Chemical Physics Letters 510 (2011) 113

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Chemical Physics Letters

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FRONTIERS ARTICLE

Magnetically responsive ordered mesoporous materials: A burgeoning family of functional composite nanomaterials
Yonghui Deng, Yue Cai, Zhenkun Sun, Dongyuan Zhao
Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials and Advanced Materials Laboratory, Fudan University, Shanghai 200433, PR China

a r t i c l e

i n f o

a b s t r a c t
Magnetic mesoporous materials, as a family of novel functional nanomaterials, have attracted increasing attention due to their unique properties. Much work has been done to synthesize these materials and to explore applications in various elds, such as catalysis, separation, hyperthermia, drug delivery, and MR imaging. This Letter reviews the synthesis approaches, which can be grouped into three categories, i.e. solgel coating, post-loading, and nanocasting approaches. Emphasis is placed on the elucidation of the design principles, synthesis strategies and the propertiesapplications relationship of the mesoporous materials. 2011 Elsevier B.V. All rights reserved.

Article history: Available online 3 May 2011

1. Ordered mesoporous materials Ordered mesoporous materials are a type of porous molecular sieves with pore size of 2.050 nm which are aligned in 2-D or 3D arrays throughout the materials. In this article, unless otherwise specied, mesoporous materials refer to ordered mesoporous materials. Retrospectively, the research interest in mesoporous materials originated from conventional zeolites and molecular sieves possessing ordered micropores (<2.0 nm) in the early 1990s when scientists were pursuing systems with large pores for heavy petroleum oil conversion. Since their discovery [1,2], mesoporous materials have stimulated a great interest among various elds spanning chemistry, materials science, biomedicine, and bioengineering. The extensive research has been carried out due to their unique features, including tunable pore size, high surface area, large pore volume, and controllable framework composition, which endow them with great application potential in elds such as catalysis, adsorption, separation, fuel cell, sensor, enzyme immobilization, electrode materials [39]. Therefore, considerable effort has been devoted to synthesis, structure analysis, as well as
Abbreviations: APS, c-aminopropyltriethoxysilane; BET, BrunauerEmmett Teller; BTME, 1,2-bis(trimethoxysilyl)ethane; CTAB, cetyltrimethylammonium bromide; CTAC, cetyltrimethylammonium chloride; C18TMS, n-octadecyltrimethoxysilane; 2-D, two-dimensional; 3-D, three-dimensional; EG, ethylene glycol; EISA, evaporation induced self-assembly; FESEM, eld-emission scanning electron microscopy; FETEM, eld-emission transmission electron microscopy; MRI, magnetic resonance imaging; NIR, near infrared; OTAB, octadecyl-trimethylammoniumbromide; PEG, poly(ethylene glycol); PMO, periodic mesoporous organosilica; P123, poly(ethylene oxide)b-poly(propylene oxide)b-poly(ethylene oxide) (EO20PO70EO20); SEM, scanning electron microscopy; TEM, transmission electron microscopy; TEOS, tetraethyl orthosilicate; XRD, X-ray diffraction. Corresponding author. E-mail address: dyzhao@fudan.edu.cn (D. Zhao). 0009-2614/$ - see front matter 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.cplett.2011.04.093

applications, which led to an exponential increase in publications within the past decades (Figure 1), and the production of a large number of mesoporous materials with varying chemical compositions and pore structures. The synthesis approaches for mesoporous materials can be basically categorized into two groups, soft- and hard-templating. The former usually relies on the use of surfactant molecules or amphiphilic block copolymers as templates. The template molecules interact with framework precursors and cooperatively assemble into hybrid composites with ordered mesostructures (Figure 2A). After co-solidication, the template molecules in the mesostructured composites can be removed by calcination or solvent extraction, giving rise to the mesoporous materials. The latter approach is usually realized through casting the pre-synthesized mesoporous materials as hard-templates with various guest precursors, in situ conversion of them into the target species in the mesopore channels, and nally removal of the hard templates through either chemical dissolution or combustion (Figure 2B). Using the two synthesis methods, continuous progresses have been achieved in mesoporous materials through various strategies, including solution-phase self-assembly [1,2,1013], solvent evaporation induced self-assembly (EISA) and nanocasting [1420]. And with the ever advancing characterization techniques, such as Cryo-TEM, 3-D electron tomography, researchers are now able to precisely elucidate the pore structures, features, and related parameters and understand formation mechanism of mesoporous materials. 2. Magnetic nanomaterials and magnetic mesoporous materials With the rapid progress in modern nanoscience and nanotechnology, mesoporous materials as a family of unique nanomaterials, have garnered increasing interest in elds, including chemistry,

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Figure 1. Increase in the number of publications on mesoporous materials from years 19852009. Source, ISI; keyword, mesoporous materials.

materials science, and biomedicine. Recently, functionalization of mesoporous materials with novel physical and chemical properties has emerged as one of the new research directions in the community of porous materials. Various approaches have been developed to integrate functional nanomaterials (quantum dots [21], magnetic nanoparticles [22], plasmonic metal nanorods [23]) within mesoporous materials, resulting in a great variety of functional materials that combine their excellent properties. Magnetic nanoparticles have received considerable attention in the past several decades due to their unique magnetic properties and potential applications in magnetic uid, data storage, catalysis, biotechnology/biomedicine, magnetic resonance imaging, and environmental remediation [2433]. Different methods have been developed for synthesis of magnetic nanoparticles, including chemical co-precipitation, thermal decomposition, solvothermal synthesis and so on [3439]. Combination of magnetic

nanoparticles and mesoporous materials is undoubtedly of a great interest to the development of novel functional materials, because the magnetic nanoparticles can provide unique magnetic properties that are very useful for the applications in catalysis, drug delivery, cell and tissue imaging, hyperthermal therapy and so on. Several excellent review articles have been reported about the synthesis and applications of functionalized mesoporous materials [4047], including magnetic mesoporous materials [40]. In this review, we mainly focus on the elucidation of the design principles and synthesis strategies of magnetic mesoporous materials. Generally, the magnetic components in the magnetically responsive mesoporous materials are magnetic metals or alloys (e.g. Fe, Co, Ni, or PtFe) or oxides such as MFe2O4 (M = Fe, Co, Ni, Zn, etc.) and c-Fe2O3. Because of their low toxicity [48], iron oxide nanoparticles have been widely used in the synthesis of magnetic composite materials. From a viewpoint of their practical applications, magnetic mesoporous composites should meet several criteria as follows. Firstly, the magnetic components should be free from being etched in application media, which is important to maintenance of their magnetic property. Secondly, for application in magnetic separation, the magnetic mesoporous materials should possess saturation magnetization (Ms) enough to ensure a rapid response to the applied magnetic eld. Thirdly, the mesopores should be accessible so that the high surface area and large pore volume can be used for the applications. Besides, superparamagnetism is usually highly desired, because it can prevent the magnetic composite particles from irreversible aggregation and ensure an excellent dispersibility once applied magnetic eld is removed. While for some biorelated applications, such as MRI contrast-enhancing agent and drug delivery, the materials should have high water dispersibility, uniform size, biocompatible surface and low cytotoxicity. To date, extensive work has been done in pursuit of magnetic mesoporous materials with desired structure, morphology, and surface property for diverse applications. The synthesis approaches for magnetic mesoporous materials can be grouped into three categories. The rst one is the solgel coating method that is based on encapsulation of magnetic particles with mesoporous shells using surfactants, amphiphilic block

Figure 2. Two approaches to synthesis of mesoporous materials: (A), soft-templating; (B), hard-templating synthesis.

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copolymers or organosilanes as templates [4968]. The second one is post-loading method based on either direct introduction of magnetic nanoparticles into the pre-synthesized mesoporous materials or impregnation with a precursor solution followed by in situ conversion of the precursor into magnetic nanoparticles [6975]. The third method is co-nanocasting which features the replication of mesoporous materials (e.g. mesoporous silica SBA-15) with a magnetic nanocomposite by using hard-templating synthesis strategy [7682]. In general, guest species and magnetic nanoparticle precursors (usually metal salts or organometallic compounds) are employed to ll the pore channels of mesoporous material templates and then in situ converted into magnetic nanoparticles, and after removal of the templates, magnetic mesoporous materials can be obtained. Using these methods, magnetic mesoporous materials with different morphologies, including particles [49], spheres [50,56,65], and rods [61], have been synthesized and applied for separation, bioimaging, hyperthermal therapy [64], drug delivery [67]and so on [40]. 2.1. Solgel coating approach Solgel process is a versatile approach to coat target objects (nanoparticles, thin lms, nanowires) with silica, metal oxides or polymers and create functional nanocomposites with pre-designed nanostructures. It features the hydrolysis and condensation of precursors and deposition of the precipitated nanosized oligomers on the objects of interest. In the synthesis of magnetic mesoporous materials, hydrolyzed precursors (e.g. TEOS) and surfactants, i.e. the templates, co-assemble into composite micelles through electrostatic interaction. As the hydrolysis and condensation proceed, the composite micelles aggregate, precipitate from the solution, and deposit on the magnetic particles (or protected magnetic particles, e.g. silica-coated magnetite), forming an ordered mesostructured layers. The subsequent removal of surfactants by calcination or solvent extraction results in coreshell composites with magnetic cores and mesopore shells. Obviously, the key to the successful coating process is to achieve a heterogeneous nucleation of mesostructures on the magnetic particles, namely precipitation

of the mesostructured composites preferably on magnetic particles. This preferable coating process is directly related to the surface chemistry of magnetic particles, i.e. their afnity toward the template molecules and coating species (e.g. silica). Usually, the common magnetic iron oxide particles are hydrophilic and have an isoelectric point (IEP) at around pH 7.0 [37]. For magnetite, the IEP is at pH 6.8. Therefore, in a basic solution for growth of mesoporous silica shell, magnetite particles can adsorb cationic CTAB molecules which can also interact with silica species through electrostatic interaction, and thus becoming the preferred location for depositing mesostructured composites (Figure 3a). Hydrophobic magnetic nanoparticles synthesized via a high-temperature reaction are usually stabilized by hydrophobic capping agents (e.g. oleic acid) and can be readily converted into hydrophilic nanoparticles by adsorption of CTAB molecules through hydrophobic hydrophobic interaction, and the bimolecular layer stabilized magnetic nanoparticles can serve as nucleation seeds for growth of mesostructured composite layer (Figure 3b). Based on these two solgel routes, lots of magnetic mesoporous materials have been synthesized by using different strategies, such as basic alcoholic solution, and inverse-microemulsion. The combination of magnetic particles with mesoporous materials through solgel coating method was rst reported by Xu and coworkers. [49] In this work, commercial magnetite particles ($3 lm in diameter) was rst coated with a dense silica through a solgel process using sodium silicate as a precursor in a basic aqueous solution. Afterward, the particles were coated by an assembled layer of CTAC through electrostatic interaction by soaking in the surfactant solution, and the resulting surfactant modied magnetite@silica particles were used as seeds for further coating growth of mesoporous silica shells through the Stber method, and after calcination in nitrogen, mesoporous magnetitesilica composite particles with mesopores of $2.5 nm and BET surface area of $52.3 m2/g were nally obtained. However, because the commercial magnetites with large ferromagnetic particles and poor water dispersibility were used for the solgel coating process, the obtained mesoporous magnetitesilica composites showed irregular morphology and ill-dened mesostructure and were easy

Figure 3. Surfactant-mediated solgel coating approach to magnetic mesoporous materials using hydrophilic (a) or (b) hydrophobic magnetic nanoparticles.

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to aggregate. Additionally, the calcination to remove CTAC templates could inevitably sinter the silica-coated magnetic particles and caused an irreversible aggregation of the magnetic mesoporous materials. Recently, we demonstrated a facile synthesis of magnetic mesoporous silica microspheres with well-dened coreshell structure through the surfactant involved solgel process (Figure 4a) [50]. Hydrophilic magnetite particles with excellent water dispersibility were rst synthesized through a solvothermal reaction and further coated by a layer of condensed silica through Stber method to produce the coreshell Fe3O4@nSiO2 microspheres. By using CTAB as a template, a uniform shell of CTAB/SiO2 mesostructured composite was further deposited on the Fe3O4@nSiO2 microspheres, resulting in the Fe3O4@nSiO2@CTAB/SiO2 composites. Finally, CTAB templates were removed by acetone extraction, and magnetic mesoporous silica microspheres (Fe3O4@nSiO2@mSiO2) with unique sandwich structure were obtained. The successful synthesis was veried the successive electron microscopy characterizations (Figure 4be). The sandwich structure and unique perpendicular alignment of pore channels in the porous silica shell can be clearly visible in the high-magnication TEM images (Figure 4d and e). Notably, since the surfactant was removed by a mild solvent extraction, the obtained magnetic mesoporous silica microspheres can be easily dispersed in aqueous solution, which is important for their practical applications (e.g. drug delivery). The mesoporous silica microspheres have high saturation magnetization of 53.3 emu/ g and rapid response to applied magnetic eld due to the large mass fraction of magnetite. Owing to their high surface area ($365 m2/g) and large pore volume ($0.29 cm3/g), the magnetic mesoporous silicas exhibit excellent adsorption performance in uptake of microcystins in water with a removal efciency of up to 97%. More recently, we synthesized coreshell multi-functional mesoporous microspheres by incorporation of metal nanoparticles between the magnetic core and mesoporous silica shell [51]. The idea for designing this multifunctional mesoporous material is similar to that for the aforementioned Fe3O4@nSiO2@mSiO2 microspheres

except for an additional procedure for introduction of metal nanoparticles on the magnetic silica microspheres before the coating (Figure 5a). As shown in Figure 5b, the coreshell magnetic silica microspheres, after surface modied with c-aminopropyltriethoxysilane (APS), can be efciently decorated by negatively charged metal nanoparticles (Au or Ag), and a mesoporous silica layer can be further formed, leading to a unique nanostructure with multicomponent and multi- functionalities (Figure 5c). The metal nanoparticles supported by these novel magnetic mesoporous materials show high performance in efcient epoxidation of styrene with high conversion (72%) and selectivity (80%) to styrene oxides, and by virtue of their magnetic separability, the multifunctional mesoporous microspheres can be easily collected for recycling. Following this concept, Lins group [52] reported the up-conversion phosphor modied magnetic mesoporous silica microspheres by coating Fe3O4 nanoparticles with rst condensed silica, and then mesoporous silica and nally modifying with doped NaYF4. The obtained microspheres possess bright up-conversion luminescence, high magnetization saturation and mesoporous silica shell. This multi-functional microspheres were studied as a drug delivery system, in which the drug release behavior can be monitored by the change of the up-conversion emission intensity. With modifying this method, Tian et al. [53] synthesized coreshell magnetic mesoporous silica microspheres (Fe3O4@HMSt) by directly coating magnetite particles with a layer of mesoporous silica via a solution solgel process. These magnetic silicas showed a high capacity for a fast, convenient and efcient removal trace 1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane (DDT) from aqueous media with a high distribution coefcient (Kd, 130 103 mLg1). With a similar route, Liu et al. [54] synthesized coreshell magnetic mesoporous silica microspheres and further modied the pore walls by immobilization of large amount of Cu2+ ions. By using the Cu2+-immobilized magnetic mesoporous silicas as absorbents, they achieved a fast, efcient and selective enrichments of peptides from both standard protein digestion and complex human serum samples. Hydrophobic magnetic nanocrystals were also used to synthesize coreshell magnetic mesoporous materials through solgel

Figure 4. Synthesis route (a), electron microscopy images of (b) Fe3O4@nSiO2 microspheres (TEM) and (cf) Fe3O4@nSiO2@mSiO2 microspheres (TEM (ce), SEM (f)). Reprinted from [50].

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Figure 5. Synthesis route (a), TEM images of (b) Au nanoparticle decorated Fe3O4@nSiO2 microspheres and (c) Fe3O4@nSiO2-Au@mSiO2 microspheres. Reprinted from [51].

Figure 6. Synthesis route (a) and TEM image (b) of coreshell magnetic mesoporous silica nanospheres using hydrophobic magnetite nanocrystals. Reprinted from [56].

approach [5659]. In this case, the magnetic nanocrystals stabilized with hydrophobic capping agent should be transferred into water phase before solgel coating. Kim et al. [56] synthesized uniform magnetic mesoporous silica nanospheres (50100 nm) with coreshell structure (Figure 6a) by rst treating the hydrophobic oleic-acid stabilized magnetite nanoparticles with CTAB and then coating them with mesoporous silica shell using Stber method (Figure 6b). Later on, the same group improved the synthesis, and achieved well-controlled magnetic mesoporous silica nanospheres by coating the nanocrystals individually. After further modication with hydrophilic PEG and uorescence isothiocyanate (FITC), these magnetic mesoporous nanospheres were successfully used for multimodal imaging and drug delivery [57]. Similarly, Feng et al. [58] reported the synthesis of functionalized coreshell magnetic mesoporous silica nanospheres by rst coating CTAB/ oleic acid co-stabilized magnetite nanoparticles with mesoporous silica and then covalently binding lanthanide complex (Figure 7a). The resulting lanthanide complex modied magnetic mesoporous silica nanospheres not only possess magnetism and high porosity, but also show excellent near infrared (NIR) luminescent property, which is very important for in vivo optical imaging in disease diagnosis and therapy (Figure 7b). It is worth noting that the above mentioned magnetic mesoporous nanospheres with uniform size and are favorable for in vivo

applications including drug delivery and MRI imaging, however, because their low magnetization per particle, the applications are limited. Additionally, most of magnetic mesoporous materials based on the hydrophobic magnetic nanoparticles have low ordering of mesopore arrangement. Recently, Zhang et al. [60] have synthesized magnetic silica microspheres with ordered mesostructure by using stearic acid stabilized magnetite nanoparticles as seeds through solgel process. By using cationic surfactants with different chain length (C14TAB, C16TAB, C18TAB) as the templates, they obtained uniform magnetic mesoporous silica microspheres with diameters of 90140 nm different mesostructures (2-D hexagonal and 3-D cubic symmetries) and tunable pore sizes (2.43.4 nm). Interestingly, they also achieved the synthesis of rod-like magnetic mesoporous silica materials with helical morphology by using stearic acid stabilized magnetite nanoparticles as the seeds and cationic surfactant, OTAB, as a template [61]. The same group [62] also reported the synthesis of novel magnetic mesoporous hollow spheres with magnetite cores and PMO shell via a modied solgel process by using BTME as the silica source (Figure 8A). They rst emulsied the CTAB/oleic acid co-stabilized magnetite nanoparticles in the solution of cationic uorocarbon surfactant (C3F7O(CFCF3CF2O)2CFCF3CONH(CH2)3N+(C2H5)2CH3I, CF4) and CTAB, and obtained vesicles with embedded magnetite nanoparticles. In the coating process, the magnetic vesicles acted as seeds

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Figure 7. (A) Synthesis route of Ln(DBM)3phen-MMS (Ln = Nd, Yb) nanospheres; (B) SEM images of phen-MMS (a), Nd(DBM)3phen-MMS (b), and Yb(DBM)3phen-MMS nanospheres (c); and (d) TEM image of Yb(DBM)3phen-MMS nanospheres. Reprinted from [58].

Figure 8. (A) Synthesis route of magnetic PMO spheres. Hydrophobic Fe3O4 nanoparticles (a) before and (b) after the treatment with CTAB. (c) Formation of FC4 vesicles with encapsulated Fe3O4 nanoparticles. (d) Addition of BTME forms composite micelles surrounding the vesicles, leading to (e) magnetic PMO spheres with surfactants. (B) TEM images of magnetic PMO spheres with varying sizes and magnetite contents (ad). Reprinted from [62].

and were coated by the mesostructured CTAB/ogranosilica composites. After removing CTAB by solvent extraction, the resultant magnetic hollow spheres show an organosilica shell with ordered 2-D hexagonal mesostructure, and magnetite nanoparticles were encapsulated in individual hollow spheres. The mean size of the magnetic PMO can be tunable in the range of 13020 nm by adjusting the CF4 amount (Figure 8B(ac)), or/and by increasing the addition amount of magnetite nanoparticles, the content of magnetites can be increased, and magnetic PMO with stronger magnetic response were obtained (Figure 8B(d)). As a widely used technique in industry for the production of such as paint pigments, coatings, and pharmaceuticals, spray drying has also employed for solgel coating of magnetite particles to produce magnetic mesoporous materials. Sanchezs group [63] reported a fast synthesis of magnetic mesoporous silica microspheres based on spray drying method (Figure 9a). In this method, c-Fe2O3 nanoparticles are dispersed in acidic ethanol solution containing water and surfactants (CTAB or P123), followed by adding precursors of silica and organosilica under stirring. The resultant

transparent sol was then subjected to spray drying using an aerosol generator to produce composite microspheres. The surfactants were removed by either Soxhlet extraction with ethanol or calcination. The obtained magnetic mesoporous silica microspheres have wide size distribution ranging 0.15.0 lm, 2-D hexagonal mesostructure, tunable pore size (2.3 and 8.0 nm templated from CTAB and P123, respectively) and relatively high magnetization (40 emu/ g) (Figure 9b). Due to the presence of superparamagnetic c-Fe2O3 nanoparticles, the microspheres display interesting behavior for hyperthermia and an excellent T2 effect for magnetic resonance imaging. Similarly, Vallet-Regi and coworkers [64] synthesized magnetic mesoporous silica microspheres by using the versatile spray drying method with Pluronic P123 as a template. The obtained microspheres were successfully used for drug release and hyperthermia therapy of solid tumors. Evidently, the spray drying approach is relatively simple and versatile method for the synthesis of magnetic mesoporous microspheres and other composite microspheres. However, owing to the difculty in controlling the aerosol generation dynamics and the fast solvent induced

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Figure 9. Synthesis procedure with inset presentative SEM image (a) of the magnetic mesoporous silica microspheres with embedded c-Fe2O3 nanoparticles (templated by P123). Reprinted from [63].

Figure 10. (a) Synthesis route, (b) TEM image (c) room temperature magnetization curve of (d) ibuprofen released from the coreshell structured magnetic mesoporous silica with disordered mesopores. Reprinted from [65].

self-assembly process in the droplets, it remains a great challenge to produce high quality magnetic mesoporous microspheres with uniform size, well-controlled distribution of magnetic nanoparticles and control of mesopore arrangement. Apart from surfactants and amphiphilic block copolymers, organic silanes with long carbon chains have also been employed as pore forming agents in the synthesis of magnetic mesoporous materials with disordered mesopores. In this regards, Shi and coworkers [65] developed a multi-step synthesis approach to magnetic mesoporous materials with well-dened coreshell structure (Figure 10a). Water-dispersible hematite (a-Fe2O3) particles were rst coated with silica using Stber method. The obtained aFe2O3@SiO2 spheres were then coated them with an organicinorganic hybrid layer through solgel process by using TEOS and C18TMS. The C18 silanes and templates were burned out via calcination, leaving disordered mesopores in the silica shell. Finally, through high-temperature annealing in a hydrogen/nitrogen

mixed gas, the low magnetization hematite cores were converted into magnetite, and magnetic mesoporous silica microspheres with a mean diameter of 270 nm, strong magnetization of 27.3 emu/g (Figure 10b and c), disordered mesopores (3.8 nm) and high surface area (273 m2/g) were obtained. By using ibuprofen as a model drug, the release behavior in a simulated body uid was studied, showing a slow and prolonged drug release process (Figure 10d). Interestingly, the same group [66] developed a kind of rattle-like microspheres with silica-coated magnetite core encapsulated in the hollow mesoporous silica shell by hydrothermally treating the aforementioned a-Fe2O3@SiO2@C18SiO2 microspheres before calcination in air and hydrogen reduction treatment. The formation of hollow structure is demonstrated to be related with the different shrinkage degree of the condensed silica layer and the hybrid C18 silica outer shell. During hydrothermal treatment the silica underwent a further condensation and shrinkage, while the hybrid C18 silica shell shrunk little due to the inhibition effect of C18. Through

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Figure 11. SEM (a) and TEM (b) images of the monodisperse iron oxide/silica nanocomposite spheres after being calcined at 1000 C. Reprinted from [72].

the similar strategy, they also synthesized magnetic nanoellipsoids by coating the ellipsoidal Fe2O3 particles with disordered mesoporous silica shell for drug delivery and bioimaging [67]. It is worth mentioning that, when high-temperature calcination is employed to remove the organic templates and generate mesopores, sintering of magnetic mesoporous silica materials could inevitably occur, and this is apparently unfavorable to their dispersibility in solution. In addition, although using magnetic particles with large sizes can lead to high magnetization microspheres, they do not have superparamagnetism because the magnetic particle size is much larger than the critical size (10 15 nm). Inverse microemulsion strategies have also been employed to synthesize magnetic mesoporous materials. In these systems, the magnetic nanoparticles were emulsied and dispersed in water/ oil microemulsion by using nonionic surfactants, such as Brij-type and polyoxyethylene(5) nonylphenyl ether. During the hydrolysis and condensation of TEOS and C18TMS, the magnetic nanoparticles can be coated with C18silica shells. After calcination, the silica shells with disordered mesopores can be formed on the magnetic nanoparticles [68]. 2.2. Post loading approach Initially, loading magnetic nanoparticles into pre-synthesized porous materials was proposed to develop magnetically separable porous materials. These materials can be used as a support of noble metal catalysts in liquid-phase catalysis, and fast extraction of pollution macromolecules (heavy metal ions, organic contents) in water. Pioneering work was done through impregnation of the activated carbon using iron precursors solution and in situ precipitating magnetic nanoparticles in the pores [83,84]. By virtue of the capillary motion of the precursor solution in the mesopores, Tartajs group [69] reported a synthesis of superparamagnetic mesoporous silica composites. Firstly, the mesopores of the presynthesized mesoporous silica (e.g. SBA-15) were soaked in iron nitrate solution, and the obtained Fe(III)-SBA-15 powders were then slightly impregnated with reductive EG, and nally the loaded Fe(III) species was reduced inside the mesopores by thermal treatment at 450 C in N2. The obtained samples retained the ordered mesostructure with a high loading amount (up to 32 wt.%) of magnetic nanoparticles inside the pores ($8.9 nm). Compared to the parent SBA-15 (BET surface area of 690 m2/g, pore volume of 1.21 cm3/g), the magnetic SBA-15 samples have much lower surface area and pore volume (330 m2/g and 0.56 cm3/g, respectively) due to the introduced magnetic nanoparticles. Usually, using the impregnation method with iron solution, it is difcult to avoid the formation of magnetic nanoparticles on the surface of the mesoporous silica particles [70,71]. To overcome it, Nakamura and coworkers proposed an effective post-loading method [72]. They rst synthesized MCM41-type mesoporous

silica spheres with uniform diameter of 650 nm and radiallyaligned mesopores of $2.5 nm. The silica spheres were then impregnated with a furfuryl alcohol with dissolved ferrocenecarbaldehyde (iron precursor), followed by in situ polymerization. Due to the high solubility of the iron precursor in furfuryl alcohol (>2 g/ mL) and the in situ polymerization, a large amount of ferrocenecarbaldehyde were conned in the mesopores with the assistance of the polymer. After calcination at 1000 C, the ferrocenecarbaldehyde could be converted into c-Fe2O3. The obtained magnetic composite spheres with smooth surface, magnetization of about 6.2 emu/g and very low surface area ($10 m2/g) (Figure 11). This impregnation process can be used as an alternative strategy to synthesize magnetic mesoporous materials; however, there is always a balance between loading amount of magnetic nanoparticles and the porosity of the materials. Large loading amount can block the mesopores and decrease the porosity. Recently, Fuertes et al. [73] proposed an effective strategy to synthesize magnetic mesoporous carbon with both high mass fraction of magnetic component and high surface area (Figure 12). In this method, hollow spheres with disordered mesopores were repeatedly impregnated with an ethanol solution of iron nitrate. And the iron species were converted in the cages into iron oxide by thermal treatment in N2. The resultant magnetic mesoporous carbon materials have typical magnetic core of tiny crystallized iron oxide nanoparticles (8.015 nm), and mesoporous shell with the thickness of 50 nm and disordered mesopores of 2.03.5 nm (Figure 13a and b). The magnetic mesoporous carbon spheres with a low loading (20 wt.%) of iron oxides possess a mean pore size of $3.3 nm, high surface area up to 1370 m2/g, large pore volume of 1.36 cm3/g and magnetization of 9.5 emu/g (Figure 13c). They exhibit excellent performance in immobilization of a large amount (122 mg/g after 24 h adsorption) of lysozyme (Figure 13d). Interestingly, by a similar approach, they also synthesized magnetic mesoporous carbon capsules with magnetic nanoparticles incorporated in the mesoporous shells [74]. Lee et al. [75] adopted a bi-solvent impregnation method to synthesize magnetic mesoporous silica microspheres (Figure 14a). They rst impregnated the pre-synthesized solid core/mesoporous silica microspheres with an ethanol solution containing Co(NO3)2 and Fe(NO3)3 with the help of dioctyl ether containing small amount of polyoxyethylene(5)nonylphenyl ether. The impregnated samples were annealed at high temperature in air, and magnetic mesoporous silica microspheres decorated with CoFe2O4 nanoparticles were obtained (Figure 14b). The magnetic mesoporous silica microspheres can be endocytosed and internalized by both immortalized mouse broblast (NIH-3T3) and human breast cancer (MCF-7), suggesting a promised application as therapeutic drug carriers. The post loading approach shows some advantage over the sol gel method, i.e. the shape, size, monodispersity of the parent mesoporous materials can be well retained during the whole process.

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Figure 12. Illustration of the synthesis procedure. carbon capsule (A) before and (B) after loading inorganic precursor; (C) inorganic nanoparticles encapsulated within the mesoporous carbon shell. (1) Filling of the carbon capsule with the inorganic precursor; (2) conversion of the inorganic precursor into inorganic nanoparticles. Reprinted from [73].

Figure 13. (a) SEM and TEM (inset) images, (b) nitrogen sorption isotherm and pore size distribution (inset) and (c) magnetization curves at 300 K of CS-FexOy-20 (d) Immobilization of the lysozyme on the CS-FexOy-20 nanocomposite (inset: magnetic separation of the CS-FexOy-20 particles loaded with lysozyme). Reprinted from [73].

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Figure 14. (a) The synthesis route and TEM image (b) of magnetic mesoporous microspheres with CoFe2O4 nanoparticles decorated mesoporous shell. Reprinted from [75].

Figure 15. Synthesis route (a) and TEM image (b) of magnetic mesoporous carbons by using SBA-15 as a template. Reprinted from [80].

However, the drawback of this post-loading method is that the mesopores of the parent materials can be usually blocked by the magnetic nanoparticles, which results in very a low surface area, low pore volume, and poor accessibility of pores. Therefore, it is difcult to achieve a high loading amount of magnetic nanoparticles to produce high-magnetization magnetic mesoporous materials. Most importantly, because the magnetic nanoparticles in the composite materials are exposed in the mesopores or easily accessible, they are susceptible to etching in acidic solution in practical applications and thus lose their magnetism. 2.3. Nanocasting synthesis Nanocasting is an effective pathway to synthesize mesoporous replicas, which usually involves the impregnation of the mesoporous materials (e.g. SBA-15) hard templates with a certain precursor driven by the capillary force, in situ conversion of the precursors in the mesopore channels into target compositions, and nally removal of the hard templates. [7679] This approach can also applied to synthesize magnetic mesoporous materials. In general, mesoporous silica with relatively large pore sizes, e.g. SBA-15, is more suitable for use as a hard-template, because they can provide more space for loading precursor and magnetic nanoparticles. Lee et al. [80] synthesized magnetic mesoporous carbons by using SBA15 as a template (Figure 15). They rst lled the mesopores with pyrrole by vapor inltration, and further soaked the pyrrole-SBA-

15 composites in FeCl3 solution to initiate the polymerization of pyrrole. During carbonization in N2, the Fe2+ ions in the poly(pyrrole) matrix were converted to magnetic a-Fe and Fe3C nanoparticles. Finally, magnetic mesoporous carbon materials were obtained through dissolving the silica template. The presence of superparamagnetic nanoparticles was veried by the XRD and TEM observations (Figure 16). Herein, FeCl3 serves as both oxidative catalyst and source of magnetic nanoparticles. The magnetic mesoporous carbons possess BET surface area of 643 m2/g, pore volume of 0.60 cm3/g, pore size of 2.9 nm, and magnetization saturation of 30 emu/g, which makes them good candidates as an adsorbent, and electrode materials for bioelectrocatalysis. Shi and coworkers [81] have developed a co-casting approach to magnetic mesoporous materials by using SBA-15 as a template. The mesoporous silica was rst impregnated with a mixed solution of furfuryl alcohol and oxalic acid. After ethanol evaporation and polymerization of furfuryl alcohol at 90 C, the obtained composite was impregnated in FeCl3 ethanol solution, and subjected to carbonization at 600 C in argon. Finally, the silica template was removed by dissolving in NaOH solution, and magnetic mesoporous c-Fe2O3/C composite was obtained (Figure 16a and b). For comparison, a reference sample (Fe/meso-C) was also prepared by impregnation of mesoporous carbon with FeCl3. It was found that the magnetic nanoparticles in the Fe/meso-C sample were supported on the carbon framework with a mean size of 25 nm which were estimated from TEM images (Figure 16c) and

Y. Deng et al. / Chemical Physics Letters 510 (2011) 113

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Figure 16. TEM images (a and b) of the magnetic mesoporous carbon c-Fe2O3/C synthesized by using SBA-15 as a hard-template through a co-casting approach. (c) TEM image of the reference sample (Fe/meso-C), (d) XRD patterns of (1) c-Fe2O3/C and (2) Fe/meso-C composites. Reprinted from [81].

much larger than that (about 5 nm) of the c-Fe2O3/C obtained from the co-casting method. It suggests that the growth of magnetic iron oxide can be restrained in the carbon walls along the pore channels of the SBA-15 template. The smaller size in the c-Fe2O3/C sample was also conrmed by the XRD measurement (Figure 16d). By varying FeCl3 amount, they succeeded in adjusting the iron oxide content in the mesoporous c-Fe2O3/C. Because the iron oxide nanoparticles are embedded in carbon matrix, the c-Fe2O3/C materials show excellent Paramagnetism and magnetic separability, which makes them good candidate in applications of separation and adsorption. By adopting a synthesis strategy similar to that from Lee et al. [80], Jaroniec and coworkers [82] prepared N-doped and graphitic mesoporous carbons incorporated with magnetic nanoparticles by using both SBA-15 and SBA-16 as templates. The resulting mesoporous carbons have N-doped graphitized framework and embed magnetic iron (c-Fe) and iron carbide (Fe3C) nanoparticles. Apart from the above mentioned three approaches, other methods have also been employed to synthesize magnetic mesoporous materials. For example, Sen and coworkers [84] reported a simplied approach to magnetic mesoporous silica by directly mixing an aqueous dispersion of magnetite nanoparticles with a gel solution containing a surfactant (CTAB), silica precursor (TEOS), and the catalyst sodium hydroxide. The resultant coreshell magnetic particles show structure with thin mesopore shell (1020 nm), low regularity of mesostructure and saturation magnetization (Ms) of 82 emu/g at 300 K. Owing to their magnetic separability and high surface area, the magnetic mesoporous silica shows an excellent

performance (nearly 100% recovery of bound DNA) in binding and elution of sheared salmon sperm DNA at physiological pH (7.2). This direct method is suitable for large-scale synthesis, but it can not produce high-quality magnetic mesoporous materials with well-controllable parameters, including morphologies, structures, and well-protected magnetic components. 3. Summary and outlook Magnetic mesoporous materials have exhibited great application potential in many elds, including MRI, environmental protection, and hyperthermia, because they possess magnetic properties and the high porosity, ordered structure and tunable pore sizes. This review summarizes and elucidates the synthesis methodologies for magnetic mesoporous materials including solgel coating, post-loading, and nanocasting approaches. Coating or encapsulating magnetic nanoparticles with mesoporous materials through solgel process by controlling interface interaction has been demonstrated as a versatile approach to coreshell magnetic mesoporous materials. More importantly, through this approach, other functional nanoparticles (Au [51], quantum dots [56]) could be introduced to construct multi-functional and multi-component mesoporous materials. To date, most of the reported solgel coating syntheses greatly depend on the use of cationic surfactants, such as CTAB, as a template, and as a result, the obtained magnetic mesoporous materials are limited to have a mesopore size of less than 3.0 nm. This may limit their applications in bio-elds such as protein separation, enzyme immobilization. Exploration of

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solgel strategies to synthesize magnetic mesoporous materials with large mesopores is in high demand. Post-loading methods can retain the morphology and size uniformity, but usually result in blockage of the mesopore channels and low surface area and pore volume. Designing special mesoporous materials, such as hollow mesoporous spheres [73] as the host for loading magnetic nanoparticles can overcome this problem. Nanocasting usually leads magnetic components to expose surrounding media, which is not desired in most application occasions, especially in acidic solution. Although considerable achievements have been made in the past decades, the synthesis of magnetic mesoporous materials with high magnetization, large mesopores (>3.0 nm), and uniform size and morphology is still a challenge. And most of magnetic mesoporous materials are limited to have nonmagnetic components of silica, or carbon. Much work is needed to be done to explore new methods and strategies for the synthesis of magnetic mesoporous silicas in a controllable way. In the long run, the research interest may follow two main directions. One is the in vivo application based research (e.g. MRI, drug delivery, hyperthermal cancer therapy) that requires magnetic mesoporous materials with small size (around 100 nm), uniform size and morphology, excellent water dispersibility, biocompatible surface, and low cytotoxicity. Another is the regular separationadsorption application based research (e.g. absorbent for environment remediation, catalyst carrier, biomacromolecule separation) that requires high magnetization (Ms), functionalizable surface, tunable pore size, diverse nonmagnetic components, high surface area, and large pore volume. Magnetic mesoporous materials will likely enjoy their popularity in many contexts various research communities once a controllable and large-quantitative synthesis is realized.

Acknowledgements This work was supported by NSF of China (20 890 121, 20 871 030, 21 073 040), State Key Basic Research Program of PRC (2009AA033701 and 2009CB930400), Shanghai Leading Academic Discipline Project (B108), Doctoral Program Foundation of State Education Commission of China (200 802 461 013), and Science & Technology Commission of Shanghai Municipality (08DZ2270500).

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Y. Deng et al. / Chemical Physics Letters 510 (2011) 113 Yonghui Deng received his BS degree in chemistry from Nanchang University (2000) and his Ph.D. in polymer chemistry & physics from Fudan University (2005) under the supervision of Prof. Shoukuan Fu. In 2005, he joined Prof. Dongyuan Zhao group as a postdoctoral researcher in Fudan University. In 2007, he became an Associate Professor in department of chemistry at Fudan University. He has coauthored over 50 papers in refereed journals and led 6 Chinese patents. His research interest includes block copolymer design and selfassembly, porous materials, functional nanomaterials, and plasmonics.

13 Zhenkun Sun obtained his B.S. degree in 2008. He is currently a third-year Ph. D. student under the supervision of Prof. Dongyuan Zhao in Department of Chemistry of Fudan University. He has coauthored 6 papers in referred journals. His research focuses on the synthesis, functionalization and application of ordered mesoporous materials.

Yue Cai obtained her B.S. degree in chemistry from Fudan University in 2010. She is now a rst-year Ph.D. student at Duke University under the supervision of Prof. Jie Liu. Her current research involves controlling the growth of carbon nanotubes for nanoelectronics and composite materials.

Dongyuan Zhao received his B.S. (1984), M.S. (1987) and Ph.D. (1990) from Jilin University. He carried out postdoctoral research at the Weizmann Institute of Science (199394), University of Houston (199596), and University of California at Santa Barbara (199698). He is a Professor (Cheung Kong Professorship) in the Department of Chemistry at Fudan University since 1998. He was elected as a member of the Chinese Academy of Science in 2007. He has published more than 400 scientic papers and hold 39 patents. His research interests mainly include synthesis, assembly, structure and application of ordered mesoporous materials and microporous molecular sieves.