Oxidative desulfurization of model and real oil samples using Mo supported on hierarchical alumina–silica: Process optimization by Box–Behnken experimental design

The catalytic performance of Mo supported on hierarchical alumina–silica(Si/Al = 15) with Mo loadings of 3, 6 and 15 wt% was investigated for the oxidative desulfurization(ODS) of model and real oil samples. Hierarchical alumina–silica(h Al–Si) was synthesized by economical and ecofriendly silicate-1 seed-induced route using cetyltrimethylammonium bromide(CTAB) as mesoporogen. The effect of CTAB on the structure of catalyst was studied by characterization techniques. The results revealed that 6%Mo/h Al–Si had the highest sulfur removal compared to the other catalyst loadings. The effect of operating parameters was evaluated using Box–Behnken experimental design. The optimal desulfurization conditions with the 6%Mo/h Al–Si catalyst were determined at oxidation temperature of 67 ℃, oxidation time of 42 min, H2O2/S molar ratio of 8 and catalyst dosage of 0.008 g·ml^-1 for achieving a conversion of 95%. Under optimal conditions, different sulfur-containing compounds with initial concentration of 1000 ppm, Dibenzothiophene(DBT), Benzothiophene(BT) and Thiophen(Th), showed the catalytic oxidation reactivity in the order of DBT > BT>Th. According to the regeneration experiments, the 6%Mo/h Al–Si catalyst was reused 4 times with a little reduction in the performance. Also, the total sulfur content of gasoline and diesel after ODS process reached 156.6 and 4592.2 ppm, respectively.

Effect of Sodium Tripolyphosphate and Silica Fume on Hydration of High Alumina Cement

It was found that silica fume can reduce the maximum hydration heat release rate of cement by microcalorimetry,inhibit CAH_(10),promote the generation of C_(3)AH_(6)and strätlingite C_(2)ASH_(8),or promote the conversion of CAH_(10)to C_(3)AH_(6).Sodium tripolyphosphate can retard the early hydration of cement,have a slight effect on 1 d hydration products of cement and inhibit the generation hydration products.Sodium tripolyphosphate and silica fume can promote the early hydration of cement,advance the formation of C_(2)ASH_(8)or the conversion from CAH_(10)to C_(3)AH_(6)at 1 d.

Combined Promoting Effects of Specific Organic Functional Groups and Alumina Surface Characteristics for the Design of a Highly Efficient NiMo/Al_(2)O_(3) Hydrodesulfurization Catalyst

To prepare a highly efficient NiMo/Al_(2)O_(3) hydrodesulfurization catalyst,the combined effects of specific organic functional groups and alumina surface characteristics were investigated.First,the correlation between the surface characteristics of four different alumina and the existing Mo species states was established.It was found that the Mo equilibrium adsorption capacity can be used as a specific descriptor to quantitatively evaluate the changes in surface characteristics of different alumina.A lower Mo equilibrium adsorption capacity for alumina means weaker metal-support interaction and the loaded Mo species are easier to transform into MoS2.However,the Mo-O-Al bonds still exist at the metal-support interface.The introduction of cationic surfactant hecadecyl trimethyl ammonium bromide(CTAB)can further improve Mo species dispersion through electrostatic attraction with Mo anions and interaction of its alkyl chain with the alumina surface;meanwhile,the introduction of ethylenediamine tetraacetic acid(EDTA)can complex with Ni ions to enhance the Ni-promoting effect on Mo.Therefore,the NiMo catalyst designed using alumina with lower Mo equilibrium adsorption capacity and the simultaneous addition of EDTA and CTAB exhibits the highest hydrodesulfurization activity for 4,6-dimethyl dibenzothiophene because of its proper metal-support interaction and more well-dispersed Ni-Mo-S active phases.

Nano-alumina@cellulose-coated separators with the reinforcedconcrete-like structure for high-safety lithium-ion batteries

Separators play a critical role in the safety and performance of lithium-ion batteries.However,commercial polyolefin separators are limited by their poor affinity with electrolytes and low melting points.In this work,we constructed a reinforced-concrete-like structure by homogeneously dispersing nano-Al_(2)O_(3) and cellulose on the separators to improve their stability and performance.In this reinforcedconcrete-like structure,the cellulose is a reinforcing mesh,and the nano-Al_(2)O_(3) acts as concrete to support the separator.After constructing the reinforced-concrete-like structure,the separators exhibit good stability even at 200℃(thermal shrinkage of 0.3%),enhanced tensile strain(tensile stress of 133.4 MPa and tensile strains of 62%),and better electrolyte wettability(a contact angle of 6.5°).Combining these advantages,the cells with nano-Al_(2)O_(3)@cellulose-coated separators exhibit stable cycling performance and good rate performance.Therefore,the construction of the reinforced-concretelike structure is a promising technology to promote the application of lithium-ion batteries in extreme environments.

Silica nanoparticle design for colorectal cancer treatment:Recent progress and clinical potential

Colorectal cancer(CRC)is the third most common cancer worldwide and the second most common cause of cancer death.Nanotherapies are able to selectively target the delivery of cancer therapeutics,thus improving overall antitumor eff-iciency and reducing conventional chemotherapy side effects.Mesoporous silica nanoparticles(MSNs)have attracted the attention of many researchers due to their remarkable advantages and biosafety.We offer insights into the recent advances of MSNs in CRC treatment and their potential clinical application value.

Gypsum-based Silica Gel Humidity-controlling Composite Materials:Preparation,Characterization,and Performance

Gypsum was used as substrate,and silica gel was mixed into substrate at a certain mass ratio to prepare humidity-controlling composites;moreover,the moisture absorption and desorption properties of gypsum-based composites were compared with adding different silica gel particle size and proportion.The morphological characteristics,the isothermal equilibrium moisture content curve,moisture absorption and desorption rate,moisture absorption and desorption stability,and humidity-conditioning performance were tested and analyzed.The experimental results show that,compared with pure-gypsum,the surface structure of the gypsum-based composites is relatively loose,the quantity,density and aperture of the pores in the structure increase.The absorption and desorption capacity increase along with the increase of silica gel particle size and silica gel proportion.When 3 mm silica gel particle size is added with a mass ratio of 40%,the maximum equilibrium moisture content of humidity-controlling composites is 0.161 g/g at 98% relative humidity(RH),3.22 times that of pure-gypsum.The moisture absorption and desorption rates are increased,the equilibrium moisture absorption and desorption rates are 2.68 times and 1.61 times that of pure-gypsum at 58.5% RH,respectively.The gypsum-based composites have a good stability,which has better timely response to dynamic humidity changes and can effectively regulate indoor humidity under natural conditions.

New Data on Coal, Gypsum, Iron and Silica Sand Deposits and Geochemical Exploration (Pakistan): Revision of 25 Years History of Dinosaur Discoveries from Pakistan

Discoveries of many coal seams at depths by drilling carried by Geological Survey of Pakistan in Sor Range and Harnai Gochina, extended the coal seams at depth which is challenge for mine owners to exploit feasibly. Bed to bed gypsum samplings (and their chemical analyses) of huge gypsum deposits from Sulaiman foldbelt is a base for industrialist and also planers to develop cement and gypsum industries to increase export and foreign exchange for the development of area and Pakistan. Low and high grade sedimentary iron deposits, silica sand and uranium host rocks and their extensions in Sulaiman and Kirthar foldbelts are presented. Anomalies of a few base metals arise as a result of geochemical exploration carried at part of Loralai District of Balochistan. Theropod dinosaurs were frequent in India, while Poripuchian titanosaurs (Sauropoda, Dinosauria) were frequent in Pakistan. Besides some ichnotaxa, many bone taxa such as 1 titanosauriform, 14 titanosaurian sauropod (including one new titanosaur), and 3 theropod dinosaurs are established from Pakistan. Among these 12 titanosaur species and 3 theropod species are named in about 10 km2 area of Vitakri dome and 2 titanosaur species are named in about a few hundred square meter area of Mari Bohri (Kachi Bohri) which is about 10 km westward from Vitakri dome. Pakistan is a unique country which discoverd 14 diversified titanosaurs in a short area and also in a short period (67 - 66 million years ago/Ma). About 400 bones found from a few meter thick upper part of upper shale horizon of latest Maastrichtian Vitakri Formation which is base for titanosaur taxa. Cranial material is in low fraction (but include significant diverse snouts), caudal vertebrae are prominent, the cervicals, dorsals and sacrals have significant numbers, forelimb and hind limb bones have balanced fraction. Humeri, femora and tibiae are most common. To know the position of Pakistani titanosaurs among titanosaurs and sauropods, there is a need to extend list of characters for phylogenetic analyses. This broad feature list should include main characters of titanosaurs from Pakistan and also from global world.

Green synthesis of ZSM-5 using silica fume and catalytic co-cracking of lignin and plastics for production of monocyclic aromatics

ZSM-5 with hierarchical pore structure was synthesized by a simple two-step hydrothermal crystallization from silica fume without using any organic ammonium templates.The synthesized ZSM-5 were oval shaped particles with a particle size about 2.0 μm and weak acid-dominated with proper Brønsted(B)and Lewis(L)acid sites.The ZSM-5 was used for catalytic co-cracking of n-octane and guaiacol,lowdensity polyethylene(LDPE)and alkali lignin(AL)to enhance the production of benzene,toluene,ethylbenzene and xylene(BTEX).The most significant synergistic effect occurred at n-octane/guaiacol at 1:1 and LDPE/AL at 1:3,under the condition,the achieved BTEX selectivity were 24%and 33%(mass)higher than the calculated values(weighted average).The highest BTEX selectivity reached 88.5%,which was 3.7%and 54.2%higher than those from individual cracking LDPE and AL.The synthesized ZSM-5 exhibited superior catalytic performance compared to the commercial ZSM-5,indicating potential application prospect.

Al-modified yolk-shell silica particle-supported NiMo catalysts for ultradeep hydrodesulfurization of dibenzothiophene and 4,6-dimethyldibenzothiophene:Efficient accessibility of active sites and suitable acidity

Yolk-shell SiO2 particles(YP)with center-radial meso-channels were fabricated through a simple and effective method.Al-containing YP-supported NiMo catalysts with different Al amounts(NiMo/AYP-x,x=Si/Al molar proportion)were prepared and dibenzothiophene(DBT)and 4,6-dimethyl-dibenzothiophene(4,6-DMDBT)were employed as the probes to evaluate the hydrodesulfurization(HDS)catalytic performance.The as-prepared AYP-x carriers and corresponding catalysts were characterized by some advanced characterizations to obtain deeper correlations between physicochemical properties and the HDS performance.The average pore sizes of series AYP-x supports are above 6.0 nm,which favors the mass transfer of organic sulfides.The cavity between the yolk and the shell is beneficial for the enrichment of S-containing compounds and the accessibility between reactants and active metals.Aluminum embedded into the silica framework could facilitate the formation of Lewis(L)and Brønsted(B)acid sites and adjust the metal-support interaction(MSI).Among all the as-synthesized catalysts,NiMo/AYP-20 catalyst shows the highest HDS activities.The improved HDS activity of NiMo/AYP-20 catalyst is attributed to the perfect combination of excellent structural properties of the yolk-shell mesoporous silica,enhanced acidity,moderate MSI,and good accessibility/dispersion of active components.

Residual stress modeling of mitigated fused silica damage sites with CO_(2)laser annealing

A numerical model based on measured fictive temperature distributions is explored to evaluate the residual stress fields of CO_(2)laser-annealed mitigated fused silica damage sites.The proposed model extracts the residual strain from the differences in thermoelastic contraction of fused silica with different fictive temperatures from the initial frozen-in temperatures to ambient temperature.The residual stress fields of mitigated damage sites for the CO_(2)laser-annealed case are obtained by a finite element analysis of equilibrium equations and constitutive equations.The simulated results indicate that the proposed model can accurately evaluate the residual stress fields of laser-annealed mitigated damage sites with a complex thermal history.The calculated maximum hoop stress is in good agreement with the reported experimental result.The estimated optical retardance profiles from the calculated radial and hoop stress fields are consistent with the photoelastic measurements.These results provide sufficient evidence to demonstrate the suitability of the proposed model for describing the residual stresses of mitigated fused silica damage sites after CO_(2)laser annealing.

Effect of inorganic salt impurities on seeded precipitation of silica hydrate from sodium silicate solution

To clarify the precipitation of silica hydrate from the real desilication solutions of aluminosilicate solid wastes by adding seeds and improve integrated waste utilization,the seeded precipitation was studied using synthesized sodium silicate solution containing different inorganic salt impurities.The results show that sodium chloride,sodium sulfate,sodium carbonate,or calcium chloride can change the siloxy group structure.The number of high-polymeric siloxy groups decreases with increasing sodium chloride or sodium sulfate concentration,which is detrimental to seeded precipitation.Calcium chloride favors the polymerization of silicate ions,and even the chain groups precipitate with the precipitation of high-polymeric sheet and cage-like siloxy groups.The introduced sodium cations in sodium carbonate render a more open network structure of high-polymeric siloxy groups,although the carbonate ions favor the polymerization of siloxy groups.No matter how the four impurities affect the siloxy group structure,the precipitates are always amorphous opal-A silica hydrate.

Silica-modified Pt/TiO_(2) catalysts with tunable suppression of strong metal-support interaction for cinnamaldehyde hydrogenation

Tuning Strong Metal-support Interactions(SMSI)is a key strategy to obtain highly active catalysts,but conventional methods usually enable TiO_(x) encapsulation of noble metal components to minimize the exposure of noble metals.This study demonstrates a catalyst preparation method to modulate a weak encapsulation of Pt metal nanoparticles(NPs)with the supported TiO_(2),achieving the moderate suppression of SMSI effects.The introduction of silica inhibits this encapsulation,as reflected in the characterization results such as XPS and HRTEM,while the Ti^(4+) to Ti^(3+) conversion due to SMSI can still be found on the support surface.Furthermore,the hydrogenation of cinnamaldehyde(CAL)as a probe reaction revealed that once this encapsulation behavior was suppressed,the adsorption capacity of the catalyst for small molecules like H_(2) and CO was enhanced,which thereby improved the catalytic activity and facilitated the hydrogenation of CAL.Meanwhile,the introduction of SiO_(2) also changed the surface structure of the catalyst,which inhibited the occurrence of the acetal reaction and improved the conversion efficiency of C=O and C=C hydrogenation.Systematic manipulation of SMSI formation and its consequence on the performance in catalytic hydrogenation reactions are discussed.

Formation mechanism of nanopores in dense films of anodic alumina

Constant-current anodization of pure aluminum was carried out in non-corrosive capacitor working electrolytes to study the formation mechanism of nanopores in the anodic oxide films.Through comparative experiments,nanopores are found in the anodic films formed in the electrolytes after high-temperature storage(HTS)at 130°C for 240 h.A comparison of the voltage-time curves suggests that the formation of nanopores results from the decrease in formation efficiency of anodic oxide films rather than the corrosion of the electrolytes.FT-IR and UV spectra analysis shows that carboxylate and ethylene glycol in electrolytes can easily react by esterification at high temperatures.Combining the electronic current theory and oxygen bubble mold effect,the change in electrolyte composition could increase the electronic current in the anodizing process.The electronic current decreases the formation efficiency of anodic oxide films,and oxygen bubbles accompanying electronic current lead to the formation of nanopores in the dense films.The continuous electronic current and oxygen bubbles are the prerequisites for the formation of porous anodic oxides rather than the traditional field-assisted dissolution model.

Silica Gel Supported Trifluoromethanesulfonic Acid Catalyzed Beckmann Rearrangement of Cyclohexanone Oxime in Liquid Phase

The liquid phase Beckmann rearrangement of cyclohexanone oxime (CHO) using fuming sulfuric acid as a catalyst is a traditional method for preparing ε-caprolactam (CPL). This process has drawbacks, such as environmental pollution, corrosion of equipment, and low added value of by-product ammonium sulfate. This article designed and prepared a green silica gel-supported trifluoromethanesulfonic acid catalyst for the liquid-phase Beckmann rearrangement of CHO to prepare (CPL). The influencing factors of catalyst preparation and the optimal reaction conditions for Beckmann rearrangement were investigated. It was found that the optimal conditions for catalyst preparation were as follows: raw material silica gel:trifluoromethanesulfonic acid = 1:0.2 (mass ratio), room temperature, stirring time of 2.5 hours, and solvent of acetonitrile, silica gel mesh size is 100 - 200. The optimal reaction conditions for Beckmann rearrangement are CHO: catalyst = 1:2 (mass ratio), temperature of 130˚C, solvent of benzonitrile, volume of 30 mL/g CHO, and reaction time of 4 hours. Under the above conditions, the conversion of CHO is 90%, and the selectivity of CPL is 90%.

Effect of Slag Basicity on Alumina Dissolution and Diffusivity:A High-temperature Confocal Laser Scanning Microscopy Study

Alumina is one of the crucial and extensively utilized refractory components.As the refractory wear due to dissolution at elevated temperatures during operation is a major threat to refractory lifespan,quantifying dissolution is important for developing cost-effective and resource-efficient refractories.This study investigated the dissolution of alumina particles in two silicate and one calcium aluminate slags at 1450,1500,and 1550°C using high-temperature confocal laser scanning microscopy(HT-CLSM).Dissolution was quantified in terms of diffusivity,with all influencing factors,including Stefan flow and bath movement,incorporated into the determination process.The trends observed in total dissolution time and diffusivity in three slags at three experimental temperatures could not be explained solely on the basis of slag basicity.Two parameters,considering the influencing factors,were introduced to explain these trends.Furthermore,the linear trend observed in Arrhenius plots of diffusivities supports the diffusivity results.Additionally,good agreement between the diffusivities of alumina in one silicate slag obtained via CLSM and rotating finger test investigations verified the reliability of the results.

Theoretical study on the effective thermal conductivity of silica aerogels based on a cross-aligned and cubic pore model

Aerogel nanoporous materials possess high porosity, high specific surface area, and extremely low density due to their unique nanoscale network structure. Moreover, their effective thermal conductivity is very low, making them a new type of lightweight and highly efficient nanoscale super-insulating material. However, prediction of their effective thermal conductivity is challenging due to their uneven pore size distribution. To investigate the internal heat transfer mechanism of aerogel nanoporous materials, this study constructed a cross-aligned and cubic pore model(CACPM) based on the actual pore arrangement of SiO_(2) aerogel. Based on the established CACPM, the effective thermal conductivity expression for the aerogel was derived by simultaneously considering gas-phase heat conduction, solid-phase heat conduction, and radiative heat transfer. The derived expression was then compared with available experimental data and the Wei structure model. The results indicate that, according to the model established in this study for the derived thermal conductivity formula of silica aerogel, for powdery silica aerogel under the conditions of T = 298 K, a_(2)= 0.85, D_(1)= 90 μm, ρ = 128 kg/m^(3), within the pressure range of 0–10^(5)Pa, the average deviation between the calculated values and experimental values is 10.51%. In the pressure range of 10^(3)–10^(4)Pa, the deviation between calculated values and experimental values is within 4%. Under these conditions, the model has certain reference value in engineering verification. This study also makes a certain contribution to the research of aerogel thermal conductivity heat transfer models and calculation formulae.

Effects of Different Raw Materials and Additions on Wave Transparency of Alumina Fiber Products

Fiber products for microwave kilns were prepared using alumina fibers with alumina contents of 72 mass%and 80 mass%,and calcined alumina powder(4-6μm)as the main raw materials,silica sol as the binder,and cationic starch as the flocculant.Effects of different raw materials and their additions on the wave transparency of fiber products were researched.The results show that as the alumina fiber(72%)addition increases,the heating rate of the samples first decreases and then increases,and the corresponding wave transparency of the sample first increases and then decreases.When the alumina fibers addition is 40 mass%and the alumina powder addition is 30 mass%,the prepared microwave kiln lining material has a higher mullite content,which improves the wave transparency of the sample.The sample prepared from alumina fibers with an alumina content of 80%has a suitable glass-mullite phase ratio,performs lower overall dielectric constant and good wave transparency,and is a suitable lining material for microwave kilns.

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.

The Influence of Carbon Nanotubes and Nano-Silica Fume on Enhancing the Damping and Mechanical Properties of Cement-Based Materials

This paper conducted experimental studies on the damping and mechanical properties of carbon nanotube-nanosilica-cement composite materials with different carbon nanotube contents. The damping and mechanical properties enhancement mechanisms were analyzed and compared through the porosity structure test, XRD analysis, and scanning electron microscope observation. The results show that the introduction of nanosilica significantly improves the dispersion of carbon nanotubes in the cement matrix. At the same time, the addition of nanosilica not only effectively reduces the critical pore size and average pore size of the cement composite material, but also exhibits good synergistic effects with carbon nanotubes, which can significantly optimize the pore structure. Finally, a rationalization suggestion for the co-doping of nanosilica and carbon nanotubes was given to achieve a significant increase in the flexural strength, compressive strength and loss factor of cement-based materials.

Aluminum and Activated Alumina Powder Additions on Microwave Synthesis of Al_(4)SiC_(4)

Aiming at improving the properties of magnesia carbon materials,silicon aluminum carbide(Al_(4)SiC_(4))containing materials were prepared using industrial aluminum powder,silicon carbide powder,and graphite as raw materials,and activated alumina powder as an additive,mixing thoroughly,pressing into cylinders and then firing at 1200℃for 30 min in a carbon embedded atmosphere by the microwave method.The effects of the aluminum powder addition(20%and 24%,by mass)and activated alumina powder addition(0,3%,5%and 7%,by mass)on the microwave synthesis of Al_(4)SiC_(4) as well as the effect of the obtained Al_(4)SiC_(4) containing material on the properties of magnesia carbon bricks were studied.The results show that:compared with the samples with 20%aluminum powder,those with 24%aluminum powder generate more Al_(4)SiC_(4).With the activated alumina powder addition increasing from 0 to 7%,the amount of Al_(4)SiC_(4) generated increases first and then decreases.Compared with the sample without activated alumina powder,the samples with activated alumina powder show lower bulk density and higher apparent porosity.With the activated alumina powder addition increasing from 3%to 7%,the bulk density of the samples increases first and then decreases,while the apparent porosity of the samples shows an opposite trend.The optimal additions are 24%aluminum powder and 5%activated alumina powder,and Al_(4)SiC_(4) synthesized in this sample has a hexagonal plate structure.With the synthesized Al_(4)SiC_(4) containing material added,the magnesia carbon brick has slightly increased cold modulus of rupture,basically the same modulus of elasticity and improved oxidation resistance.