as X-ray diffraction (XRD), Brunauer, Emmett and Teller (BET), SEM (scanning electron microscopy)/TEM (transmission electron microscopy)/HRTEM (high-resolution TEM), FTIR (Fourier transform infrared spectroscopy)/Raman, XPS (X-ray photoelectron spectroscopy), 57Fe Mössbauer spectroscopy etc.; thirdly, some important conventional Fe-based catalysts were introduced, including iron oxides and oxyhydroxides, zero-valent iron (ZVI) and iron disulfide and oxychloride; fourthly, the modification strategies of Fe-based catalysts were discussed, such as microstructure controlling, introduction of support materials, construction of core-shell structure and incorporation of new metal-containing component; Finally, concluding remarks were given and the future perspectives for further study were discussed. This review will provide important information to further advance the development and application of Fe-based catalysts for water treatment.

Co(III)-Salen immobilized cellulose nanocrystals for efficient catalytic CO2 fixation into cyclic carbonates under mild conditions.

Searching for green, recyclable and highly efficient catalyst for the synthesis of cyclic carbonates from CO2 is of great importance because it is profitable for reducing the greenhouse effects and meets the principles of green chemistry. Herein, a series of cellulose nanocrystals, either the pristine or modified ones (TEMPO oxidized and Co(III)salen immobilized), were explored as catalysts for cycloaddition of epoxides and carbon dioxide. The impact of surface properties on the performance of the as-made catalysts was investigated. Co(III)-salen grafted cellulose nanocrystals was proven to be the most effective catalyst in this study, which could afford excellent yield up to 99 % after 24 h even under low CO2 pressures of 0.1 MPa. They can be easily recovered and reused for at least 4 times, demonstrating their excellent stability. We found that the surface functional groups such as enriched sulfate or carboxylic groups could also account for the enhanced catalytic activity. This work highlights the applications of green and sustainable nanoparticles in a cycloaddition reaction and offers a sustainable solution in industrial catalysis related to CO2 conversions.

One-pot construction of nitrogen-rich polymeric ionic porous networks for effective CO2 capture and fixation.

Facile preparation of ionic porous networks (IPNs) with large and permanent porosity is highly desirable for CO2 capture and transformation but remains a challenge. Here we report a one-pot base-mediated construction of nitrogen-rich IPNs through a combination of nucleophilic substitution and quaternisation chemistry from H-imidazole. This strategy, as proven by the model reactions of 1H-imidazole or 1-methyl-1H-imidazole with cyanuric chloride, allows for fine regulation of porosity and physicochemical properties, leading to nitrogen-rich IPNs featuring abundant ionic units and radicals. The as-prepared networks, termed IPN-CSUs, efficiently capture CO2 (80.1 cc g-1 at 273 K/1 bar) with an ideal CO2/N2 selectivity of 139.7. They can also effectively catalyse the cycloaddition reaction between CO2 and epoxides with high yields of up to 99% under mild conditions (0.1 MPa, 298 K), suggesting their possible applications in the fields of both selective molecular separation and conversion. Unlike the previously known strategies generally involving single coupling chemistry, our strategy combining two coupling routes in one pot appears to be unique and potentially applicable to other building blocks.

Effect of Molecular Architecture and Composition on the Aggregation Pathways of POEGMA Random Copolymers in Water.

Understanding of the temperature-induced phase transition of poly(oligo(ethylene glycol) methyl ether methacrylate) (POEGMA) random copolymers with varied composition remains largely incomplete. Upon heating they can form either macroscopically phase-separated aggregates or micelles. We examined the effect of polymer architecture by rationally designing and synthesizing various POEGMA copolymer structures via atom transfer radical polymerization using OEGMA monomers of different EO lengths. Micelle formation occurred for copolymers with a small fraction of long side chains counterbalanced by an appropriate number of short side chains, while macroscopic phase separation occurred for other copolymer compositions. In some copolymer compositions and architectures, micelle formation followed by macroscopic phase separation occurred, and the temperature of these phase transitions could be tailored accordingly. This new strategy allows the control over the microstructure and specific transition temperatures enabling, for instance, the preparation of nanocarriers for encapsulating hydrophobic compounds.

Evaluation of the Spring Seedling Project-Zhaotong Program: A study of a novel continuing medical education program for rural doctors in China.

OBJECTIVE: To evaluate the effectiveness of the Spring Seedling Project-Zhaotong program, a novel continuing medical education program, to improve the knowledge and skills of rural doctors in China. DESIGN: An uncontrolled single-group pre- and post-intervention design based on quantitative and qualitative methods. SETTING: Zhaotong is a prefecture-level city located in Yunnan, China. PARTICIPANTS: A total of 1866 country doctors practising in Zhaotong were enrolled. INTERVENTIONS: The Zhaotong program consisted of three stages: remote education, workshops conducted in Zhaotong and field training in Shanghai. MAIN OUTCOME MEASURES: The effectiveness of the remote education and Zhaotong workshop stages was assessed based on differences between pre- and post-training test scores. Qualitative comments were collected to assess the experience of country doctors following the Shanghai field training stage. RESULTS: In total, 1866 country doctors (46.9% males; mean age: 38.2 ± 9.2 years) participated in the program. The average score of the post-training test was higher than that of the pre-training test, both online (P < .001) and offline (P < .001). In regard to the Zhaotong workshops, with the exception of incisions/suturing, the average scores of cardiopulmonary resuscitation, gynaecological examinations and child growth/development were improved after training (P < .001). Qualitative analysis showed that Shanghai field training enhanced understanding of general practice, with the majority of country doctors indicating that they would apply what they learned in daily practice. CONCLUSION: This study introduced an comprehensive form of continuing medical education for rural doctors in Zhaotong and proved the effectiveness of this program and also provided a reference point for the future development of continuing medical education.