Ionic Liquid-Accelerated Growth of Covalent Organic Frameworks with Tunable Layer-Stacking.

Layer-stacking behaviors are crucial for two-dimensional covalent organic frameworks (2D COFs) to define their pore structure, physicochemical properties, and functional output. So far, fine control over the stacking mode without complex procedures remains a grand challenge. Herein, we proposed a "key-cylinder lock mimic" strategy to synthesize 2D COFs with a tunable layer-stacking mode by taking advantage of ionic liquids (ILs). The staggered (AB) stacking (unlocked) COFs were exclusively obtained by incorporating ILs of symmetric polarity and matching molecular size; otherwise, commonly reported eclipsed (AA) stacking (locked) COFs were observed instead. Mechanistic study revealed that AB stacking was induced by a confined interlocking effect (CIE) brought by anions and bulky cations of the ILs inside pores ("key" and "cylinder", respectively). Excitingly, this strategy can speed up production rate of crystalline powders (e.g., COF-TAPT-Tf@BmimTf2N in merely 30 minutes) under mild reaction conditions. This work highlights the enabling role of ILs to tailor the layer stacking of 2D COFs and promotes further exploration of their stacking mode-dependant applications.

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.

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.

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.

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.

A Vinylene-Bridged Conjugated Covalent Triazine Polymer as a Visible-Light-Active Photocatalyst for Degradation of Methylene Blue.

The development of new photocatalytic platforms using novel semiconductor material is an important challenge. Herein, a sp2 carbon-conjugated covalent triazine polymer (sp2 c-CTP-4), featuring a vinylene bridge and extended π-conjugation, is prepared as a highly efficient photocatalyst for degradation of methylene blue. sp2 c-CTP-4 exhibits substantial semiconducting properties such as enhanced charge transfer and prolonged lifetime of carriers compared to its counterparts with CN or CC connections, likely due to its extended π-delocalization with an unencumbered CC bridge. Moreover, benefiting from its high chemical stability, the as-made catalyst can be recycled five times with good retention of photocatalytic activity. This study provides a new pathway for constructing a robust platform for efficient photocatalysis and gives insight into the structure-property relationship of conjugated polymers.

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.

Amphiphilic Cellulose Nanocrystals for Enhanced Pickering Emulsion Stabilization.

Sulfated cellulose nanocrystals (CNC) with high surface charge density are inadequate for stabilizing oil-water emulsions, which limits their applications as interfacial stabilizers. We performed end-group modification by introducing hydrophobic chains (polystyrene) to CNC. Results showed that the modified CNC are more effective in emulsifying toluene and hexadecane than pristine CNC. Various parameters were investigated, such as concentration of particles, electrolytes, and polarity of solvents on the characteristics of the emulsions. This study provides strategies for the modification of cellulose nanocrystals to yield amphiphilic nanoparticles that enhance the stability of emulsions. Such systems, bearing biocompatible and environmentally friendly characteristics, are attractive for use in a wide range of industries spanning food, biomedicine, pharmaceuticals, cosmetics, and petrochemicals.

Metal Organic Framework with Coordinatively Unsaturated Sites as Efficient Fenton-like Catalyst for Enhanced Degradation of Sulfamethazine.

A novel Fenton-like catalyst, metal organic framework MIL-100(Fe) with FeII/FeIII mixed-valence coordinatively unsaturated iron center (CUS-MIL-100(Fe)), was synthesized, characterized, and used for the degradation of sulfamethazine (SMT). The catalytic performance of CUS-MIL-100(Fe) was investigated on the basis of various parameters, including initial pH, H2O2 concentration, catalyst dosage, and initial SMT concentration. The results showed that CUS-MIL-100(Fe) could effectively degrade SMT, with almost 100% removal efficiency within 180 min (52.4% mineralization efficiency), under the reaction conditions of pH 4.0, 20 mg L-1 SMT, 6 mM H2O2, and 0.5 g L-1 catalyst. Moreover, CUS-MIL-100(Fe) displayed a higher catalytic activity than that of MIL-100(Fe) for SMT degradation. Combined with the physical-chemical characterization, the enhanced catalytic activity can be ascribed to the incorporation of FeII and FeIII CUSs (coordinatively unsaturated metal sites), the large specific surface area, as well as the formation of mesopores. Furthermore, CUS-MIL-100(Fe) exhibited a good stability and reusability. The possible catalytic mechanism of CUS-MIL-100(Fe) was tentatively proposed.

Stimuli-Responsive Cellulose Nanocrystals for Surfactant-Free Oil Harvesting.

Cellulose nanocrystals with grafted binary polymer brushes (CNC-BPB), poly(oligoethylene glycol) methacrylate (POEGMA) and poly(methacrylic acid) (PMAA), were prepared by cerium-mediated polymerization in aqueous solution. The physical properties of CNC-BPB can be controlled by external triggers, such as temperature and pH, which can be utilized to stabilize and destabilize oil-water emulsions. By virtue of the modifications, these bifunctionalized CNCs diffused to the oil-water interface and stabilized the oil droplets at high pHs. When the pH was lowered to 2, strong hydrogen bonding between POEGMA and PMAA chains grafted on the CNC induced the coalescence of the emulsion droplets, resulting in the phase separation of oil and water. For emulsions stabilized by CNC-POEGMA and free PMAA mixtures, instantaneous coalescence was not observed at low pHs. Successive stabilization-destabilization over 5 cycles was demonstrated by modulating the pH with the addition of acid or base without any loss in efficiency. This work demonstrates that functional sustainable nanomaterials can be used for small scale oil-water separations, particularly for oil droplet transportation and harvesting of lipophilic compounds.

Stimuli-responsive Pickering emulsions: recent advances and potential applications.

Pickering emulsions possess many advantages over traditional surfactant stabilized emulsions. For example, Pickering emulsions impart better stability against coalescence and, in many cases, are biologically compatible and environmentally friendly. These characteristics open the door for their use in a variety of industries spanning petroleum, food, biomedicine, pharmaceuticals, and cosmetics. Depending on the application, rapid, but controlled stabilization and destabilization of an emulsion may be necessary. As a result, Pickering emulsions with stimuli-responsive properties have, in recent years, received a considerable amounts of attention. This paper provides a concise and comprehensive review of Pickering emulsion systems that possess the ability to respond to an array of external triggers, including pH, temperature, CO2 concentration, light intensity, ionic strength, and magnetic field. Potential applications for which stimuli-responsive Pickering emulsion systems would be of particular value, such as emulsion polymerization, enhanced oil recovery, catalyst recovery, and cosmetics, are discussed.

Dual responsive pickering emulsion stabilized by poly[2-(dimethylamino)ethyl methacrylate] grafted cellulose nanocrystals.

A weak polyelectrolyte, poly[2-(dimethylamino)ethyl methacrylate] (PDMAEMA), was grafted onto the surface of cellulose nanocrystals via free radical polymerization. The resultant suspension of PDMAEMA-grafted-cellulose nanocrystals (PDMAEMA-g-CNC) possessed pH-responsive properties. The grafting was confirmed by FTIR, potentiometric titration, elementary analysis, and thermogravimetric analysis (TGA); the surface and interfacial properties of the modified particles were characterized by surface tensiometer. Compared to pristine cellulose nanocrystals, modified CNC significantly reduced the surface and interfacial tensions. Stable heptane-in-water and toluene-in-water emulsions were prepared with PDMAEMA-g-CNC. Various factors, such as polarity of solvents, concentration of particles, electrolytes, and pH, on the properties of the emulsions were investigated. Using Nile Red as a florescence probe, the stability of the emulsions as a function of pH and temperature was elucidated. It was deduced that PDMAEMA chains promoted the stability of emulsion droplets and their chain conformation varied with pH and temperature to trigger the emulsification and demulsification of oil droplets. Interestingly, for heptane system, the macroscopic colors varied depending on the pH condition, while the color of the toluene system remained the same. Reversible emulsion systems that responded to pH were observed and a thermoresponsive Pickering emulsion system was 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.

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.

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.