New families of mesoporous materials

Abstract

Mesoporous materials have been paid much attention in both scientific researches and practical applications. In this review, we focus on recent developments on preparation and functionalization of new families of mesoporous materials, especially non-siliceous mesoporous materials invented in our research group. Replica synthesis is known as the method to synthesize mesoporous materials composed of various elements using originally prepared mesoporous replica. This strategy has been applied for the syntheses of novel mesoporous materials such as carbon nanocage and mesoporous carbon nitride. Carbon nanocage has a cage-type structure with huge surface area and pore volume, which exhibits superior capabilities for biomolecular adsorption. Mesoporous carbon nitride was synthesized, for first time, by using mixed material source of carbon and nitrogen simultaneously. As a totally new strategy for synthesis of mesoporous materials, the elemental substitution method has been recently proposed by us. Direct substitution of component elements in original mesoporous materials, with maintaining structural regularity, provided novel mesoporous materials. According to this synthetic strategy, mesoporous boron nitride and mesoporous boron carbon nitride have been successfully prepared, for first time. In addition to these material inventions, hybridization of high functional materials, such as biomaterials, to mesoporous structure has been also developed. Especially, immobilization of proteins in mesopores was systematically researched, and preparation of peptidehybridized mesoporous silica was demonstrated. These new families of mesoporous materials introduced in this review would have high potentials in future practical applications in wide ranges from electronics and photonics to environmental and medical uses.     

New families of mesoporous materials

Mesoporous materials have been paid much attention in both scientific researches and practical applications. In this review, we focus on recent developments on preparation and functionalization of new families of mesoporous materials, especially non-siliceous mesoporous materials invented in our research group. Replica synthesis is known as the method to synthesize mesoporous materials composed of various elements using originally prepared mesoporous replica. This strategy has been applied for the syntheses of novel mesoporous materials such as carbon nanocage and mesoporous carbon nitride. Carbon nanocage has a cage-type structure with huge surface area and pore volume, which exhibits superior capabilities for biomolecular adsorption. Mesoporous carbon nitride was synthesized, for first time, by using mixed material source of carbon and nitrogen simultaneously. As a totally new strategy for synthesis of mesoporous materials, the elemental substitution method has been recently proposed by us. Direct substitution of component elements in original mesoporous materials, with maintaining structural regularity, provided novel mesoporous materials. According to this synthetic strategy, mesoporous boron nitride and mesoporous boron carbon nitride have been successfully prepared, for first time. In addition to these material inventions, hybridization of high functional materials, such as biomaterials, to mesoporous structure has been also developed. Especially, immobilization of proteins in mesopores was systematically researched, and preparation of peptide-hybridized mesoporous silica was demonstrated. These new families of mesoporous materials introduced in this review would have high potentials in future practical applications in wide ranges from electronics and photonics to environmental and medical uses.     

Lysozyme adsorption onto mesoporous materials: effect of pore geometry and stability of adsorbents

In this paper, adsorption of lysozyme onto two kinds of mesoporous adsorbents (KIT-5 and AISBA-15) has been investigated and the results on the effects of pore geometry and stability of the adsorbents are also discussed. The KIT-5 mesoporous silica materials possess cage-type pore geometry while the AISBA-15 adsorbent has mesopores of cylindrical type with rather large diameter (9.7 nm). Adsorption of lysozyme onto AISBA-15 aluminosilicate obeys a Langmuir isotherm, resulting in pore occupation of 25 to 30%. In contrast, the KIT-5 adsorbents showed very small adsorption capacities for the lysozyme adsorption, typically falling in 6 to 13% of pore occupation. The cage-type KIT-5 adsorbents have narrow channel (4 to 6 nm) where penetration of the lysozyme (3 x 3 x 4.5 nm) might be restricted. The KIT-5 adsorbent tends to collapse after long-time immersion in water, as indicated by XRD patterns, while the AISBA-15 adsorbent retains its regular structure even after immersion in basic water for 4 days. These facts confirm superiority of the AISBA-15 as an adsorbent as compared with the KIT-5 mesoporous silicates. This research strikingly demonstrates the selection of mesoporous materials is crucial to achieve efficient immobilization of biomaterials in aqueous environment.     

Adsorption performance of VOCs in ordered mesoporous silicas with different pore structures and surface chemistry

Ordered mesoporous silicas with different pore structures, including SBA-15, MCM-41, MCM-48 and KIT-6, were functionalized with phenyltriethoxysilane by a post-synthesis grafting approach. It was found that phenyl groups were covalently anchored onto the surface of mesoporous silicas, and the long-range ordering of the mesoporous channels was well retained after the surface functionalization. The static adsorption of benzene and the dynamic adsorption of single component (benzene) and bicomponent (benzene and cyclohexane) on the original and functionalized materials were investigated. As indicated by the adsorption study, the functionalized silicas exhibit improvement in the surface hydrophobicity and affinity for aromatic compounds as compared with the original silicas. Furthermore, the pore structure and the surface chemistry of materials can significantly influence adsorption performance. A larger pore diameter and cubic pore structure are favorable to surface functionalization and adsorption performance. In particular, the best adsorption performance observed with phenyl-grafted KIT-6 is probably related to the highest degree of surface functionalization, arising from the relatively large mesopores and bi-continuous cubic pore structure which allow great accessibility for the functional groups. In contrast, functionalized MCM-41 exhibits the lowest adsorption efficiency, probably owing to the small size of mesopores and 1D mesoporous channels.     

Synthesis of polyaniline-coated ordered mesoporous carbon and its enhanced electrochemical properties

Pore surface of ordered mesoporous carbon (OMC) was coated with a thin layer of polyaniline by chemical polymerization of aniline monomers. Structure characterizations, such as N₂ adsorption analysis, small angle X-ray diffraction and transmission electron microscopy, demonstrate that polyaniline is well distributed on the pore surface of OMC. As evidenced by constant current charge–discharge test, specific capacitance of polyaniline-coated ordered mesoporous carbon (PCOMC) reaches as high as 602.5 F/g, which is much higher than that of OMC, due to the incorporation of polyaniline onto the pore surface of OMC. However, the capacitive behavior deteriorated somewhat due to the narrowed pore size and extra faradiac reactions caused by the incorporation of polyaniline.     

The State of Research Regarding Ordered Mesoporous Materials in Batteries

Ordered mesoporous materials, porous materials with a pore size of 2–50 nm which are prepared via the sol–gel process using surfactant molecular aggregates as a template to assemble channels through the interfacial action of organic and inorganic substances, have recently triggered a heated debate. In addition to applications in the catalytic cracking of heavy oils and residues, the manufacturing of graft materials, the purification of water, the conversion of automobile exhaust, biochips, and the treatment of environmental pollutants via photocatalysts, ordered mesoporous materials have drawn substantial attention in the field of electrochemical energy storage due to advantages such as large specific surface area, uniform and continuously adjustable pore size, and orderly arrangement. Here, a general summary and appraisal of the study of ordered mesoporous materials for batteries in recent years is given, including the synthesis methods, meso/nanostructural features, and electrochemical capabilities of such materials.     

Ordered nanoporous polymer-carbon composites

Nanostructured organic materials, particularly those constructed with uniform nanopores, have been sought for a long time in materials science. There have been many successful reports on the synthesis of nanostructured organic materials using the so-called, 'supramolecular liquid crystal templating' route. Ordered nanoporous polymeric materials can also be synthesized through a polymerization route using colloidal or mesoporous silica templates. The organic pore structures constructed by these approaches, however, are lower in mechanical strength and resistance to chemical treatments than nanoporous inorganic, silica and carbon materials. Moreover, the synthesis of the organic materials is yet of limited success in the variation of pore sizes and structures, whereas a rich variety of hexagonal and cubic structures is available with tunable pore diameters in the case of the inorganic materials. Here we describe a synthesis strategy towards ordered nanoporous organic polymers, using mesoporous carbon as the retaining framework. The polymer-carbon composite nanoporous materials exhibit the same chemical properties of the organic polymers, whereas the stability of the pores against mechanical compression, thermal and chemical treatments is greatly enhanced. The synthesis strategy can be extended to various compositions of hydrophilic and hydrophobic organic polymers, with various pore diameters, connectivity and shapes. The resultant materials exhibiting surface properties of the polymers, as well as the electric conductivity of the carbon framework, could provide new possibilities for advanced applications. Furthermore, the synthesis strategy can be extended to other inorganic supports such as mesoporous silicas.     

球壳状纳米介孔腔内药物释放特性的分子动力学研究

有序纳米介孔材料的有序性、大的比表面积、孔道均匀等特性使其在药物装载、吸附、释放等方面得到广泛的应用。近年来研究者对介孔材料在药物控释方面的研究主要是通过材料制备、表征以及吸附药物后介孔材料的性能测试等几方面实现的。大多数报道都是采用实验的方法进行研究,关于模拟计算方面的研究很少,力场的选择更是模拟计算的一项挑战。依据介孔材料的独特结构构建了球壳状纳米介孔腔内药物分子释放模型,通过分子动力学的方法计算分析了药物分子的释放特性,重点考察了药物分子大小、溶液环境、介孔腔结构特征对其释放特性的影响。     

Mesoporous carbon nanosheets derived from tubular halloysite and furfuryl alcohol with different concentrations

Mesoporous carbon nanosheets with high surface areas and large total pore volumes were prepared using tubular halloysite as inorganic matrix and furfuryl alcohol (FA) as carbon precursor by a template-like method. Field emission scanning electron microscope, high-resolution transmission electron microscopy (HRTEM) and nitrogen adsorption analysis were employed to characterize the morphologies and pore structures of the samples. It is found that tunable mesoporous carbons can be obtained by adjusting FA volume concentration. Lowering FA concentration leads to an increase in the BET specific surface area and narrowing of the mesopore size distribution.     

介孔材料可控合成及在核工业中的应用研究进展

介绍了介孔材料可控合成方法及研究进展,综述了介孔材料在核工业中的应用,如用于放射性核素的吸附、分离和废物固化等,并对介孔材料控制合成和应用前景进行了展望。提出应对介孔材料进行孔道结构及形貌控制合成、修饰或功能化研究,制备具有短孔道特殊形貌的介孔材料,提高其吸附性能和选择性;寻求更经济可行的合成路线,降低介孔材料的生产成本,逐步实现产业化;深入研究可控合成机理及介孔材料对放射性核素的吸附机理。     

有机金属盐基介孔碳的制备及其电化学性能研究

以乙二胺四乙酸钙为原料,采用直接碳化法制备介孔碳电极材料。N2吸附测试表明,所制备的碳材料为典型的介孔材料,材料的比表面积随着碳化温度的升高而增加,平均孔径呈现先增加后减小的趋势。电化学测试表明,CaC-700、CaC-800和CaC-900具有优异的电化学电容特性,在较高的输出功率下仍能保持较高的能量密度,说明介孔表面在高功率输出时能够得到较充分的利用。这类介孔碳在对能量密度和功率密度都有较高要求的场合具有良好的应用前景。     

磁性多孔碳材料的研究进展

磁性多孔碳材料同时具有磁性和多孔性质,其拥有丰富的孔道结构、高的比表面积、高孔容、良好的活性位点和磁性可分离等优异的性能,可以很好的解决多孔碳材料在应用过程中难分离回收等问题,因此,磁性多孔碳材料已经在吸附领域得到广泛的应用。按照孔径大小、磁性强弱以及组合方式的不同将磁性多孔碳材料进行了分类,并综述了近年来磁性多孔碳材料的制备方法以及吸附应用,最后,对磁性多孔碳材料的应用前景进行了展望。     

同步合成模板炭化法制备双电层电容器电极用中孔炭材料的研究

以正硅酸乙酯为模板硅源，间苯二酚—甲醛凝胶为炭前驱体，采用同步合成模板炭化(SSTCM)法制备了具有可控结构的中孔炭材料。炭材料的比表面积可达1500m^2/g，平均孔径在3nm～10nm之间。经过酸催化水解预处理的二氧化硅模板前驱体溶液与间苯二酚—甲醛溶液混合，碱性条件下使两者的溶胶凝胶反应同步发生，得到有机，无机凝胶混合物。再经炭化、HF去模，制得SSTCM炭材料。N2等温吸脱附研究表明，与炭前驱体聚合物同步合成的结构可调的二氧化硅模板，导致了SSTCM炭材料可控中孔结构的形成。循环伏安研究表明，采用这种同步合成模板炭化法制备的SSTCM炭材料质量比容量达270F／g，炭材料具有的典型中孔结构使其可能成为一种理想的双电层电容器电极材料。     

2-Mercaptothiazoline modified mesoporous silica for mercury removal from aqueous media

Mesoporous silicas (SBA-15 and MCM-41) have been functionalized by two different methods. Using the heterogeneous route the silylating agent, 3-chloropropyltriethoxysilane, was initially immobilized onto the mesoporous silica surface to give the chlorinated mesoporous silica Cl-SBA-15 or Cl-MCM-41. In a second step a multifunctionalized N, S donor compound (2-mercaptothiazoline, MTZ) was incorporated to obtain the functionalized silicas denoted as MTZ-SBA-15-Het or MTZ-MCM-41-Het. Using the homogeneous route, the functionalization was achieved via the one step reaction of the mesoporous silica with an organic ligand containing the chelating functions, to give the modified mesoporous silicas denoted as MTZ-SBA-15-Hom or MTZ-MCM-41-Hom. The functionalized mesoporous silicas were employed as adsorbents for the regeneration of aqueous solutions contaminated with Hg (II) at room temperature. SBA-15 and MCM-41 functionalized with MTZ by the homogeneous method present good mercury adsorption values (1.10 and 0.7mmolHg (II)/g of silica, respectively). This fact suggests a better applicability of such mesoporous silica supports to extract Hg (II) from aqueous solutions. In addition, it was observed the existence of a correlation between mercury adsorption with pore size and volume since, SBA-15 with lower areas and higher pore sizes functionalized with sterically demanding ligands, show better adsorption capacities than functionalized MCM-41.     

In Vivo Bio‐Safety Evaluations and Diagnostic/Therapeutic Applications of Chemically Designed Mesoporous Silica Nanoparticles

The remarkable progress of nanotechnology and its application in biomedicine have greatly expanded the ranges and types of biomaterials from traditional organic material‐based nanoparticles (NPs) to inorganic biomaterials or organic/inorganic hybrid nanocomposites due to the unprecedented advantages of the engineered inorganic material‐based NPs. Colloidal mesoporous silica NPs (MSNs), one of the most representative and well‐established inorganic materials, have been promoted into biology and medicine, and shifted from extensive in vitro research towards preliminary in vivo assays in small‐animal disease models. In this comprehensive review, the recent progresses in chemical design and engineering of MSNs‐based biomaterials for in vivo biomedical applications has been detailed and overviewed. Due to the intrinsic structural characteristics of elaborately designed MSNs such as large surface area, high pore volume and easy chemical functionalization, they have been extensively investigated for therapeutic, diagnostic and theranostic (concurrent diagnosis and therapy) purposes, especially in oncology. Systematic in vivo bio‐safety evaluations of MSNs have revealed the evidences that the in vivo bio‐behaviors of MSNs are strongly related to their preparation prodecures, particle sizes, geometries, surface chemistries, dosing parameters and even administration routes. In vivo pharmacokinetics and pharmacodynamics further demonstrated the effectiveness of MSNs as the passively and/or actively targeted drug delivery systems (DDSs) for cancer chemotherapy. Especially, the advance of nano‐synthetic chemistry enables the production of composite MSNs for advanced in vivo therapeutic purposes such as gene delivery, stimuli‐responsive drug release, photothermal therapy, photodynamic therapy, ultrasound therapy, or anti‐bacteria in tissue engineering, or as the contrast agents for biological and diagnostic imaging. Additionally, the critical issues and potential challenges related to the chemical design/synthesis of MSNs‐based “magic bullet” by advanced nano‐synthetic chemistry and in vivo evaluation have been discussed to highlight the issues scientists face in promoting the translation of MSNs‐based DDSs into clinical trials.     

Generalized Access to Mesoporous Inorganic Particles and Hollow Spheres from Multicomponent Polymer Blends

Mesoporous inorganic particles and hollow spheres are of increasing interest for a broad range of applications, but synthesis approaches are typically material specific, complex, or lack control over desired structures. Here it is reported how combining mesoscale block copolymer (BCP) directed inorganic materials self‐assembly and macroscale spinodal decomposition can be employed in multicomponent BCP/hydrophilic inorganic precursor blends with homopolymers to prepare mesoporous inorganic particles with controlled meso‐ and macrostructures. The homogeneous multicomponent blend solution undergoes dual phase separation upon solvent evaporation. Microphase‐separated (BCP/inorganic precursor)‐domains are confined within the macrophase‐separated majority homopolymer matrix, being self‐organized toward particle shapes that minimize the total interfacial area/energy. The pore orientation and particle shape (solid spheres, oblate ellipsoids, hollow spheres) are tailored by changing the kind of homopolymer matrix and associated enthalpic interactions. Furthermore, the sizes of particle and hollow inner cavity are tailored by changing the relative amount of homopolymer matrix and the rates of solvent evaporation. Pyrolysis yields discrete mesoporous inorganic particles and hollow spheres. The present approach enables a high degree of control over pore structure, orientation, and size (15–44 nm), particle shape, particle size (0.6–3 µm), inner cavity size (120–700 nm), and chemical composition (e.g., aluminosilicates, carbon, and metal oxides).     

N-doped ordered mesoporous carbon spheres derived by confined pyrolysis for high supercapacitor performance

Herein, we report a confined pyrolysis strategy to prepare mesoporous carbon nanospheres by which surface area of carbon spheres is increased, pore size is enlarged and effective N-doping is achieved. In this method, the mesoporous polymer sphere as carbon precursor and 2-methylimidazole as nitrogen precursor are encapsulated in a compact silica shell which provides a confined nano-space for the pyrolysis treatment. The in situ generated gases from mesoporous polymer sphere and 2-methylimidazole under pyrolysis diffuse into the pores of mesoporous polymer sphere in the confined compact silica shell, resulting in increased surface area, larger pore size and N-doping due to self-activation effect. As electrodes in supercapacitor, the N-doped mesoporous carbon nanospheres exhibit a significantly enhanced specific capacitance of 326 F g⁻¹ at 0.5 A g⁻¹, which is 2 times higher than that of mesoporous carbon spheres under unconfined pyrolysis condition, exhibiting its potential for electrode materials with high performance.     

Immobilization of lysozyme onto pore-engineered mesoporous AISBA-15

In this research, hydrothermally stable mesoporous AISBA-15 materials have been used as adsorbents for systematic research on the lysozyme adsorption. Stability of the AISBA-15 adsorbents and the lysozyme molecules after the adsorption experiments for several days in aqueous solutions were confirmed by X-ray diffraction (XRD) measurement and FT-IR spectroscopy, respectively. The amount of the lysozyme adsorption can easily be controlled by the pore diameter and pore volume the mesoporous adsorbent, but an unreasonable effect of the surface area on the protein adsorption capacity was observed. The results of the effect of the pore diameter on the lysozyme adsorption suggest that the adsorption might partially be influenced by kinetically favorable edge-on type orientation on the confined mesopore. However, the final adsorption amount of the lysozyme can be well regenerated by models based on the side-on adsorption in dense packing. The present research also confirms the importance of appropriate "pore-engineering" for immobilization of bio-function on mesoporous materials.     

高性能超级电容器有序中孔炭材料的研制

采用微湿含浸法制备了一系列具有不同比表面积和孔径分布的超级电容器有序中孔炭材料。采用液氮吸附脱附等温线、小角XRD以及TEM表征了有序中孔炭的孔结构,在1MEt4NBF4|PC电解液中测试了其电化学性能。结果表明,所制得的有序中孔炭的BET比表面积随糠醇加入量的增加先增加后减小,糠醇加入量少制得具有CMK-5结构的有序中孔炭,加入量多制得的CMK-3结构。电化学性能测试结果表明,在1mA·cm-2的充放电电流密度下各有序中孔炭材料比电容的大小顺序与其BET比表面积的大小顺序基本一致,具有CMK-3结构的有序中孔炭的倍率性能最好,并且也好于无序中孔炭的。     

Carboxyl group functionalization of mesoporous carbon nanocage through reaction with ammonium persulfate

Carbon nanocage, a three dimensional cage type mesoporous carbon with very high surface area and pore volume, has been functionalized with carboxyl groups for the first time via a simple oxidation using ammonium persulfate solution (APS). The carboxyl groups functionalized carbon nanocage materials have been unambiguously characterized by various sophisticated instruments such as FT-IR, HRSEM-EDX, XRD, nitrogen adsorption, and HRTEM. The degree of carboxyl group functionalization has been controlled by the simple adjustment of the oxidation parameters such as oxidation time, APS concentration and oxidation temperature. FT-IR spectroscopy combined with the HRSEM-EDX has been used to provide a quantitative analysis of the carboxyl groups on the surface of the carbon nanocage materials before and after the APS treatment. In addition, the effect of the oxidation parameters on the structural order and the textural parameters of the carbon nanocage materials has been studied. It has been found that the role of oxidation parameters is highly critical to obtain carbon nanocage materials with a high density of carboxyl groups without affecting the structural order and the pore parameters. Thus, the reaction parameters have been carefully optimized and the best condition for the preparation of carboxyl group functionalized carbon nanocage with well-ordered structure has been proposed.