The Capture and Catalytic Conversion of CO_(2) by Dendritic Mesoporous Silica-Based Nanoparticles

Dendritic mesoporous silica nanoparticles own three-dimensional center-radial channels and hierarchical pores,which endows themselves with super-high specific surface area,extremely large pore volumes,especially accessible internal spaces,and so forth.Dissimilar guest species(such as organic groups or metal nanoparticles)could be readily decorated onto the interfaces of the channels and pores,realizing the functionalization of dendritic mesoporous silica nanoparticles for targeted applications.As adsorbents and catalysts,dendritic mesoporous silica nanoparticles-based materials have experienced nonignorable development in CO_(2)capture and catalytic conversion.This comprehensive review provides a critical survey on this pregnant subject,summarizing the designed construction of novel dendritic mesoporous silica nanoparticles-based materials,the involved chemical reactions(such as CO_(2)methanation,dry reforming of CH_(4)),the value-added chemicals from CO_(2)(such as cyclic carbonates,2-oxazolidinones,quinazoline-2,4(1H,3H)-diones),and so on.The adsorptive and catalytic performances have been compared with traditional silica mesoporous materials(such as SBA-15 or MCM-41),and the corresponding reaction mechanisms have been thoroughly revealed.It is sincerely expected that the in-depth discussion could give materials scientists certain inspiration to design brand-new dendritic mesoporous silica nanoparticles-based materials with superior capabilities towards CO_(2)capture,utilization,and storage.

Fabrication and characterization of tungsten-containing mesoporous silica for heterogeneous oxidative desulfurization

A series of functional,tungsten-containing mesoporous silica materials（W-SiO2） have been fabricated directly from an ionic liquid that contained imidazole and polyoxometalate,which acted as mesoporous template and metal source respectively.These materials were then characterized through X-ray diffraction（XRD）,transmission electron microscopy（TEM）,Raman spectroscopy,Fourier transform infrared spectra（FTIR）,diffuse reflectance spectra（DRS）,and N2 adsorption-desorption,which were found to contain tungsten species that were effectively dispersed throughout the structure.The as-prepared materials W-SiO2 were also found to possess a mesoporous structure.The pore diameters of the respective sample W-SiO2-20 determined from the TEM images ranged from 2 to 4 nm,which was close to the average pore size determined from the nitrogen desorption isotherm（2.9 nm）.The materials were evaluated as catalysts for the heterogeneous oxidative desulfurization of dibenzothiophene（DBT）,which is able to achieve deep desulfurization within 40 min under the optimal conditions（Catalyst（W-SiO2-20）= 0.01 g,temperature = 60℃,oxidant（H2O2）= 20 μL）.For the removal of different organic sulfur compounds within oil,the ability of the catalyst（W-SiO2-20） under the same conditions to remove sulfur compounds decreased in the order：4,6-dimethyldibenzothiophene Dibenzothiophene Benzothiophene 1-dodecanethiol.Additionally,they did not require organic solvents as an extractant in the heterogeneous oxidative desulfurization process.After seven separate catalytic cycles,the desulfurization efficiency was still as high as 90.3%.From the gas chromatography-mass spectrometer analysis,DBT was entirely oxidized to its corresponding sulfone DBTO2 after reaction.A mechanism for the heterogeneous desulfurization reaction was proposed.

Facile H2O2 Hydrothermal Synthesis of Bimodal Mesoporous Silica MCM-48 Spheres

The ordered bimodal mesoporous silica MCM-48 spheres were facile synthesized by mild- temperature post-synthesis H2O2 hydrothermal treatment of as-synthesized MCM-48. The results showed that H2O2 is indispensable for simultaneously removing organic templates and forming ordered bimodal mesoporous silica MCM-48 spheres. The bimodal mesoporous MCM-48 was characterized by X-ray diffraction, transmission electron micrographs, FT-IR, and N2 adsorption-desorption, and a possible mechanism was proposed for the formation of bimodal mesoporous MCM-48.

Gold nanoparticle stabilization within tailored cubic mesoporous silica:Optimizing alcohol oxidation activity

Stabilizing gold nanoparticles（AuNPs） within a desired size range is critical to realize their promising catalytic performance in many important reactions.Herein,we investigate the anti-sintering properties of cubic mesoporous silica（FDU-12） as a function of pore entrance size.Simple adjustments to the type of organic template and reaction temperature enable the successful synthesis of FDU-12 with controllable entrance sizes（ 3,3-5 and 7 nm）.Excellent anti-sintering properties are observed for FDU-12 with a sub-5-nm entrance size（3-5 nm） over a wide loading concentration（1.0-8.3 wt%） and the AuNPs can be stabilized within a 4.5-5.0-nm range after calcination at 550 ℃in air for 5 h.Smaller entrance size（ 3 nm） prevents ingress of 3-nm AuNPs to the mesopores and results in low loading capacity and sintering.Conversely,FDU-12 possessing a larger entrance size（7 nm） shows promising anti-sintering properties at high loading concentrations,although catalytic performance is significantly lost at lower concentrations（e.g.2.1 wt%,14.2 ± 5.5 nm）.Different anti-sintering mechanisms are proposed for each of the different FDU-12 entrance sizes.Additionally,catalytic data indicates that the obtained 4.5-nm AuNPs supported on FDU-12 with a sub-5-nm entrance size exhibit excellent mass-specific activity（1544 mmol g_（Au）^（-1） h^（-1）） and selectivity（ 99%）at 230 ℃ for the gas-phase selective oxidation of cyclohexanol.

Selective catalytic oxidation of NO over iron and manganese oxides supported on mesoporous silica

The selective catalytic oxidation （SCO） of NO was studied on a catalyst consisting of iron-manganese oxide supported on mesoporous silica （MPS） with different Mn/Fe ratios. Effects of the amount of manganese and iron, oxygen, and calcination temperature on NO conversion were also investigated. It was found that the Mn-Fe/MPS catalyst with a Mn/Fe molar ratio of 1 showed the highest activity at the calcination temperature of 400 °C. The results showed that over this catalyst, NO conversion reached 70% under the condition of 280 °C and a space velocity of 5000 h-1. SO2 and H2O had no adverse impact on the reaction activity when the SCO reaction temperature was above 240 °C. In addition, the SCO activity was suppressed gradually in the presence of SO2 and H2O below 240 °C, and such an effect was reversible after heating treatment.

Photocatalytic Oxidative Desulfurization of Dibenzothiophene on TiO2 Modified Bimodal Mesoporous Silica

By using the bimodal mesoporous silica(BMMS) as the carrier and butyl titanate as the titanium source, the TiO_2/BMMS catalyst was prepared. The samples were characterized by XRD, XRF, N_2 adsorption and desorption, FTIR, UVvis,SEM, EDS, and TEM techniques. The test results showed that TiO_2 was amorphous, the TiO_2/BMMS catalyst had an ordered bimodal mesoporous structure, and the chemical interaction existed between BMMS and TiO_2. Since the TiO_2/BMMS had a lower band gap, its photocatalytic activity was better than TiO_2. Under UV irradiation a one-pot PODS system was set up, using TiO_2/BMMS as the catalyst, H_2O_2 as the oxidant, and methanol as the solvent. The TiO_2/BMMS catalyst showed better photocatalytic activity than the mono-modal mesoporous TiO_2/SBA-15 catalyst, and the desulfurization rate of dibenzothiophene(DBT) over TiO_2/BMMS catalyst could reach 99._2%. The TiO_2/BMMS catalyst also had so good stability that the desulfurization rate of DBT did not drop apparently after 8 cycles of reusing, and could still be close to 90%.

In Situ Synthesis of Fluorescent Mesoporous Silica–Carbon Dot Nanohybrids Featuring Folate Receptor-Overexpressing Cancer Cell Targeting and Drug Delivery

Multifunctional nanocarrier-based theranostics is supposed to overcome some key problems in cancer treatment.In this work,a novel method for the preparation of a fluorescent mesoporous silica–carbon dot nanohybrid was developed.Carbon dots(CDs),from folic acid as the raw material,were prepared in situ and anchored on the surface of amino-modified mesoporous silica nanoparticles(MSNs–NH2) via a microwave-assisted solvothermal reaction.The as-prepared nanohybrid(designated MSNs–CDs) not only exhibited strong and stable yellow emission but also preserved the unique features of MSNs(e.g.,mesoporous structure,large specific surface area,and good biocompatibility),demonstrating a potential capability for fluorescence imagingguided drug delivery.More interestingly,the MSNs–CDs nanohybrid was able to selectively target folate receptor-overexpressing cancer cells(e.g.,HeLa),indicating that folic acid still retained its function even after undergoing the solvothermal reaction.Benefited by these excellent properties,the fluorescent MSNs–CDs nanohybrid can be employed as a fluorescence-guided nanocarrier for the targeted deliveryof anticancer drugs(e.g.,doxorubicin),thereby enhancing chemotherapeutic efficacy and reducing side effects.Our studies may provide a facile strategy for the fabrication of multifunctional MSN-based theranostic platforms,which is beneficial in the diagnosis and therapy of cancers in future.

SYNTHESIS OF MESOPOROUS POLY(STYRENE-co-MALEIC ANHYDRIDE)/SILICA HYBRID MATERIALS VIA A NONSURFACTANT-TEMPLATED SOL-GEL PROCESS

Mesoporous poly(styrene-co-maleic anhydride)/silica hybrid materials have been prepared. The synthesis was achieved by the HCl-catalyzed sol-gel reactions of tetraethyl orthosilicate (TEOS) and styrene-maleic anhydride copolymer in the presence of 3-aminopropyl triethoxysilane (APTES) as a coupling agent and citric acid as a nonsurfactant template or pore-forming agent, followed by ethanol extraction. Characterization results from nitrogen sorption isotherms and powder X-ray diffraction indicate that polymer-modified mesoporous materials with large specific surface areas (e.g. 900 m(2)/g) and pore volumes (e.g. 0.6 cm(3)/g) could be prepared. As the citric acid concentration is increased, the specific surface areas, pore volumes and pore diameters of the hybrid materials increase.

Oxidation of NO over cobalt oxide supported on mesoporous silica

Cobalt oxide catalysts supported on mesoporous silica （Co3O4/MPS） were prepared, characterized and applied for catalytic oxidation of NO. Effects of catalyst supports, calcination temperatures, H2O and SO2 on NO conversion were investigated. The samples were also characterized by BET, XRD, FTIR and TG/DTG. The results suggested that Co3O4/MPS catalyst calcined at 573 K had the smallest crystal particles and the best surface dispersion. This catalyst had the highest activity and yielded 82% NO conversion at 573 K, at a space velocity of 12000 h^-1. Although the conversion of NO decreased with the introduction of H2O, it could be restored completely after removing residual H2O from Co3O4/MPS catalyst by heating at 573 K. In the presence of SO2, the oxidation activity decreased and COSO4 was detected on the catalyst. The NO conversion decreased to 30.2% in the presence of SO2 and H2O. It could not be restored completely after cutting off H2O and SO2. The deactivation of the catalyst in the presence of SO2 and H2O was attributed to the formation of cobalt sulfate species.

Synthesis and Characterization of Carboxyl-terminated Polyethylene Glycol Functionalized Mesoporous Silica Nanoparticles

Colloidal mesoporous silica nanoparticles functionalized with carboxy-terminated polyethylene glycol(CMS-PEG-COOH) were successfully synthesized by covalently grafting dicarboxy-terminated polyethylene glycol(HOOC-PEG-COOH) on the surface of the amino functionalized CMS nanoparticles with amide bond as a cross linker. Moreover, the structural and particle properties of CMS-PEG-COOH were characterized by nuclear magnetic resonance spectroscopy(1 H-NMR), transmission electron microscopy(TEM), dynamic light scattering(DLS), nitrogen adsorption-desorption measurements, X-ray diffraction(XRD), and Fourier transform infrared spectroscopy(FT-IR). The nanomaterials presented a relatively uniform spherical shape morphology with diameters of about 120 nm,and favorable dispersibility in weak acid solution. The CMSPEG-COOH exhibited no changes in the state of amorphous, while the mesopores sizes of 5.25 nm might provide the nanomaterials with large capacity for the loading and releasing of drugs. So the results indicated that CMSPEG-COOH might be a critical nanomaterial for drug delivery system in the future.

Low-cost preparation of mesoporous silica with high pore volume

Mesoporous silica materials with high pore volume were successfully prepared by the chemical precipitation method, with water glass and a biodegradable nonionic surfactant polyethylene glycol （PEG）. The obtained materials were characterized by transmission electron microscopy （TEM）, scanning electron microscopy （SEM）, thermo gravimetric analyzer and differential scanning calorimetry （TG-DSC）, nitrogen adsorption-desorption measurements, and X-ray diffraction （XRD）. The results showed that the changes of the pore parameters depended on both the surfactant content and heat treatment temperature. When the content of PEG was 10wt% and the obtained PEG/SiO2 composite was heated at 600℃, the mesoporous silica with a pore volume of 2.2 cma/g, a BET specific surface area of 361.55 m^2/g, and a diameter of 2-4 μm could be obtained. The obtained mesoporous silica materials have potential applications in the fields of paint and plastic, as thickening, reinforcing, and flatting agents.

An Oxidative Desulfurization Catalyst Based on Bimodal Mesoporous Silica Containing Quaternary Ammonium Heteropolyphosphamolybdenum

A bimodal mesoporous silica(BMMS) modified with amphiphilic compound(C_(19)H_(42)N)_3(PMo_(12)O_(40))(CTA-PMO) was prepared by the two-step impregnation method. Firstly, H3PMo12O40 was introduced into the bimodal mesoporous silica via impregnation, then C_(19)H_(42)NBr(CTAB) was grafted on the surface of BMMS containing H3PMo12O40 based on the chemical reaction between quaternary ammonium compound and the phosphomolybdic acid, and then the catalyst CTAPMO/BMMS was obtained. The samples were characterized by XRD, N_2 adsorption and desorption, FTIR, 31P-NMR, 29Si-NMR and TEM analyses. It is shown that the catalyst has a typical bimodal mesoporous structure, in which the small mesopore diameter is about 3.0 nm and the large mesopore diameter is about 5.0 nm. The chemical interaction happens between the Keggin structure and silica group of BMMS. Compared with the mono-modal porous Hβ and SBA-15 zeolites modified with CTA-PMO, CTA-PMO/BMMS showed better catalytic activity in the oxidative conversion of dibenzothiophene(DBT), and the desulfurization rate can reach about 94% with the help of extraction, and the catalyst can be separated by filtration and reused directly. The catalytic oxidative desulfurization mechanism on CTA-PMO/BMMS was proposed and verified.

pH-responsive mesoporous silica nanoparticles employed in controlled drug delivery systems for cancer treatment

In the fight against cancer, controlled drug delivery systems have emerged to enhance the therapeutic efficacy and safety of anti-cancer drugs. Among these systems, mesoporous silica nanoparticles （MSNs） with a functional surface possess obvious advantages and were thus rapidly developed for cancer treatment. Many stimuli-responsive materials, such as nanopartides, polymers, and inorganic materials, have been applied as caps and gatekeepers to control drug release from MSNs. This review presents an overview of the recent progress in the production of pH-responsive MSNs based on the pH gradient between normal tissues and the tumor microenvironment. Four main categories of gatekeepers can respond to acidic conditions. These categories will be described in detail.

Synthesis of mesoporous high‐silica zeolite Y and their catalytic cracking performance

Mesoporous high‐silica zeolite Y with advantages of improved accessibility of acid sites and mass transport properties is highly desired catalytic materials for oil refinery,fine chemistry and emerg‐ing biorefinery.Here,we report the direct synthesis of mesoporous high‐silica zeolite Y(named MSY,SiO_(2)/Al2O_(3)≥9.8)and their excellent catalytic cracking performance.The obtained MSY mate‐rials are mesoporous single crystals with octahedral morphology,abundant mesoporosity and ex‐cellent(hydro)thermal stability.Both the acid concentration and acid strength of H‐form MSY are obviously higher than those of commercial ultra‐stable Y(USY),which should be attributed to the uniform Al distribution of MSY zeolite.The H‐MSY displays an obviously reduced deactivation rate and improved catalytic activity in the cracking reaction of bulky 1,3,5‐triisopropylbenzene(TIPB),as compared with its mesoporogen‐free counterpart and USY.In addition,H‐MSY was investigated as catalyst for the cracking of industrial heavy oil.The MSY‐based catalyst(after aging at 800 oC in 100%steam for 17 h)exhibits superior conversion(7.64%increase)and gasoline yield(16.37%increase)than industrial fluid catalytic cracking(FCC)catalyst under the investigated conditions.

Determination of Average Wall Thickness of Mesoporous Silica

Small Angle X-ray Scattering (SAXS) experiment using Synchrotron Radiation as X-ray source was used to determine the average wall thickness of mesoporous silica prepared by condensation of tetraethylorthosilicate (TEOS) using non-ionic alkylpolyethyleneoxide (AEO(9)) surfactant as templates. The results agreed with that of high-resolution TEM (HRTEM) measurement.

Preparation and Characterization of Carboxyl Functionalized Fluorescent Mesoporous Silica Nanoparticles Containing 8-Hydroxyquinolinate Zinc Complexes

Fluorescent mesoporous silica nanoparticles functionalized with carboxyl group(Znq-CMSCOOH) were successfully synthesized by in situ formation route of 8-hydroxyquinolinate zinc complexes in channels of mesoporous silica nanoparticles and post-grafting of carboxyl group on the surface. Moreover,the particle size and structural properties of Znq-CMS-COOH were characterized by transmission electron microscopy(TEM),field emission scanning electron microscopy(FE-SEM),dynamic light scattering(DLS),Fourier transform infrared spectroscopy(FT-IR),UV-vis spectrometer, fluorescence spectrometer and nitrogen adsorption-desorption measurements. The obtained results suggest that the Znq-CMS-COOH presents the uniform spherical shape with the mean diameter of about 85 nm and the obvious wormhole arrangement mesoporous. In addition, the Znq-CMS-COOH possesses green fluorescence with the emission peaks at 495 nm. So the Znq-CMS-COOH, which is beneficial to further modification and tracing, might be a great potential carrier for applying in drug delivery system in the future.

Location and size regulation of manganese oxides within mesoporous silica for enhanced antibiotic degradation

Refractory antibiotics in domestic wastewater are hard to be completely eliminated by conventional methods,and then lead to severe environmental contamination and adverse effects on public health.In present work,advanced oxidation processes(AOPs)are adopted to remove the antibiotic of sul-fachloropyridazine(SCP).Nanosized Mn_(2)O_(3) was fabricated on the SBA-15 material to catalytically acti-vate potassium peroxydisulfate(PDS)to generate reactive oxygen radicals of.OH and SO_(4).for SCP degradation.The effects of location and size of Mn_(2)O_(3) were explored through choosing either the as-made or template free SBA-15 as the precursor of substrate.Great influences from the site and size of Mn_(2)O_(3) on the oxidation activity were discovered.It was found that Mn_(2)O_(3) with a large size at the exterior of SBA-15(Mn-tfSBA)was slightly easier to degrade SCP at a low manganese loading of 1.0-2.0 mmol.g;however,complete SCP removal could only be achieved on the catalyst of Mn_(2)O_(3) with a refined size at the interior of SBA-15(Mn-asSBA).Moreover,the SO_(4).species were revealed to be the decisive radicals in the SCP degradation processes.Exploring the as-made mesoporous silica as a support provides a new idea for the further development of environmentally friendly catalysts.

Synthesis of Highly ordered Large Size Mesoporous Silica and Effect of Stabilization as Enzyme Supports in Organic Solvent

FSM 16, MCM 41 and SBA 15 types of hexagonal mesoporous silica with a highly ordered 2 dimensional structure were synthesized by using different silicon sources and surfactants. In the 2 dimensional silicate framework, pore size can be uniformly controlled by the combined use of the surfactants having different alkyl chain lengths and the swelling agents(triisopropyl benzene). The pore diameter of FSM 16 and MCM 41 can be expanded to be 10 nm, SBA 15 to be 15 nm. The crystal regularity was decreased with the increase of the pore diameter. In FSM 16 derived from kanemite(silicon source) and MCM 41 from water glass, their anionic characteristics on the pore wall may be stronger than those of SBA 15 derived from oligomeric tetramethoxysilane(TMOS). We have successfully used FSM 16 and MCM 41 to immobilize the enzyme having cationic residues below isoelectric point. The level of adsorption of enzymes in FSM 16 and MCM 41 was relatively high, but was low in SBA 15 support. The mechanism of enzyme to be adsorbed in mesoporous silica was suggested to be the ionic interactions. In aqueous solutions, horseradish peroxidase(HTP) was immobilized in FSM 16 with 8.9 nm mesopores and the highest loading amount(183 mg/mg FSM) was obtained, but for the FSM 16 of pore diameter 30 nm only an amount of 28 mg/mg FSM was obtained. The catalytic activity in the organic solvent was high when HRP was immobilized in FSM 16 and MCM 41, but it was low in case of SBA 15.

Loading of tacrolimus containing lipid based drug delivery systems into mesoporous silica for extended release

Many studies had been focused on designing tacrolimus sustained release preparations based on solid dispersion technique, but no one had tried to employ mesoporous silica as the carrier material to realize this goal. The purpose of this study was to develop a novel, simple and environmental friendly drug loading method with mesoporous silica to obtain tacrolimus sustained-release preparation. Tacrolimus was firstly dissolved in the molten mixed lipid composed of Compritol 888 ATO and Gelucire 50/13 to prepare a drug loaded lipid-based drug delivery systems(LBDDS), then the liquid LBDDS was adsorbed by mesoporous silica to transfer the liquid into solid powder, ie. the tacrolimus sustained release silica-lipid hybrid(SLH). The SLH was characterized by SEM, CLSM, XRPD and DSC, and the in vitro drug release was tested using a paddle method. SEM and CLSM observation showed that the LBDDS was efficiently distributed throughout the pores of the silica. The results of DSC and XRPD illustrated that the lipid existed inside the silica at amorphous state. The drug-loaded SLH showed good flowability, compressibility, compactibilty and two-phase in vitro drug release process within 24 hours, which did not change obviously even after storage at 40 °C for 10 d.The present study provided a novel and simple method to prepare tacrolimus sustained release powder, which provided a feasible solution to solidify the liquid LBDDS of not only extended drug release behavior, but also improved stability and micromeritic properties.

Amino functionalized chiral mesoporous silica nanoparticles for improved loading and release of poorly water-soluble drug

In the present paper, chiral mesoporous silica nano-cocoon(A-CMSN) functionalized with amino group was synthesized, and its loading and release of indomethacin(IMC), a poorly soluble drug, was studied. Due to the use of chiral anionic surfactants as a template, ACMSN possessed 2D hexagonal nano-cocoon morphology with curled channels on its surface, which was quite different from another 2D hexagonal mesoporous silica nanoparticles(MCM-41) with straightway channels. After being loaded into the two silica carriers by hydrogen bond, crystalline IMC converted to amorphous form, leading to the improved drug dissolution. And IMC loading capacity of A-CMSN was higher than MCM-41 because curled loading process originating from curvature chiral channels can hold more drug molecules. Compared with IMC, IMC loaded A-CMSN presented obviously fast release throughout the in vitro release experiment, while IMC loaded MCM-41 released faster than IMC at the initial 5 h then showed controlled slow release afterwards, which was closely related to the mesoporous silica nanoparticles and different channel mesostructures of these two carriers. A-CMSN possessed nano-cocoon morphology with curled 2D hexagonal channel and its channel length was shorter than MCM-41, therefore IMC molecules can easily get rid of the constraint of A-CMSN then to be surrounded by dissolution medium.