溶胶-凝胶法制备生物活性有机-无机杂化材料的研究进展

已经应用于临床的骨修复材料主要是生物活性陶瓷和金属如钛及其合金制成的生物材料,它们能与生物骨结合但与人体松质骨相比弹性模量高且柔韧性较低。需要研究一种具有与天然生物骨相类似力学性能的生物活性材料。目前已通过溶胶-凝胶法分别用PDMS、明胶、MPS及PTMO与无机系统合成了生物活性的有机-无机杂化材料,材料通过在有机基体中引入Ca2+和特殊的功能化基团如Si—OH等获得生物活性。其今后主要发展方向在于有机成分的引入以达到最佳的柔韧性和力学强度以及作用机理的研究以提高生物活性。

二氧化硅基有机-无机防腐蚀杂化膜的制备及性能

传统的钢铁表面覆膜技术如磷化、铬酸盐钝化等污染严重,硅烷化和有机-无机杂化涂层用于金属预处理则具有耐温、耐腐蚀等优点,又利于环保。以正硅酸乙酯、γ-氨丙基三乙氧基硅烷为原料,采用溶胶-凝胶法制备了SiO2基有机-无机杂化材料。通过红外光谱对不同温度处理的杂化材料进行了分析,以差示扫描量热法研究了杂化材料在不同温度下的吸放热反应,结合对杂化溶胶涂覆于钢铁基体表面形成涂层的塔菲尔曲线分析,对杂化膜的保护性能进行了研究。结果表明:涂层试样在N2气氛下300℃热处理,可以保证涂层中Si-O-Si键等最大程度地键合,并有效保留了有机组分,从而有利于保证杂化材料涂层的完整性,较大地提高了基体钢铁的耐腐蚀性能,可作为金属表面涂装处理工序中良好的中间过渡层。

硅烷偶联剂对硅溶胶及其膜层表面开裂性的改性效果

为了改善硅溶胶膜层的开裂性,使用甲基三氧甲基硅烷和KH-570 2种硅烷偶联剂对硅溶胶正硅酸乙酯进行改性。比较了2种偶联剂对硅溶胶膜层的影响,应用金相显微观察、傅立叶红外光谱(FT-IR)、扫描电镜观察等系统研究了偶联剂KH-570对硅溶胶及其膜层的改性效果。结果表明:2种硅烷偶联剂都可以明显减少膜层的裂纹,使其表面更加平整;在同样的用量下,偶联剂KH-570对减少涂层表面裂纹的效果更加明显;加入KH-570偶联剂的硅溶胶体系内由于生成了有机-无机杂化的网络结构而有效地减缓了膜层开裂性,提高了其耐蚀性能。

Synthesis and characterization of hybrid organic-inorganic materials based on EA-MAn-APTES and silica

Poly (EA-MAn-APTES)/silica hybrid materials were successfully prepared fromEthyl acrylate (EA), maleic anhydride (MAn) and tetraethoxysilane (TEOS) in the presence of acoupling agent 3-aminopropyltriethoxysilane (APTES),by free-radical solution polymerization and insitu sol-gel process. The mass fraction of TEOS varied from 0 to 25%. The hybrid materials werecharacterized by the methods of FT-IR spectra, solvent extraction, scanning electron microscope (SEM), transmission electron microscope (TEM), differential scanning calorimetry (DSC) andthermogravimetric analysis (TGA) measuring apparatus to get their structures, gel contents,morphologies, particle sizes and thermal performances. The results show that the covalent bonds arebetween organic and inorganic phases, gel contents in the hybrid materials are much higher, theSiO_2 phase is well dispersed in the polymer matrix, silicon dioxide exist at nanoscale in thecomposites and have excellent thermal stability.

Effect of cerium ion(Ⅲ) on corrosion resistance of organic-inorganic hybrid coating on surface of aluminum-tube used in refrigeration equipment

Organic?inorganic hybrid coating on the surface of aluminum-tube used in refrigeration equipment using cerium ion (III) as the additive was fabricated by sol?gel method, and the structure of the coating was confirmed by FT-IR. The results of the characterization show that the corrosion resistance of the coating with 1.5 mmol/L cerium ion (III) gains significant improvement, in which the colour retention time of CuSO4 extends to 500 s, the anti-acid and alkali corrosion rates reduce by 67% and 70% compared with the blank one, respectively, and the salt spray tests also show good corrosion resistance. The electrochemical tests demonstrate that the self-corrosion current density and potential of the sample with hybrid coating are about 2.877×10?7 A/cm2 and?0.550 V, respectively. The metallographic and SEM images show that the hybrid coating is uniform and dense, and the EDS analysis confirms that the coating is mainly composed of Al, Si and Ce elements.

Inorganic-organic hybrid photocatalysts:Syntheses,mechanisms,and applications

Inorganic-organic hybrid materials are promising for application in the field of photocatalysis because of their excellent properties.Therefore,their syntheses,mechanisms,and applications are reviewed in this paper.First,we introduce the role of inorganic-organic photocatalysts,their advantages and disadvantages,and their design principles.Second,we present the top-down and bottom-up synthesis methods of the hybrid materials.The interaction between inorganic and organic components in hybrid materials is discussed,followed by how to improve inorganic-organic photocatalysts.Third,the applications of hybrid materials in the field of photocatalysis,such as realizing hydrogen evolution,organic pollutant degradation,heavy metals and CO_(2) reduction,sterilization,and nitrogen fixation,are examined.Finally,the application prospects and development directions of inorganic-organic hybrid materials are explored and the unsolved problems are described.

Synthesis and Characterization of Poly(St-co-BA) Latex with an Organic-Inorganic Hybrid Compound as Emulsifier

A poly (St-co-BA) latex was successfully synthesized by using an organic-inorganic hybrid compound (OIHC), an aliphatic carboxylate sodium/nano-silica composite, as the emulsifier, and investigated by particle size analyzer, transmission electron microscope (TEM), optical contact angle measurement (OCA) and dynamic mechanical analyzer (DMA). It was found that the protective agent, sodium polyacrylate (PA),could obviously improve the polymerization stability and the functional monomer, glycidyl methacrylate (GMA), could enhance the store stability of the latex. The particle size of poly(St-co-BA) latex decreased and then leveled off as OIHC content increased. TEM shows that the prepared polymers were actually organic-inorganic nanocomposites, and these films have better waterproof property than those prepared by traditional poly(St-co-BA) latex or organic silicone modified poly(St-co-BA) latex. The nanocomposite polymer has much higher glass transition temperature than organic silicone modified poly(St-co-BA) polymer containing the same organic silicone content.

Layered Double Hydroxide Modified by PEGylated Hyaluronic Acid as a Hybrid Nanocarrier for Targeted Drug Delivery

In recent years, organic-inorganic hybrid nanocarriers are explored for effective drug delivery and preferable disease treatments. In this study, using 5-fluorouracil(5-FU)as electronegative model drug, a new type of organic-inorganic hybrid drug delivery system(LDH/HA-PEG/5-FU)was conceived and manufactured by the adsorption of PEGylated hyaluronic acid(HA-PEG)on the surface of layered double hydroxide(LDH, prepared via hydrothermal method)and the intercalation of 5-FU in the interlamination of LDH via ion exchange strategy. The drug loading amount of LDH/HA-PEG/5-FU achieved as high as 34.2%. LDH, LDH/5-FU and LDH/HA-PEG/5-FU were characterized by FT-IR, XRD, TGA, laser particle size analyzer and SEM. With the benefit of p Hdegradable feature of LDH and enzyme-degradable feature of HA, LDH/HA-PEG/5-FU showed p H-degradable and enzyme-degradable capacity in in vitro drug release. Moreover, the drug carrier LDH/HA-PEG contained biocompatible PEG and tumor-targeted HA, resulting in lower cytotoxicity and better endocytosis compared with LDH in vitro. It was suggested that the organic-inorganic hybrid drug delivery system, which was endowed with the properties of controlled release, low toxicity and tumor-targeting delivery for ameliorative cancer therapy, was advisable and might be applied further to fulfill other treatments.

Preparation and Characterization of Hybrid Aqueous Dispersions Composed of Silica Sol and Poly(styrene-co-acrylate)

A stable silica sol with 3-5 nm in diameter, which can form homogeneous film without crack, was prepared and characterized. Then, the inorganic-organic hybrid aqueous dispersion composed of such a silica sol and an emulsion of styrene （St） and acrylate （Ac） copolymer was prepared and the hybrid effect between the silica sol and poly（St-co-Ac） was observed by Fourier transform infra-red （FT-IR） spectroscope. The toughness of the film prepared by this kind of hybrid aqueous dispersion was excellent, as it was enhanced appreciably by commixing with a small amount of poly（St-co-Ac） emulsion. Some amino-polysiloxane modified hybrid aqueous dispersions were also prepared and the properties of the modified dispersions and their films were investigated. The experimental results showed that the film prepared with such an amino-polysiloxane modified hybrid dispersion exhibited excellent hydrophobicity and low surface energy after heat treatment for 1.5 h, during which the formation of the graft copolymer was observed. The surface energy of this film decreases as a result of the enrichment of siloxane segments on the film surface.

Aromatic bromination with hydrogen production on organic‐inorganic hybrid perovskite‐based photocatalysts under visible light irradiation

Aromatic bromides are important chemicals in nature and chemical industries.However,their tra‐ditional synthesis routes suffer from low atomic economy and pollutant formation.Herein,we show that organic-inorganic hybrid perovskite methylammonium lead bromide(MAPbBr_(3))nanocrystals stabilized in aqueous HBr solution can achieve simultaneous aromatic bromination and hydrogen evolution using HBr as the bromine source under visible light irradiation.By hybridizing MAPbBr_(3) with Pt/Ta_(2)O_(5) and poly(3,4‐ethylenedioxythiophene)polystyrene sulfonate as electron‐and hole‐transporting motifs,aromatic bromides were achieved from aromatic compounds with high yield(up to 99%)and selectivity(up to 99%)with the addition of N,N‐dimethylformamide or its analogs.The mechanistic studies revealed that the bromination proceeds via an electrophilic attack pathway and that HOBr may be the key intermediate in the bromination reaction.

Crystallographic Characterization of the Novel Inorganic-organic Hybrid Coordinated Polymer: [(C_(22)H_(50)N_2)(Ag_2I_4)]_n

A novel coordinated polymer [(C22H50N2)(Ag2I4)]n([C22H50N2]2+ = N,N?-1,2- ethylence-bis(N,N?-dimethyl octane ammonium) (EDO)) was synthesized by the reaction of AgI and EDO at room temperature with pH = 6.8, and structurally characterized by means of X-ray single- crystal diffraction. It crystallizes in triclinic, space group P1 with a = 9.6080(1), b = 12.7643(2), c = 7.2157(8) ? a = 100.835(8), ?= 91.030(3), ? = 91.297(9)o, (C21.50H48.50Ag2I4N2), Mr = 1058.46, V = 868.71(19) 3, Z = 1, Dc = 2.023g/cm3, F(000) = 497.5, ?MoKa) = 4.692 mm-1, the final R = 0.0623 and wR = 0.1949 for 2641 observed reflections with I > 2s(I). The title compound consists of cations ([C22H50N2]2+) and anion chain (Ag2I42-)∞ which are combined by static attracting forces in the crystal to form the so-called organic-inorganic hybrid material.

Polarized Electronic Spectra of Organic/Inorganic Hybrid Materials of Chiral Schiff Base Ni（ll） or Cu（ll） Complexes and Disperse Red 1 or Azobenzene in PMMA Films

We have prepared new chiral Schiff base complexes, and copper（Ⅱ） （2） to investigate steric effect of ligands for 1 and bis（N-R-l-phenylethyl-5- methoxysalicydenaminato） nickel（Ⅱ） （1） 2 and known bis（N-R-l-phenylethyl-3,5-dichlorosalicydenaminato） nickel（Ⅱ） （3） and copper（Ⅱ） （4）. By using two kinds of photochromic dyes, disperse red 1 （DRI） and azobenzene （AZ）, we investigated the efficiency of increasing optical anisotropy of organic/inorganic hybrid materials of 1 through 4＋AZ or DRI＋PMMA in polymethylmethacrylate （PMMA） cast films by Weigert effect （and compared with cis-trans isomerization by alternate UV and visible light for 3 and 4 to previous study）. Gradual increase of optical anisotropy was observed for all the hybrid materials regardless of flexibility of Schiff base complexes, and the degree of dichroism and weak intermolecular interactions were discussed based on polarized absorption electronic spectra.

Charge Localization Induced by Reorientation of FA Cations Greatly Suppresses Nonradiative Electron-Hole Recombination in FAPbI3 Perovskites:a Time-Domain Ab Initio Study

Recent experiments report the rotation of FA(FA=HC[NH2]2+)cations significantly influence the excited-state lifetime of FAPbI3.However,the underlying mechanism remains unclear.Using ab initio nonadiabatic(NA)molecular dynamics combined with time-domain density functional simulations,we have demonstrated that reorientation of partial FA cations significantly inhibits nonradiative electron-hole recombination with respect to the pristine FAPbI3 due to the decreased NA coupling by localizing electron and hole in different positions and the suppressed atomic motions.Slow nuclear motions simultaneously increase the decoherence time,which is overcome by the reduced NA coupling,extending electron-hole recombination time scales to several nanoseconds and being about 3.9 times longer than that in pristine FAPbI3,which occurs within sub-nanosecond and agrees with experiment.Our study established the mechanism for the experimentally reported prolonged excited-state lifetime,providing a rational strategy for design of high performance of perovskite solar cells and optoelectronic devices.

席夫碱Mo(VI)功能化介孔SiO2的制备及其催化烯烃环氧化研究

采用共缩聚法制备有机-无机杂化材料,以介孔SiO_2材料为载体,分别嫁接席夫碱配体和配位乙酰丙酮钼,得到Mo(VI)席夫碱修饰的介孔SiO_2(Mo-SB-Cl-SiO_2-0.5-1).所制备的材料采用XRD,SEM,N2吸附-脱附和TEM技术对其结构进行了表征.考察了Mo-SB-Cl-SiO_2-0.5-1催化液相烯烃环氧化性能,结果表明:Mo-SB-Cl-SiO_2-0.5-1催化剂对烯烃环氧化具有高的转化率和优良的催化活性.与后嫁接法制备的催化剂相比,Mo-SB-Cl-SiO_2-0.5-1催化剂催化活性得到明显提高,催化环己烯环氧化的转化率和选择性分别为85%和>99%.在不同烯烃的研究中,环辛烯具有最高的转化率和选择性,分别为87%和>99%.催化剂重复使用4次后,环己烯的转化率没有明显下降,选择性仍然高达98%,表明Mo-SB-Cl-SiO_2-0.5-1具有较好的催化稳定性.

Two-dimensional organic-inorganic hybrid perovskite: from material properties to device applications

The two-dimensional（2D） perovskite（including pure-2D and quasi-2D） is formed by introducing large-group ammonium halides into conventional bulk perovskite. In the past twenty years, 2D perovskite materials were widely developed with the enriched species and advanced physicalknowledge in material characteristics as well as optoelectronic device applications. To review achievments in 2D perovskite,the fundamental mechanism and properties of 2D perovskite are introduced to offer insight into device performance.Moreover, the preparation methods of 2D perovskite films are summarized and compared. The latest successful applications of the 2D perovskite in the solar cells and light-emitting diodes fields, especially the advanced stability of 2D perovskite solar cells（PeSCs） and the efficient 2D perovskite lightemitting diodes（PeLEDs）, are also achieved. Furthermore, the challenges and outlook of 2D perovskite materials are proposed.

Inorganic cesium lead halide CsPbX_3 nanowires for long-term stable solar cells

ABX3-type organic-inorganic hybrid halide perovskite materials have been recognized as promising candidates for optoelectronic applications. However, poor stability of organic-inorganic hybrid perovskite hinders their forward long-term utilization and hence an effective strategy is needed to replace the organic part with an inorganic cation. Herein, all inorganic CsPbI3 nanowires with a di- ameter of 50-100 nm are synthesized on fluorine-doped tin oxide glass via a simple solution-dipping process, which are further transformed into CsPbBr3 nanowires through a so- lution-phase halide exchange method. A phase change from non-perovskite to perovskite structure is observed during the ion substitution process of I- by Br-, which is elaborated by X-ray diffraction, absorption and photoluminescence spectra. We for the first time apply the as-formed CsPbI3 and CsPbBr3 nanowires into perovskite solar cells, yielding power conversion efficiency of 0.11% and 1.21%, respectively. The inorganic CsPbBr3 nanowire solar cell shows impressive sta- bility which still remains 99% of the initial power conversion efficiency even after 5500 h aging.

Directing nucleation and growth kinetics in solution-processed hybrid perovskite thin-films

A heightened understanding of nucleation and growth mechanisms is paramount if effective solution processing of organic-inorganic perovskite thin-films for optoelectronic applications is to be achieved. Many fabri- cation techniques have been utilized previously to develop high-performance perovskite layers but there remains an absence of a unifying model that describes accurately the formation of these materials from solution. The present study provides a thorough analysis of nucleation and growth kinetics underpinning the development of hybrid organic-in- organic perovskite thin-films. Through precise control of the perovskite growth conditions the spacing of heteroge- neous nucleation sites was varied successfully from several hundred nanometers to several hundred microns. The crystalline regions surrounding these nuclei were found to comprise clusters of highly-oriented crystal domains exceed- ing 100 pm in diameter. However, no beneficial correlation was found between the size of these well-oriented grain-clus- ters and the optoelectronic performance. The formation of the perovskite microstructure features characteristics of both classical and non-classical growth mechanisms. The insights into perovskite thin-film growth developed by the present study provide clear implications for the development of future hybrid perovskite microstructures.

Transition metal oxides as hole-transporting materials in organic semiconductor and hybrid perovskite based solar cells

Organic polymer solar cells （OSCs） and organic-inorganic hybrid perovskite solar cells （PSCs） have achieved notable progress over the past several years. A central topic in these fields is exploring electronically efficient, stable and effective hole-transporting layer （HTL） materials. The goal is to enhance hole-collection ability, reduce charge recombination, increase built-in voltage, and hence improve the performance as well as the device stability. Transition metal oxides （TMOs） semiconductors such as NiOx, CuOx, CrOx, MoOx, WO3, and V2O5, have been widely used as HTLs in OSCs. These TMOs are naturally adopted into PSC as HTLs and shows their importance. There are similarities, and also differences in applying TMOs in these two types of main solution processed solar cells. This concise review is on the recent developments of transition metal oxide HTL in OSCs and PSCs. The paper starts from the discussion of the cation valence and electronic structure of the transition metal oxide materials, followed by analyzing the structure-property relationships of these HTLs, which we attempt to give a systematic introduction about the influences of their cation valence, electronic structure, work ftmction and film property on device performance.

A novel organic-inorganic hybrid monolith for trypsin immobilization

In proteomics, attention has focused on various immobilized enzyme reactors (IMERs) for the realization of high throughput digestion. In this report, a novel organic-inorganic hybrid monolith based IMER was prepared in a 100 μm i.d. capillary with 3-glycidoxypropyltrimethoxysilane (GLYMO) as the monomer and tetraethoxysilane (TEOS) as the crosslinker. Trypsin immobilization was achieved via the reaction between vicinal diol groups, which were obtained from hydrolysis of epoxy groups, and the amino groups of trypsin. Bovine serum albumin was digested thoroughly by this IMER in 47 s. After micro-reverse phase liquid chromatography-tandem mass spectrometry (μRPLC-MS/MS) analysis and database searching, beyond 35% sequence coverage was obtained, and the result was comparable to that of 12 h in solution digestion. The present IMER has potential for high throughput digestion.

Flexible organic-inorganic hybrid photodetectors with n-type phenyl-C61-butyric acid methyl ester （PCBM） and p-type pearl-like GaP nanowires

Flexible photodetectors have become a focus of current researches because they may offer some unique applications in various new areas that require flexible, lightweight, and mechanical shock-resistive sensing elements. In this work, we designed flexible organic-inorganic hybrid photodetectors on various flexible substrates, including polyethylene terephthalate （PET）, common Sellotape and polydimethylsiloxane （PDMS）, with n-type phenyl-C61-butyric acid methyl ester （PCBM） and p-type pearl-like GaP nanowires （NWs） as the active materials. The as-fabricated hybrid devices exhibited an optimized performance superior to the device made of pristine GaP NWs, with a fast response time （43 ms） and high on/off ratio （-170）. Under different bending conditions, the flexible hybrid photodetectors demonstrated excellent flexibility and electrical stability, which make them very promising for further large-scale, high sensitivity and high speed photodetector applications.