Solvent-free nanocasting toward universal synthesis of ordered mesoporous transition metal sulfide@N-doped carbon composites for electrochemical applications

Transition metal sulfides (TMSs) have a wide range of applications owing to their intriguing properties.Significant efforts have been devoted to nanostructuring TMSs to enhance their properties and performance,still there is a high need in general synthesis of TMS nanostructures.Herein,for the first time,a simple solvent free reactive nanocasting approach that integrates solid precursor loading,in-situ sulfuration and carbonization into a single heating step is developed for the universal synthesis of ordered mesoporous TMS@N-doped carbon composites (denoted as OM-TMS@NCs) with methionine (Met) and metal chlorides as the precursors and the mesoporous silica (SBA-15) as the hard template.A series of OM-TMS@NCs with a hexagonal mesostructure,ultra-high surface areas (430-754 m2·g-1),large pore volumes (0.85-1.32 cm3·g-1),and unique TMS stoichiometries,including MoS2,Fe7S8,Co9S8,NiS,Cu7S4 and ZnS,are obtained.Two distinct structure configurations,namely,highly dispersed ultrathin TMS nanosheets within NCs and TMS@NC co-nanowire arrays,can be obtained depending on different metals.The structure evolution of the OM-TMS@NCs over the solvent-free nanocasting process is studied in detail for a deep understanding of the synthesis.As demonstrations,these materials are promising for electrocatalytic hydrogen evolution reaction and lithium ion storage with high performances.

Mesoporous carbon adsorbents from melamine–formaldehyde resin using nanocasting technique for CO_2 adsorption

Mesoporous carbon adsorbents, having high nitrogen content, were synthesized via nanocasting technique with melamine-formaldehyde resin as precursor and mesoporous silica as template. A series of adsorbents were prepared by varying the carbonization temperature from 400 to 700°C. Adsorbents were characterized thoroughly by nitrogen sorption, X-ray diffraction（XRD）, scanning electron microscopy（SEM）, transmission electron microscopy（TEM）, thermogravimetric analysis（TGA）, elemental（CHN） analysis, Fourier transform infrared（FTIR） spectroscopy and Boehm titration. Carbonization temperature controlled the properties of the synthesized adsorbents ranging from surface area to their nitrogen content, which play major role in their application as adsorbents for CO2 capture.The nanostructure of these materials was confirmed by XRD and TEM. Their nitrogen content decreased with an increase in carbonization temperature while other properties like surface area, pore volume, thermal stability and surface basicity increased with the carbonization temperature. These materials were evaluated for CO2 adsorption by fixed-bed column adsorption experiments. Adsorbent synthesized at 700°C was found to have the highest surface area and surface basicity along with maximum CO2 adsorption capacity among the synthesized adsorbents. Breakthrough time and CO2 equilibrium adsorption capacity were investigated from the breakthrough curves and were found to decrease with increase in adsorption temperature. Adsorption process for carbon adsorbent-CO2 system was found to be reversible with stable adsorption capacity over four consecutive adsorption-desorption cycles. From three isotherm models used to analyze the equilibrium data, Temkin isotherm model presented a nearly perfect fit implying the heterogeneous adsorbent surface.

Synthesis of a new ordered mesoporous NiMoO_4 complex oxide and its efficient catalytic performance for oxidative dehydrogenation of propane

Highly ordered mesoporous NiMoO4 material was successfully synthesized using mesoporous silica KIT-6 as hard template via vacuum nanocasting method. The structure was characterized by means of XRD, TEM, N2 adsorption-desorption, Raman and FT-IR. The mesoporous NiMoO4 with the coexistence of a-NiMoO4 and fl-NiMoO4 showed well-ordered mesoporous structure, a bimodal pore size distribution and crystalline framework. The catalytic performance of NiMoOa was investigated for oxidative dehydrogenation of propane. It is demonstrated that the mesoporous NiMoO4 catalyst with more surface active oxygen species showed better catalytic performance in oxidative dehydrogena- tion of propane in comparison with bulk NiMoO4.

Pore structure effects on the kinetics of methanol oxidation over nanocast mesoporous perovskites

Mesoporous LaMnO3 perovskite catalysts with high surface area were synthesized by using the recently developed hard templating method designated as ＂nanocasting＂.Ordered mesoporous silica designated as SBA-15 was used as the hard template.It was found that the surface area of the nanocast perovskites can be tuned（80–190 m2/g）by varying the aging temperature of the SBA-15 template.Nanocast LaMnO3 catalysts showed high conversion efficiencies for the total oxidation of methanol under steady state conditions,the one with the highest value of surface area being the best catalysts,as expected.Kinetic studies were performed for all of the synthesized catalysts.Rate constants were found to vary in accordance with the specific surface area of the nanocast catalyst which depends on the aging temperature of the parent template.From the rate constants obtained from experimental conversions at various space velocities（19500 to 78200 h〈sup〉–1）,values of activation energy and pre-exponential factor for the three nanocast LaMnO3 catalysts were determined by the linear regression of the Arrhenius plot.It is observed that the activation energy for all the catalysts remain constant irrespective of the variation in specific surface area.Further,a linear relationship was found to exist between the pre-exponential factor and specific surface areas of the catalysts indicating that the rates per unit surface area remains the same for all the catalysts.

用于合成新型1,3,5-三芳基吡唑啉衍生物的磷钨酸铯盐的纳米塑形、模板合成及结构研究(英文)

The elimination of the silica matrix of composites by HF occurred by a two-step reaction deposition of a Cs2.5H0.5PW12O40(CsHPW) salt nanocrystal.We used 2D hexagonal SBA-15 silica as a template for the nanofabrication of CsHPW nanoparticles.Nanocast CsHPW materials are stable against leaching and colloidization in polar solvents.The catalytic performance of the nanocast CsHPW materi-als exceeded that of bulk Cs2.5H0.5PW12O40,which is the most active among the acidic HPW salts.A series of novel 1,3,5-triaryl-pyrazoline derivatives were synthesized by the reaction between chalcone and phenylhydrazine in high yield in the presence of CsHPW salt nanocrystals.

Synthesis of Ordered Cubic Periodic Mesoporous Silica with High Hydrothermal Stability

1 Introduction Since its first discovery in 1992, ordered mesoporous silica material with large pore size, high surface area, and high pore volume has attracted great attention for the potentially wide application in catalysis, adsorption, separation, and ion exchange, etc. However, the poor hydrothermal stability of mesoporous silica has limited its wide application in industry. Therefore, in the last 10 years, many studies have been dedicated to improving the hydrothermal stability of mesoporous silica. Xiao et al.

Synthesis of Mesostructured Iron Oxides with Potential As(V) Adsorption Application

Mesostructured iron oxides（MIOs） were nanocasted from a plugged hexagonal templated silica（PHTS） with a Brunauer-Emmett-Teller（BET） surface area of 694 m 2 /g.Results of X-ray diffraction（XRD）,transmission electron microscopy（TEM） and N 2 adsorption-desorption suggest that the nanocasted MIOs are synthetic hematite（α-Fe2O3） with a wormhole-like mesoporous network.As（V） adsorption test shows that the selected MIO—MIO-500（calcinated at 500 °C） with a BET surface area of 82 m^ 2 /g has a maximum adsorption capacity of 5.39 mg/g for As（V）,which is 2.5 times as large as that of natural hematite adsorbent.The study suggests that MIOs could be potentially used as the adsorbent of As（V） in wastewater.

Facile Synthesis of Porous Carbon Nitride Spheres with Hierarchical Three-Dimensional Mesostructures for CO_(2) Capture

Porous carbon nitride(CN)spheres with partially crystalline frameworks have been successfully synthesized via a nanocasting approach by using spherical mesoporous cellular silica foams(MCFs)as a hard template,and ethylenediamine and carbon tetrachloride as precursors.The resulting spherical CN materials have uniform diameters of ca.4μm,hierarchical three-dimensional(3-D)mesostructures with small and large mesopores with pore diameters centered at ca.4.0 and 43 nm,respectively,a relatively high BET surface area of~550 m^(2)/g,and a pore volume of 0.90 cm^(3)/g.High-resolution transmission electron microscope(HRTEM)images,wide-angle X-ray diffraction(XRD)patterns,and Raman spectra demonstrate that the porous CN material has a partly graphitized structure.In addition,elemental analyses,X-ray photoelectron spectra(XPS),Fourier transform infrared spectra(FT-IR),and CO_(2) temperature-programmed desorption(CO_(2)-TPD)show that the material has a high nitrogen content(17.8 wt%)with nitrogen-containing groups and abundant basic sites.The hierarchical porous CN spheres have excellent CO_(2) capture properties with a capacity of 2.90 mmol/g at 25℃and 0.97 mmol/g at 75℃,superior to those of the pure carbon materials with analogous mesostructures.This can be mainly attributed to the abundant nitrogen-containing basic groups,hierarchical mesostructure,relatively high BET surface area and stable framework.Furthermore,the presence of a large number of micropores and small mesopores also enhance the CO_(2) capture performance,owing to the capillary condensation effect.

Mesoporous Co3O4 as an electrocatalyst for water oxidation

MesoporousCo3O4 has been prepared using porous silica as a hard template via a nanocasting route and its electrocatalytic properties were investigated as an oxygen evolution catalyst for the electrolysis of water. The ordered mesostructured Co3O4 shows dramatically increased catalytic activity compared to that of bulk Co3O4. Enhanced catalytic activity was achieved with high porosity and surface area, and the water oxidation overpotential （η） of the ordered mesoporous Co3O4 decreases significantly as the surface area increases. The mesoporous Co3O4 also shows excellent structural stability in alkaline media. After 100 min under 0.8 V （versus Ag/AgC1） applied bias, the sample maintains the ordered mesoporous structure with little deactivation of the catalytic properties.

Catalytic oxidation of benzene over nanostructured porous Co_3O_4-CeO_2 composite catalysts

Mesostructured Co3O4-CeO2 composite was found to be an effective catalytic material for the complete oxidation of benzene. The Co3O4-CeO2 catalysts with different Co/Ce ratios （mol/mol） were prepared via the nanocasting method and the mesostructure was replicated from two-dimensional （2D） hexagonal SBA-15 and three-dimensional （3D） cubic KIT-6 silicas, respectively. All the obtained Co3O4-CeO2 catalysts exhibited the similar symmetry with the parent silicas and well ordered mesostructures. The Co3O4- CeO2 catalysts with 2D mesostructure showed lower catalytic activities than the corresponding 3D materials. The Co3O4-CeO2 catalyst nanocasted from KIT-6 and with the Co/Ce ratio of 16/1 possessed the best catalytic benzene oxidation activity due to larger quantities of surface hydroxyl groups and surface oxygenated species. The mesostructured Co3O4-CeO2 material thus shows great potential as a promising eco-environmental catalyst for benzene effective elimination.

Controlling synthesis and gas-sensing properties of ordered mesoporous In2O3-reduced graphene oxide(r GO) nanocomposite

Herein, we describe a strategy for fabricating ordered mesoporous In2O3-reduced graphene oxide(r GO)nanocomposite through ultrasonic mixing, where ordered mesoporous In2O3 nanoparticles are synthesized via the nanocasting route by using mesoporous silica as a hard template, which possess ordered mesostructure with a large surface area of 81 m2g-1, and r GO nanosheets are synthesized from graphite via graphene oxide(GO) as intermediate. After coupled with r GO, mesoporous In2O3 could maintain its ordered mesostructure. We subsequently investigate the gas-sensing properties of all the In2O3 specimens with or without r GO for different gases. The results exhibit the ordered mesoporous In2O3-r GO nanocomposite possesses significantly enhanced response to ethanol even at low concentration levels, superior over pure mesoporous In2O3 nanoparticles. Similar strategy could be extended to other ordered mesoporous metal oxide–r GO nanocomposite for improving the gas-sensing property.