Advances in controlled-release fertilizer encapsulated by organic-inorganic composite membranes

Heavy use of conventional fertilizers can lead to negative environmental concerns.Controlled-release fertilizers(CRFs)can effectively reduce the amounts of fertilizers used,improve the availability of fer-tilizers,and which is conducive to the protection of the ecological environment and sustainable devel-opment of agriculture.Therefore,it is imperative to develop and use CRFs as an alternative to traditional fertilizers.This review aims to present the classification,raw material composition,benefits,release process,release mode,and manufacturing methods of fertilizers coated with organic-inorganic com-posite membranes(OICMs)in order to provide an overall update and summarize CRFs encapsulated by OICMs and provide an insight for future trends in the field of fertilizers.It is expected that utilizing CRFs encapsulated by OICMs and their characteristics for agricultural applications can provide innovative ideas and suggestions for developing novel CRFs suitable for modern and sustainable agriculture.

A Transparent Photoresist Made of Titanium Dioxide Nanoparticle-Embedded Acrylic Resin with a Tunable Refractive Index for UV-Imprint Lithography

Transparent photoresists with a high refractive index(RI)and high transmittance in visible wavelengths have promising functionalities in optical fields.This work reports a kind of tunable optical material composed of titanium dioxide nanoparticles embedded in acrylic resin with a high RI for ultraviolet(UV)-imprint lithography.The hybrid film exhibits a tunable RI of up to 1.67(589 nm)after being cured by UV light,while maintaining both a high transparency of over 98%in the visible light range and a low haze of less than 0.05%.The precision machining of optical microstructures can be imprinted easily and efficiently using the hybrid resin,which acts as a light guide plate(LGP)to guide the light from the side to the top in order to conserve the energy of the display device.These preliminary studies based on both laboratory and commercial experiments pave the way for exploiting the unparalleled optical properties of nanocomposite resins and promoting their industrial application.

In-situ construction of grass-like hybrid architecture responsible for extraordinary corrosion performance: Experimental and theoretical approach

Despite the engineering potential by the co-existence of inorganic and organic substances to protect vulnerable metallic materials from corrosive environments,both their interaction and in-situ formation mechanism to induce the nature-inspired composite remained less understood.The present work used three distinctive mercaptobenzazole(MB)compounds working as corrosion inhibitors,such as 2-mercaptobenzoxazole(MBO),2-mercaptobenzothiazole(MBT),and 2-mercaptobenzimidazole(MBI)in a bid to understand how the geometrical structure arising from O,S,and N atoms affected the interaction toward inorganic layer.MB compounds that were used here to control the corrosion kinetics would be interacted readily with the pre-existing MgO layer fabricated by plasma electrolysis.This phenomenon triggered the nucleation of the root network since MB compounds were seen to be adsorbed actively on the defective surface through the active sites in MB compound.Then,the molecule with twin donor atoms adjacent to the mercapto-sites affected the facile growth of the grass-like structures with‘uniform’distribution via molecular self-assembly,which showed better corrosion performance than those with having dissimilar donor atoms with the inhibition efficiency(η)of 97%approximately.The formation mechanism underlying nucleation and growth behavior of MB molecule was discussed concerning the theoretical calculation of density functional theory.

Aqueous-Phase Sorption Behaviors of Cs⁺, Co²⁺, Sr²⁺and Cd²⁺ions on some Composite Ion Exchangers

A two new hybrid “organic-inorganic” composite ion exchangers (SAM and FAM), was synthesized by the combination of inorganic ion exchanger tin (IV) silicate and tin (IV) antimonate respectively with organic polymer polyacrylamide (PAm). The sorption isotherms for Cs+, Co2+, Sr2+ and Cd2+ ions on composite ion exchanger were investigated in the range (0.0005 - 0.01M) at different reaction temperature (30℃, 45℃ and 60℃ ± 1℃). The sorption data were subjected to different sorption isotherms and the results verified that Langmuir isotherm is the best model to be applied, and the monolayer sorption capacity were calculated and was found to increase as the reaction temperature increases.

Highly Stable Perovskite Solar Cells by Reducing Residual Water-Induced Decomposition of Perovskite

Residual water-induced decomposition is one of the dominant reasons for the decay of power conversion efficiency (PCE) in perovskite solar cells (Pero-SCs). To solve this problem, we introduce traces amount of sodium hyaluronate (SH) into the perovskite active layer to reduce the remaining water during the preparation of perovskite films. Unlike the traditionally adopted passive protection of perovskite from exterior water by low surface energy coatings, this study provides active control of the interior water by the addition of a water adsorbent into the perovskite films. The encapsulated Pero-SCs with SH retain approximately 70% of their initial PCE in 4000 h, while those without SH retain 32% of their initial PCE in 1000 h under the dark and ambient atmosphere. The unencapsulated Pero-SCs with SH stored in N2 atmosphere maintain over 94% of the initial PCE in 3000 h at room temperature away from light and remain over 88% of the initial PCE in 2000 h even the devices are heated to 70 °C. It has been proven that the improved stability is mainly due to the well-controlled residual water in perovskite films. Concomitantly, the PCE of p-i-n solar cells based on (FAPbI3)0.85(MAPbBr3)0.15 is improved from 19.34% to 21.54%.

Recent Advances and Progress for the Fabrication and Surface Modification of AIE-active Organic-inorganic Luminescent Composites

Organic dyes based hybrid organic-inorganic luminescent nanomaterials with high quantum efficiency, good physical or chemical stability, and favorable biocompatibility, have attracted growing attention recently because of their important applications in the areas of biomedical imaging, chemical sensors, and light-emitting diodes(LEDs). Nevertheless, conventional fluorescence molecules suffer from aggregation-caused quenching(ACQ) when they are doped into inorganic nanomaterials. Aggregation-induced emission(AIE) is an abnormal and intriguing fluorescent phenomenon that has aroused increasing interest for various applications especially in biomedical fields. Compared with conventional organic dyes, the AIE-active molecules will emit more intense fluorescence in their aggregates or solid states. It provides an elegant route to overcome the drawbacks of conventional organic molecules. Over the past few decades, the fabrication and surface modification of various organic-inorganic luminescent composites doped with AIE-active molecules have been reported. Therefore, it is highly desirable to summarize these advances. In this review, recent advances and progress in constructing various AIEgens-doped organic-inorganic hybrid nanocomposites and their subsequent surface modification were summarized. We hope this review could further promote the research of AIE-active functional materials.

Syntheses and Crystal Structures of a Cadmium(Ⅱ) and a Zinc(Ⅱ) Complexes with the Flexible Ligand 1-Acetic Acid-2, 2'-biimidazole

Reactions of NaAcebiim （NaAcebiim = 1-acetic acid-2, 2＇-biimidazote monoso- dium salt） and cadmium or zinc nitrate produce two supramolecular architectures, namely, 1D [Cd（Acebiim）（NO3）（H20）]n （1） and 0D [Zn（Acebiim）2（H20）2]＇2H20 （2） in acidic aqueous solutions. Single-crystal X-ray diffraction analysis reveals that complex 1 crystallizes in the triclinic system, space group Pi, and 2 is of monoclinic system, space group P2 1/n. In 1, two nitrate groups link two Cd（Ⅱ） ions forming [Cd2（NO3）2（H20）2] as secondary building units that are interconnected by the Acebiim ligand into an infinite ladder. In2, the hydrogen-bonded synthon R22（16） between the N-H moieties and carboxylic acid link [Zn（Acebiim）2（H20）2], generating a 1D-extended ribbon. Moreover, hydrogen bonds and π-π interactions further stabilize the 3D supramolecular architecture.

A Novel Neodymium-tartrate Complex with Distinctive Rare Topology:Hydrothermal Synthesis and Crystal Structure

One novel neodymium-tartrate complex exhibiting distinctive rare topology,name-ly,[Nd（TTA）1.5（H2O）]·H2O（1,H2TTA = tartaric acid）,was successfully synthesized by the reaction of neodymium-oxide with H2TTA under hydrothermal conditions.Single-crystal X-ray diffraction analysis reveals that 1 belongs to the monoclinic system,space group P21/c with a = 6.0357（13）,b = 7.6106（17）,c = 24.389（5） ,β = 100.136（5）°,V = 1102.8（4） 3,Z = 4,Dc = 2.423 g·cm-3,μ = 4.763 mm-1,F（000） = 776,the final R = 0.0689 and wR = 0.2191.In complex 1,the 2D layer consisting of μ4-ligands and 4-connected Nd（III） centers is a rare example of uni-nodal net of（42.64） topology.The 2D layers are further connected by μ2-TTA2-ligands to give a 3D（42.64）（42.67.8） topological structure,where the Nd（III） atoms act as rare 5-connected topological blocks.

Synthesis and Thermoelectric Property of 1D Flexible PEDOT: p-TSA/Glass Fiber

Exploiting the thermal insulation properties of glass fiber and excellent conductivity of conducting polymer, a novel one-dimensional (1D) composite thermoelectric material, based on poly(3,4-ethylenedioxythiophene): p-toluenesulfonic acid (PEDOT: p-TSA)/glass fiber, is prepared by coating the PEDOT: p-TSA on the surface of glass fiber with in situ polymerization method. We hope the materials can bring out the performance of the “electron conductor, photon glass”. During the polymerization process, the effects of oxidant concentration and dopant mass fraction on thermoelectric properties of the materials are investigated. The group type of the polymer chain and the morphology of the samples were characterized by Fourier transform infrared spectroscopy (FT-IR) and scanning electron microscopy (SEM), respectively. The maximal Seebeck coefficient (S) and electric conductivity (σ) of the pristine sample are 32 μVK-1 and 169 Sm-1, respectively. After further post-processing with methanol, the thermoelectric properties of materials were improved, and the maximum value of S and σ increased greatly to 48.5 μVK-1 and 3184 Sm-1, respectively. The maximal power factor (PF) of materials also increased from 0.12 μWm-1 K-2 to 6.74 μWm-1 K-2. Moreover, we have proposed a preliminary explanation on the carrier transport mechanism.

A Crystalline Material Made from Oxidation of Vanadium Nitride via Foam Route

Facile method of synthesizing organic-inorganic solid foam in complex structure is presented. The synthesis method is based on the use of neutral surfactant (1-hexadecylamine, C16H33NH2) as structure directing agent and inorganic salt (vanadium nitride, VN) as precursor. The foam containing C16H33NH2 has been synthesized by evolution of oxygen gas produced spontaneously from hydrogen peroxide through a viscous VN gel. The foam from the precursor of 0.5 gVN nanopowder grows gradually, reaching about 0.3 liters 10 minutes after excess addition of H2O2 and stirring. The ultralight, crystalline material made via foam processing was observed by XRD, SEM, TEM, and FTIR.

The structure of colloidal polyethylenimine-silica nanocomposite microparticles

Deposition of silica from an organosilane tetraethoxysilane(TEOS)onto parent polyethylenimine(PEI)microgel particles produces a novel PEI-silica nanocomposite,which possesses greater adsorption ca-pacity for copper ions than either parent material.This study explores factors governing interactions of silica with the PEI matrix,along with structural features of resulting PEI-silica composite particles,to explain their properties and determine their application potential.The influence of initial TEOS/PEI mass ratio and the duration of silica deposition on the final silica content and distribution in the composite are studied.A comparative analysis of the structural architecture of chemically etched silica remnants,original PEI-silica composite particles and the parent PEI-microgel is carried out using X-ray photo-electron spectroscopy,small-angle X-ray scattering,and electron microscopy techniques.It is found that silica sol nanoparticles are evenly distributed throughout the PEI-microgel framework and interlinked with it via electrostatic interactions,enabling a structural model of the PEI-silica nanocomposite to be proposed.The chemical stability of resulting nanocomposite particles in parallel with the parent PEI-microgel is tested and shown to be robust for more than 100 days of storage in aqueous dispersions across a range of pH conditions,highlighting the application potential for these particles in copper capture.

Supramolecular Bonding Competition Enabled Nanostructure Evolution and Mechanical Reinforcement

In this work,competition between different supramolecular interactions is investigated based on a fibrous crystal composed of hydrogen-bonded cyanuric acid(CA)and amidinothiourea(ADT).Melamine(M)is found to prevail over ADT and bond to CA due to its stronger triple H-bonding affiliation,forming hollow microtubes assembled by oriented CAM crystalline arrays,as guided by the directionality of peripheral hydrogen bonds.Furthermore,competitive interaction between hydrogen bonding and ionic/covalent bonding is demonstrated by mixing Ag+ions with the CA-ADT fibers,where sulfur atoms are abstracted from ADT molecules to produce Ag_(2)S ligaments.The in situ-formed Ag_(2)S serves as a binding glue to generate CA-ADT/Ag_(2)S composites with significantly enhanced mechanical strength compared to the pristine CA-ADT fiber pellet.

Preparation and Characterization of Exfoliated Poly（ethyleneterephthalate）/Montmorillonite Nanocomposites Using Modified MMTs with Variable Content of Antimony Acetate

Poly（ethylene terephthalate） （PET）/montmorillonite （MMT） nanocomposite was prepared by the direct polymerization with MMTs modified with variable content of antimony acetate （Sb（OAc）3）, which was also used as catalyst polymerization. The modified MMTs （AS-Sb-MMT） were prepared by intercalating both Sb（OAc）3 and amphoteric surfactant （AS） into MMT layers. Nine kinds of Sb-MMTs [MMT treated with Sb（OAc）3] with different Sb content were obtained, but only six kinds of PET/MMT nanocomposites could be prepared. ICPAES was used to characterize Sb content of modified MMT, XRD was used to characterize interlayer spacing, IR spectroscopy was used to characterize composition change of Sb catalyst in modified MMT and TEM was used to investigate micromorphology of PET/MMT nanocomposites. Several results are obtained, i.e., （a） Sb content of Sb-MMT is affected by both drying temperature and washing-drying sequence, （b） compared with Na-MMT （unmodified MMT）, the change in the interlayer spacing of Sb-MMT is attributed to the solvent ethylene glycol （EG） rather than the intercalated or absorbed Sb（OAc）3, （c） based on this, a model is developed to describe the swelling of Na-MMT and modified MMT by EG and the effect of drying temperature on the interlayer spacing, （d） exfoliation state of MMT in PET matrix of nanocomposites is controlled not only by Sb content and interlayer spacing, but also by the composition of Sb catalyst in modified MMT.

ORGANIC/INORGANIC HYBRID EPOXY NANOCOMPOSITES BASED ON OCTA(AMINOPHENYL)SILSESQUIOXANE

Octa（aminophenyl）silsesquioxane （OAPS） was used as the curing agent of diglycidyl ether of bisphenol-A （DGEBA） epoxy resin. A study on comparison of DGEBA/OAPS with DGEBA/4,4＇-diaminodiphenyl sulfone （DDS） epoxy resins was achieved. Differential scanning calorimetry was used to investigate the curing reaction and its kinetics, and the glass transition of DGEBA/OAPS. Thermogravimetric analysis was used to investigate thermal decomposition of the two kinds of epoxy resins. The reactions between amino groups and epoxy groups were investigated using Fourier transform infrared spectroscopy. Scanning electron microscopy was used to observe morphology of the two epoxy resins. The results indicated that OAPS had very good compatibility with DGEBA in molecular level, and could form a transparent DGEBA/OAPS resin. The curing reaction of the DGEBA/OAPS prepolymer could occur under low temperatures compared with DGEBA/DDS. The DGEBA/OAPS resin didn＇t exhibit glass transition, but the DGEBA/DDS did, which meant that the large cage structure of OAPS limited the motion of chains between the cross-linking points. Measurements of the contact angle indicated that the DGEBA/OAPS showed larger angles with water than the DGEBA/DDS resin. Thermogravimetric analysis indicated that the incorporation of OAPS into epoxy system resulted in low mass loss rate and high char yield, but its initial decomposition temperature seemed to be lowered.

Interface science in polymer-based composite solid electrolytes in lithium metal batteries

Solid-state lithium metal batteries(SSLMBs)have attracted considerable attention as one of the most promising energy storage systems owing to their high safety and energy density.Solid electrolytes,particularly polymer-based composite solid electrolytes(CSEs),are considered promising electrolyte candidates for SSLMBs.However,theirwide application is inhibited by various electrochemical issues,such as low ionic conductivity,the growth of lithium dendrites,and poor cycling stability,which are related to interface issues within SSLMBs.In this review,the parameters related to various interfaces in the CSE of SSLMBs,including the interfaces between the polymer matrix and inorganic fillers,between the CSEs and the cathode,and between the CSEs and the lithium metal anode,are examined.Relevant issues and corresponding remediation strategies are proposed.Finally,future perspectives based on interfacial engineering and the characterization of polymer/inorganic filler interactions are proposed for building high-performance CSEs for use in SSLMBs.

Targeted Management of Perovskite Film by Co(Ⅱ)Sulfophenyl Porphyrin for Efficient and Stable Solar Cells

In the lead halide perovskite solar cells(PSCs),the redox reaction of I-and Pb^(2+) ions in perovskite materials under the fabrication and operation processes causes the formation of defects to destroy the cell efficiency and long-term stability.Herein,we have employed a Co(Ⅱ)sulfophenyl porphyrin(CoTPPS)to modify the perovskite film.The sulfonic group could coordinate with Pb2+to efficiently passivate the uncoordinated Pb^(2+).Additionally,Co^(2+) ions in CoTPPS could react with I^(2) generated under the thermal and light stress to yield the Co^(3+) and I^(-),thus achieving the regeneration of I^(-) in perovskite film.Therefore,the CoTPPS could realize the targeted management of the imperfections in perovskite film.As a result,the modified PSCs reveal the remarkably enhanced cell perfor-mance.More importantly,the CoTPPS modified device retains 75%of its initial efficiency value storing at 85℃for 2000 h and about 70%of its efficiency when being continuously illuminated at a simulated sunlight for 1200 h.This strategy tackles the chemical reaction and inhibits the defect generation,thus improving the operational stability and efficiency of PSCs.

Recent Progress in Metal-Organic Frameworks@Cellulose Hybrids and Their Applications

In recent years,metal-organic frameworks(MOFs)are attracting increasing attention due to their charming properties.However,the intrinsic fragility,powdered crystalline state,and poor processibility of MOFs hinder their further application.By this,the designs of MOF-based aerogels,hydrogels,membranes are effective ways to solve this problem.Graphene,silica,synthetic polymer and cellulose are the commonly used raw materials for fabricating MOF-based aerogels,hydrogels,and membranes.Among them,cellulose and its derivatives are the best candidates to support the powdered MOFs from the perspectives of economy,environmental protection and property.This review focuses on discussing the advantages of MOF@cellulose hybrids in applications such as water treatment,antibacterial,gas separation and adsorption,energy storage,drug delivery,catalysis,and other smart composites.MOF@cellulose-based aerogels,hydrogels and membranes can provide valuable guidance for investigating the practical application of MOFs in terms of processability,reusability,stability and easiness in handling.

Chemical sensors based on π-conjugated organic molecules and gold nanoparticles

Scientists have developed techniques for synthesizing and characterizing many new materials including conjugated small molecules, polymers and gold particles protected by conjugated organic chromophores for testing specific sensing properties in the past decade. Still, the design and synthesis or supermolecular systems fabrication of novel materials with controlled sensing properties is a significant and ongoing challenge within nanoscience and nanotechnology. Recently, our group has successfully constructed a series of chemosensors using small organic molecules, conjugated polymers and gold nanoparticles for real-time detection of specific analytes. The chemosensors show high selectivity and sensitivity in the detection of cations and biologic analytes and thus are potentially promising for applications in sensing assay system. In this review, recent sutdies on the design, synthesis and photo-physical properties of novel materials and construct of chemosensors are summarized with an emphasis on the development in our groups in recent years.

Anions Distorting Triggering Ferroelectricity in a Molecular Crystal

Recently,molecular ferroelectrics have attracted more and more attention due to their structural diversity,low cost of manufacture,and environmental-friendly processing.However,most of the design strategies for molecular ferroelectrics have focused on the selection and modification of cations,and the use of anions has been rarely reported.Here,introducing distorted[CuBr_(4)]^(2-) tetrahedra,we obtained a high curie temperature(T_(c))ferroelectric,[cyclopentylammonium]_(2)CuBr_(4),with a T_(c) as high as 393 K,and exceeding commercial and most of reported molecular ferroelectric BaTiO_(3)(393 K).Variable-temperature hysteresis loop shows the nonlinear P-E loop of the crystal under a wide temperature range.Variable-temperature single-crystal X-ray diffraction revealed that the Aizu expression can be written as mmmFmm2.In short,this work will inspire more creative strategies by exploiting the tunability of the anion module.

Chitosan-based self-healing hydrogel for bioapplications

By using an easily available PEG derivative and biopolymer chitosan, a self-healing hydrogel has been facilely prepared through the dynamic Schiff base. This biocompatible self-healing hydrogel can be used for drug-delivery, 3D cell culture and as a basic platform to develop some organic-inorganic biohybrids. This mini-review summarized recent research about that chitosan based self-healing hydrogel and related materials, and discussed some future bio-applications of that hydrogel