Highly dispersed metal incorporated hexagonal mesoporous silicates for catalytic cyclohexanone oxidation to adipic acid

Adipic acid is a dicarboxylic acid of great industrial importance,mainly used in the production of nylon-6,6 and polyurethane.The use of nitric acid as an oxidant in the industrial production of adipic acid poses significant carbon footprint to the environment.Clean adipic acid synthesis methods using a heterogeneous catalyst with H2O2 as oxidant and water as solvent have potential advantages of low catalyst cost,easy synthesis and recovery,cleanness and environmental protection.In this work,hexagonal mesoporous silicate materials were synthesized by a sol–gel method and evaluated for cyclohexanol/cyclohexanone oxidation to adipic acid.The physical and chemical properties of Fe-HMS were characterized by XRD,HR-TEM,BET and UV–Vis.The experimental results showed that Fe-HMS materials show pore sizes ranging from 2–3 nm.W-and Mo-based polyoxometalates were also evaluated and compared to the Fe-based HMS catalysts.To improve the adipic acid yield,the influence of the transition metal as well as the effect of metal loading,reaction temperature and catalyst amount on the catalytic performances of Fe-HMS have been investigated in details.When Si/Fe atomic ratio=100,Fe-HMS catalyst shows the highest activity,with a cyclohexanone conversion of 92.3%and adipic acid selectivity of 29.4%.The reaction pathway of cyclohexanone oxidation was further proposed based on experimental data.

Secondary Silicates as a Barrier to Carbon Capture and Storage in Deccan Basalt

Investigating the immobilization of CO2,previous basalt-water-CO2 interaction studies revealed the formation of carbonates over a short period,but with the extensive formation of secondary silicates(SS).The mechanisms involved in these processes remain unresolved,so the present study was undertaken to understand secondary mineral formation mechanisms.XRPD and Rietveld refinement data for neo-formed minerals show a drastic decrease in the Ca-O bond length,with the calcite structure degenerating after 80 h(hours).However,SEM images and EDS data revealed that a longer interaction time resulted in the formation of chlorite and smectite,adjacent to basalt grains which prevent basaltwater-CO2 interaction to form carbonates,thus restricting carbonate formation.As a result of this,the CO2 mineralization rate is initially high(till 80 h),but it later reduces drastically.It is evident that,for such temperature-controlled transformations,low temperature is conducive to minimizing SS surface coating at the time of mineral carbonation.

The structure and elasticity of phase B silicates under high pressure by first principles simulation

The structures and elasticities of phase B silicates with different water and iron（Fe） content are obtained by firstprinciples simulation to understand the effects of water and Fe on their properties under high pressure.The lattice constants a and b decrease with increasing water content.On the contrary,c increases with increasing water content.On the other hand,the b and c decrease with increasing Fe content while a increases with increasing Fe content.The decrease of M（metal）–O octahedral volume is greater than the decrease of SiO polyhedral volume over the same pressure range.The density,bulk modulus and shear modulus of phase B increase with increasing Fe content and decrease with increasing water content.The compressional wave velocity（Vp） and shear wave velocity（Vs） of phase B decrease with increasing water and Fe content.The comparisons of density and wave velocity between phase B silicate and the Earth typical structure provide the evidence for understanding the formation of the X-discontinuity zone of the mantle.

Pilot study on binding of bovine salivary proteins to grit silicates and plant phytoliths

Mostly fed with grass in fresh or conserved form,cattle and other livestock have to cope with silicate defence bodies from plants(phytoliths)and environmental silicates(grit),which abrade tooth enamel and could additionally interact with various salivary proteins.To detect potential candidates for silicate-binding proteins,bovine whole saliva was incubated with grass-derived phytoliths and silicates.Interactions of salivary proteins with pulverized bovine dental enamel and dentine were additionally analysed.After intense washing,the powder fractions were loaded onto 1D-polyacrylamide gels,most prominent adhesive protein bands were cut out and proteins were identified by mass spectrometry within three independent replicates.All materials were mainly bound by bovine odorant-binding protein,bovine salivary protein 30×10^(3) and carbonic anhydrase VI.The phytolith/silicate fraction showed additional stronger interaction with haemoglobinβand lactoperoxidase.Conceivably,the binding of these proteins to the surfaces may contribute to biological processes occurring on them.

Pilot study on binding of bovine salivary proteins to grit silicates and plant phytoliths

Mostly fed with grass in fresh or conserved form, cattle and other livestock have to cope with silicate defence bodies from plants （phytoliths） and environmental silicates （grit）, which abrade tooth enamel and could additionally interact with various salivary proteins. To detect potential candidates for silicate-binding proteins, bovine whole saliva was incubated with grass-derived phytoliths and silicates. Interactions of salivary proteins with pulverized bovine dental enamel and dentine were additionally analysed. After intense washing, the powder fractions were loaded onto 1D-polyacrylamide gels, most prominent adhesive protein bands were cut out and proteins were identified by mass spectrometry within three independent replicates. All materials were mainly botmd by bovine odorant-binding protein, bovine salivary protein 30× 10^3 and carbonic anhydrase VI. The phytolith/silicate fraction showed additional stronger interaction with haemoglobin β and lactoperoxidase. Conceivably, the binding of these proteins to the surfaces may contribute to biological processes occurring on them.

EFEECT OF METALLIC CATIONS ON Si-O BONDS IN SILICATES

The effect of metallic cations on the Si-O(br) bond and the Si-O(ter) bond was studied with CNDO/2 MO calculations. The characteristics of them were discussed, which were found to vary with the bonding and coordi nation situation of oxygen as well as the effect of metallic cations on oxygen. The conclusions obtained may be well used in the fields of mineralogy, geochemistry, silicate materials, pyrometallurgy and so on.

Nanostructured Organic Alkali-Soluble Silicates for Industrial Application

The work describes the properties of soluble organic silicates and their applications to obtain nanocomposite materials. We analyzed the properties of the water-soluble high-modulus silicate systems and their technology for producing. The aim of this paper is the comparison properties of binders based on liquid glass containing strong organic bases silicates. We have shown how these systems are transformed from lower to higher oligomers through the formation of the silica sol and the implementation of the sol-gel process for these oligomers. We have conducted advanced research of various aspects of the use of these materials as the binder. Advantages of strong organic bases silicates in the preparation of heat resistant, nanocomposite materials are shown. Ways to obtaining quaternary ammonium silicates and their use to produce nanocomposites are proposed. Products obtained in this way can be used as a binder in the preparation of nanostruetured composite materials, water-based paints, coatings, etc. Modifiers have been proposed for making of hybrid nanostructured composite materials by a sol-gel process. There have been shown of structuring phenomena some aspects, synthesis and application of hybrid materials based on silica with grafted polymers. It has been shown, the possibility of modifying compositions using the nanostructuring agents such as tetrafurfuryloxysilane. This paper also describes methods for the synthesis of products for modifying a sol-gel process using organic soluble silicates. We are displaying their use for the production of new nanocomposite materials and coatings for protection against various external factors.

Study on the Attack of Molten Silicates on Plasma-Sprayed Thermal Barrier Coatings

Thermal barrier coating (TBC) revolutionized the industry by allowing higher operating temperatures for equipment, such as gas turbines in the aeronautical industry. However, at high temperatures, the TBC is exposed to the attack of molten silicates, known as CMAS (Calcium-Magnesium-Alumino-Silicate), which are particles from the environment that infiltrate the TBC, causing delamination. In this study, samples coated with TBC by thermal spray and covered with CMAS were evaluated at temperatures of 1200˚C and 1250˚C. For each temperature, exposure times of 1 h and 5 h were used. Samples with longer exposure time had a considerable volume increase. The main contribution of this work was to demonstrate the non-wettability of the CMAS, even in the 5-h heat treatments, which prevented its infiltration in the deeper regions. The conditions to guarantee the formation of the silicate and its consequent wettability are also discussed.

Cementing properties of steel slag activated by sodium silicates and sodium hydroxide

Steel slag which is mainly composed of γ-Ca2SiO4 and other silicates or alumino-silicates is activated by sodium sificates and sodium hydroxide. The powders of such steel slag are usually inert to hydrate and subsequently have very low ability of cementing. But when sodium silicates and sodium hydroxide are used as activators the steel slag shows very good properties of cementing. When activated with NaOH solution the hardened slurry of the steel slag has a compressive strength of 11.13 MPa after being cured for 28 days. When activated with Na2SiO3 solution the samples after being cured for 28 days have an average compres- sive strength of 40.23 MPa. While the steel slag slurry which is only mixed with water has a compressive of 0.88 MPa after being cured for 28 days.

Spectroscopic Characterization and Quantitative Estimation of Natural Weathering of Silicates in Sediments of Dikrong River, India

The sediments samples were collected from the Dikrong River at various sites to assess the weathering nature and mineral characterization. The Fourier Transform Infrared (FTIR) and X-ray fluorescence (XRF) spectroscopic techniques have been used to characterization of minerals in the sediment samples. The plagioclase index of alteration (PIA), chemical index of alteration (CIA) and index of compositional variation (ICV) are investigated for evaluating the weathering nature in the sediment. The obtained results show the presence of quartz, feldspar in different structure and kaolinite as major minerals. Carbonates and organic carbon are found as minor minerals. The correlations of SiO2 with major elements are authenticated the presence of bulk quartz grains and primary depositional environment. The presence of metamorphosed pyrophanite (MnTiO3) in the adjoined areas is reported. The presence of infrared absorption peaks in between 1611 - 1622 cm?1 in this study is indicative to the weathered metamorphic origin of the silicate minerals. The index of compositional variation indicates the presence of less clay minerals and more rock forming minerals such as plagioclase and alkali-feldspar. The obtained results exhibit the area belongs to the intermediate silicate weathering.

Natural Mg silicates with different structures and morphologies: Reaction with K to produce K2MgSiO4 catalyst for biodiesel production

In this work, different magnesium silicate mineral samples based on antigorite, lizardite, chrysotile(which have the same general formula Mg3Si2O5(OH)4), and talc(Mg3Si4O10(OH)2) were reacted with KOH to prepare catalysts for biodiesel production. Simple impregnation with 20 wt% K and treatment at 700–900°C led to a solid-state reaction to mainly form the K2MgSiO4 phase in all samples. These results indicate that the K ion can diffuse into the different Mg silicate structures and textures, likely through intercalation in the interlayer space of the different mineral samples followed by dehydroxylation and K2MgSiO4 formation. All the materials showed catalytic activity for the transesterification of soybean oil(1:6 of oil : methanol molar ratio, 5 wt% of catalyst, 60°C). However, the best results were obtained for the antigorite and chrysotile precursors, which are discussed in terms of mineral structure and the more efficient formation of the active phase K2MgSiO4.

A New Model for Calculation of Standard Entropies of Solid Compounds Ⅳ-Calculation of Standard Entropies of Solid Complex Silicates S

This paper presents a new model for the calculation of the standard entropies of solidcomplex silicates as follows.4. =53.63+9914-72.81 J/kmol (R=0.9915, Sd=5.39)Sixty complex silicates have been investigated, and good agreement was found between theestimated and experimental entropy values.

Solid-state Syntheses, Crystal Chemistry and Optical Properties of Two Europium Oxide/sulfide Silicates, Eu2O(SiO4) and Eu5S(SiO4)3

Two europium oxide/sulfide silicates, Eu2O（SiO4） （1） and Eu5S（SiO4）3 （2）, have been synthesized using high-temperature solid-state reactions. 1 crystallizes in the monoclinic space group P21/c with a = 9.1459（7）, b = 7.1280（5）, c = 6.7655（5） ？ and ？ = 107.611（2）, belonging to the Gd2O（SiO4） structure type; 2 crystallizes in space group P63/m of the hexagonal system with a = 9.786（4） and c = 6.789（3） , belonging to the apatite Ca5Cl（PO4）3 structure type. The structure chemistry of related RE2O（SiO4） and RE5S（SiO4）3 compounds is also discussed. The optical energy gap of 2 is determined to be 2.05 eV.

Investigation of improving the thermophysical properties and corrosion resistance of RE_(2)SiO_(5)/RE_(2)Si_(2)O_(7)multiphase silicates by component design with RE doping

In this research,a novel method for regulating components in RE_(2)SiO_(5)/RE_(2)Si_(2)O_(7)multiphase silicates was developed,combining the benefits of a suitable thermal expansion coefficient(CTE)and outstanding corrosion resistance against calcium–magnesium–alumino–silicate(CMAS).This approach enhanced the overall thermophysical properties.Additionally,the results from the CMAS corrosion resistance test indicated that(Lu_(1/3)Yb_(1/3)Tm_(1/3))_(2)SiO_(5)/(Lu_(1/3)Yb_(1/3)Tm_(1/3))_(2)Si_(2)O_(7)and(Lu_(1/4)Yb_(1/4)Tm_(1/4)Er_(1/4))_(2)SiO_(5)/(Lu_(1/4)Yb_(1/4)Tm_(1/4)Er_(1/4))_(2)Si_(2)O_(7)exhibited exceptional resistance to CMAS penetration,even at temperatures up to 1500℃.To comprehend the corrosion mechanism of CMAS on these silicates,we introduced a reaction–diffusion model,which involved observing the changes in the interface between the corrosion product layer and the silicate block.This was achieved using electron backscatter diffraction(EBSD).These findings lay a theoretical basis for selecting rare earth elements in RE_(2)SiO_(5)/RE_(2)Si_(2)O_(7)multiphase silicates based on the radii of different rare earth cations.

Selective oxidation using in-situ generated hydrogen peroxide over titanosilicates

Titanosilicates are a class of heteroatom-containing zeolitic materials with tetrahedrally coordinated Ti^(4+)ions incorporated into crystalline zeolite frameworks,with TS-1,Ti-MWW and Ti-MOR as representative and attractive selective oxidation catalysts.The liquid-phase oxidations of a variety of substrates such as olefins and ketones with the green oxidant of H_(2)O_(2)over titanosilicates under mild conditions have attracted considerable research interests in the clean production of fine and bulk chemicals,among which propylene epoxidation and cyclohexanone ammoximation have been industrialized[1].

Electrical properties of iron doped apatite-type lanthanum silicates

The effect of Fe doping on the electrical properties of lanthanum silicates was investigated. The apatite-type lanthanum silicates La10Si6-xFexO27-x/2 （x=0.2, 0.4, 0.6, 0.8, 1.0） were synthesized via sol-gel process. The unit cell volume increased with Fe doping because the ionic radius of Fe3＋ ion is larger than that of Si4＋ ion. The conductivities of La10Si6-xFexO27 x/2 first increased and then decreased with the increasing of Fe content. The increase of the conductivity might be attributed to the distortion of the cell lattice, which assisted the migration of the interstitial oxygen ions. The decrease of the conductivity might be caused by the lower concentration of interstitial oxygen ions. The optimum Fe doping content in lanthanum silicates was 0.6. La10Si5.4Fe0.6O26.7 exhibited the highest ionic conductivity of 2.712× 10^-2 S/cm at 800 ℃. The dependence of conductivity on oxygen partial pressure p（O2） suggested that the conductivity of La10Si6-xFexO27-x/2 was mainly contributed by ionic conductivity.

Rare earth monosilicates as oxidation resistant interphase for SiCf/SiC CMC:Investigation of SiC_(f)/Yb_(2)SiO_(5)model composites

Model composites consisting of SiC fiber and Yb_(2)SiO_(5)were processed by the spark plasma sintering(SPS)method.The mechanical compatibility and chemical stability between Yb_(2)SiO_(5)and SiC fiber were studied to evaluate the potential application of Yb monosilicate as the interphase of silicon carbide fiber reinforced silicon carbide ceramic matrix composite(SiC_(f)/SiC CMC).Two kinds of interfaces,namely mechanical and chemical bonding interfaces,were achieved by adjusting sintering temperature.SiC_(f)/Yb_(2)SiO_(5)interfaces prepared at 1450 and 1500℃exhibit high interface strength and debond energy,which do not satisfy the crack deflection criteria based on He-Hutchison diagram.Raman spectrum analyzation indicates that the thermal expansion mismatch between Yb_(2)SiO_(5)and SiC contributes to high compressive thermal stress at interface,and leads to high interfacial parameters.Amorphous layer at interface in model composite sintered at 1550℃is related to the diffusion promoted by high temperature and DC electric filed during SPS.It is inspired that the interfacial parameters could be adjusted by introducing Yb_(2)Si_(2)O_(7)-Yb_(2)SiO_(5)interphase with controlled composition to optimize the mechanical fuse mechanism in SiC_(f)/SiC CMC.

Dispersion and Filler Network Structure of Fibrillar Silicates in Elastomers

The dispersion and filler network of fibrillar silicate（FS） in elastomers were studied. The results showed that a good dispersion of FS in matrix during mechanical blending in unvulcanized composites contributed to a strong FS filler network, different from that of traditional reinforcing fillers. Meanwhile, the filler re-aggregation during vulcanization caused by the overlapping and intertwining of FS further strengthened the filler network. The factors including Mooney viscosity and molecular polarity of elastomer, type and amount of silane coupling agents used for filler modification, that may influence the filler network, were studied. Our study helps us to understand the mechanism for the formation of filler network of FS in elastomers and provides guidance for the preparation of high performance FS/elastomer composites.

Accelerating the design of multicomponent rare earth silicates for SiC_(f)/SiC CMC by combinatorial material chip design and high throughput screening

High throughput experimentation is employed to establish a ternary system with the compositional range of 30.8 mol.%-75.7 mol.%SiO_(2),16.6 mol.%-61.7 mol.%Yb_(2)O_(3),and 6.3 mol.%-4.1 moll.%Ho_(2)O_(3) through co-sputtering deposition on one combinatorial material chip.Considering their application in advanced SiC_(f)/SiC CMC,the phase composition and mechanical properties of samples with various RE/Si ratios and Yb/Ho ratios are comprehensively investigated.Chemical stability and thermal expansion compatibility between SiC and RE silicates with different compositions are also validated.Optimized materials for the application of environmental barrier coating and interphase for SiC_(f)/SiC CMC are screened respectively according to the above trends and data.This work is a case study to establish a composition-property library for RE_(2)O_(3)-SiO_(2) compounds.It is inspired more complicated multicomponent RE silicates could be prepared and characterized by high throughput experimentation,accelerating the design and screening of promising optimal candidates.