Comparative study on Al-SBA-15 prepared by spray drying and traditional methods for bulky hydrocarbon cracking: Properties, performance and influencing factors.

Mesoporous aluminosilicates Al-SBA-15 with large pore sizes and suitable acid properties are promising substitutes to zeolites for catalytic cracking of bulky hydrocarbons without molecular diffusion limitation. The conventional processes to synthesize Al-SBA-15 are time-consuming and often suffer from low "framework" Al contents. Herein, Al-SBA-15 microspheres are synthesized using the rapid and scalable microfluidic jet spray drying technique. They possess uniform particle sizes (45-60 µm), variable surface morphologies, high surface areas (264-340 m2/g), uniform mesopores (3.8-4.9 nm) and rich acid sites (126-812 µmol/g) and high acid strength. Their physicochemical properties are compared with the counterparts synthesized using traditional hydrothermal and evaporation-induced self-assembly methods. The spray drying technique results in a higher incorporation of aluminum (Al) atoms into the silica "framework" compared to the other two methods. The catalytic cracking efficiencies of 1,3,5-triisopropylbenzene (TIPB) on the Al-SBA-15 materials synthesized using the three different methods and nanosized ZSM-5 are compared. The optimal spray-dried Al-SBA-15 exhibits the best performance with 100 % TIPB conversion, excellent selectivity (about 75 %) towards the formation of deeply cracked products (benzene and propylene) and high stability. The catalytic performances of the spray-dried Al-SBA-15 with varying Si/Al ratios are also compared. The reasons for the different performances of the different materials are discussed, where the mesopores, high acid density and strength are observed to play the most critical role. This work might provide a basis for the synthesis of mesoporous rich metal-substituted silica materials for different catalytic applications.

Ultrahigh Surface Area N-Doped Hierarchically Porous Carbon for Enhanced CO2 Capture and Electrochemical Energy Storage.

Facile synthesis of ultrahigh surface area porous carbons with well-defined functionalities such as N-doping remains a formidable challenge as extensive pore creation results in significant damage to the active sites. Herein, an ultrahigh surface area, N-doped hierarchically porous carbon was prepared through a multicomponent co-assembly approach. The resultant N-doped hierarchically porous carbon (N-HPC) possessed an ultrahigh surface area (≈1960 m2 g-1 ), a uniform interpenetrating micropore (≈1.3 nm) and large mesopore (≈7.6 nm) size, and high N-doping in the carbon frameworks (≈5 wt %). The N-HPC exhibited a high specific capacitance (358 F g-1 at 0.5 A g-1 ) as a supercapacitor electrode in aqueous alkaline electrolyte with a stable cycling performance after10 000 charge/discharge cycles. Moreover, as a CO2 absorbent, N-HPC displayed an adsorption capacity of 29.0 mmol g-1 at 0 °C under a high pressure of 30 bar.

Selective Molecular Separation by Interfacially Crystallized Covalent Organic Framework Thin Films.

Exponential interest in the field of covalent organic frameworks (COFs) stems from the direct correlation between their modular design principle and various interesting properties. However, existing synthetic approaches to realize this goal mainly result in insoluble and unprocessable powders, which severely restrict their widespread applicability. Therefore, developing a methodology for easy fabrication of these materials remains an alluring goal and a much desired objective. Herein, we have demonstrated a bottom-up interfacial crystallization strategy to fabricate these microcrystalline powders as large-scale thin films under ambient conditions. This unique design principle exploits liquid-liquid interface as a platform, allowing simultaneous control over crystallization and morphology of the framework structure. The thin films are grown without any support in free-standing form and can be transferred onto any desirable substrate. The porous (with Tp-Bpy showing highest SBET of 1 151 m2 g-1) and crystalline thin films, having high chemical as well as thermal stability, also hold the merit to tune the thickness as low as sub-100 nm. These nanostructured thin COF films demonstrate remarkable solvent-permeance and solute-rejection performance. A prominent instance is the Tp-Bpy thin film, which displays an unprecedented acetonitrile permeance of 339 L m-2 h-1 bar-1.

Mesoporous Silica Thin Membranes with Large Vertical Mesochannels for Nanosize-Based Separation.

Membrane separation technologies are of great interest in industrial processes such as water purification, gas separation, and materials synthesis. However, commercial filtration membranes have broad pore size distributions, leading to poor size cutoff properties. In this work, mesoporous silica thin membranes with uniform and large vertical mesochannels are synthesized via a simple biphase stratification growth method, which possess an intact structure over centimeter size, ultrathin thickness (≤50 nm), high surface areas (up to 1420 m2 g-1 ), and tunable pore sizes from ≈2.8 to 11.8 nm by adjusting the micelle parameters. The nanofilter devices based on the free-standing mesoporous silica thin membranes show excellent performances in separating differently sized gold nanoparticles (>91.8%) and proteins (>93.1%) due to the uniform pore channels. This work paves a promising way to develop new membranes with well-defined pore diameters for highly efficient nanosize-based separation at the macroscale.

Mesoporous TiO2@N-doped carbon composite nanospheres synthesized by the direct carbonization of surfactants after sol-gel process for superior lithium storage.

Here, we report mesoporous TiO2@N-doped carbon composite nanospheres synthesized via a double-surfactant-assisted assembly sol-gel process followed by sequential carbonization of surfactants under a N2 atmosphere. The resulting TiO2@N-doped C composite nanospheres are composed of uniformly distributed TiO2 nanocrystals with a diameter of ∼8 nm coated by a N-doped carbon layer that was formed by surfactants. Moreover, a large number of connected mesopores were observed in the nanospheres after high-temperature carbonization treatment. The synthesized nanospheres possess a large specific surface area (∼120 m2 g-1) and a large pore size (4-40 nm), with a well-defined spherical structure and a diameter in the nanoscale range. As an anode material for lithium-ion batteries (LIB), the mesoporous composite nanospheres delivered a reversible capacity of ∼117 mA h g-1 after 2000 cycles at a current rate as high as 10 C, as well as superior rate capability. The N-doped carbon layers greatly improved the overall electrical conductivity of the mesoporous TiO2 nanospheres. This study provides a remarkable synthetic route for the preparation of mesoporous TiO2-based N-doped carbon composite materials as high-performance anode materials in LIBs.

Scalable synthesis of mesoporous titania microspheres via spray-drying method.

Mesoporous TiO2 has several potential applications due to its unique electronic and optical properties, although its structures and morphologies are typically difficult to tune because of its uncontrollable and fast sol-gel reaction. In this study we have coupled the template-directed-sol-gel-chemistry with the low-cost, scalable, and environmentally benign aerosol (spray-drying) one-pot preparation technique for the fabrication of hierarchically mesoporous TiO2 microspheres and Fe3O4@mesoporous TiO2-x microspheres in a large scale. Parameters during the pre-hydrolysis and spray-drying treatment were varied to successfully control the bead diameter, morphology, monodispersity, surface area and pore size for improving their effectiveness for better application. Unlike to the previous aerosol synthetic approaches, where mainly quite a high temperature gradient with the strict control of spray-drying precursor concentration is implied, our strategy is lying on comparatively low drying temperature with an additional post-ultrasonication (further hydrolysis and condensation) route of the pre-calcined TiO2 samples. As-synthesized mesoporous microspheres have a size distribution from 500nm to 5µm, specific surface areas ranging from 150 to 162m(2)g(-1) and mean pore sizes of several nanometers (4-6nm). Further Fe3O4@mesoporous TiO2-x microspheres were observed to show remarkable selective phosphopeptide-enrichment activity which might have significant importance in disease diagnosis and other biomedical applications.

Carbon functionalized mesoporous silica-based gas sensors for indoor volatile organic compounds.

Indoor organic gaseous pollution is a global health problem, which seriously threats the health and life of human all over the world. Hence, it is important to fabricate new sensing materials with high sensitivity and efficiency for indoor volatile organic compounds. In this study, a series of ordered mesoporous silica-based nanocomposites with uniform carbon coatings on the internal surface of silica mesopore channels were synthesized through a simple template-carbonization strategy. The obtained mesoporous silica-carbon nanocomposites not only possess ordered mesostructures, high surface areas (up to ∼759m(2)g(-1)), large and tunable pore sizes (2.6-10.2nm), but also have the improved hydrophobicity and anti-interference capability to environmental humidity. The sensing performances of the mesoporous silica-carbon nanocomposites to volatile organic compounds, such as ethylbenzene, methylbenzene, benzene, methanol, acetone, formaldehyde, dichloromethane and tetrahydrofuran, were systematically investigated. The relationships between the sensing performances and their properties, including mesostructures, surface areas, pore sizes, carbon contents and surface hydrophilic/hydrophobic interactions, have been achieved. The mesoporous silica-carbon nanocomposites with hexagonal mesostructure exhibit outstanding performance at room temperature to benzene and acetone with high responses, short response (2-3s) and recovery (16-19s) time, strong anti-interference to environmental humidity, and long-term stability (less than ∼5% loss of the frequency shifts after 42days). Therefore, the obtained mesoporous silica-carbon nanocomposites have a hopeful prospect in the field of environmental air quality monitoring.

Electrochemical determination of nitrite using silver nanoparticles modified electrode.

In this work, we report the fabrication and characterization of silver nanoelectrode ensembles (Ag-NEEs) on a glassy carbon electrode. For this purpose, Ag nanoparticles (NPs) were anchored to the mercaptopropyl functionalized MCM-41 type silica spheres utilizing the chemisorption property of Ag NPs by -SH groups. The successful anchoring of Ag NPs into the silica matrix is characterized by several techniques including UV-vis diffuse reflectance and X-ray powder diffraction methods. The surface morphology of the Ag-NEEs was assessed by scanning and transmission electron microscopy (SEM and TEM respectively). Further, nitrite (NO(2)(-)) is electrocatalytically oxidized at Ag-NEEs, which leads to a sensitive determination of NO(2)(-). The fabrication, characterization, and efficient sensing of NO(2)(-) at the Ag-NEEs are presented.

Zinc phthalocyanine and silver/gold nanoparticles incorporated MCM-41 type materials as electrode modifiers.

Mercaptopropyl functionalized ordered mesoporous silica spheres were prepared (MPS). Ag or Au nanoparticles (NPs) were anchored onto the MPS materials (Ag-MPS or Au-MPS). Further, zinc phthalocyanine (ZnPc) was adsorbed into the channels and surface (MPS-ZnPc, Ag-MPS-ZnPc, Au-MPS-ZnPc). Diffuse reflectance studies revealed the successful incorporation of Ag or Au NPs inside the silica spheres with and without ZnPc. TEM images showed the uniform distribution of Ag or Au NPs in the silica spheres of different size ranging from 4 to 22 nm or 6 to 31 nm, respectively. XRD pattern showed average crystallite particle size of 18 or 28 nm for Ag or Au NPs respectively which were reduced to 14 or 16 nm on introduction of ZnPc which oxidizes the metal NPs partially. Chemically modified electrodes were prepared by coating the colloidal solutions of the silica materials on the glassy carbon (GC) electrodes. Electrocatalytic reductions of O(2) and CO(2) at the modified electrodes were studied. The presence of Ag or Au NPs was found to increase the electrocatalytic efficiency of ZnPc toward O(2) reduction by 290% or 70% based on the current density measured at -0.35 V and toward CO(2) reduction by 150% or 120% based on the current density measured at -0.60 V respectively. Catalytic rate constants were increased 2-fold for O(2) reduction and 8-fold for CO(2) reduction due to Ag or Au NPs, respectively, which act as nanoelectrode ensembles. The synergic effect of ZnPc and metal NPs on the electrocatalytic reduction of O(2) is presented.