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.

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.

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.

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.

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.

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 silica fume and glass powder for enhanced impact resistance in GGBFS-based ultra high-performance geopolymer fibrous concrete:An experimental and statistical analysis

Solid waste recycling is an economically sound strategy for preserving the environment,safeguarding natural resources,and diminishing the reliance on raw material consumption.Geopolymer technology offers a significant advantage by enabling the reuse and recycling of diverse materials.This research assesses how including silica fume and glass powder enhances the impact resistance of ultra-high-performance geopolymer concrete(UHPGC).In total,18 distinct mixtures were formulated by substituting ground granulated blast furnace slag with varying proportions of silica fume and glass powder,ranging from 10%to 40%.Similarly,for each of the mixtures above,steel fibre was added at a dosage of 1.5%to address the inherent brittleness of UHPGC.The mixtures were activated by combining sodium hydroxide and sodium silicate solution to generate geopolymer binders.The specimens were subjected to drop-weight impact testing,wherein an examination was carried out to evaluate various parameters,including flowability,density at fresh and hardened state,compressive strength,impact numbers indicative of cracking and failure occurrences,ductility index,and analysis of failure modes.Additionally,the variations in the impact test outcomes were analyzed using the Weibull distribution,and the findings corresponding to survival probability were offered.Furthermore,the microstructure of UHPGC was scrutinized through scanning electron microscopy.Findings reveal that the specimens incorporating glass powder exhibited lower cracking impact number values than those utilizing silica fume,with reductions ranging from 18.63%to 34.31%.Similarly,failure impact number values decreased from 8.26%to 28.46%across glass powder contents.The maximum compressive and impact strength was recorded in UHPGC,comprising 10%silica fume with fibres.

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.

CO_(2)-Induced Modulation of Si-O Bonds for Low Temperature Plastic Deformation of Amorphous Silica Nanoparticles with Enhanced Photoluminescence

Modulation of Si-O bonds under mild conditions has been a challenging issue in the field of material science,which is critical to manufacture highperformance silica-based optical and photonic devices.Herein,we introduce a nondestructive technique to achieve Si-O bond rearrangement,leading to plastic deformation and photoluminescence enhancement of amorphous silica nanoparticles using supercritical carbon dioxides in EtOH/H_(2)O solution under mild temperature.Specifically,plastic deformation is achieved by treating hollow mesoporous silica nanospheres using supercritical CO_(2)at 40°C under 20 MPa.Experimental and theoretical studies revealed the critical role of supercritical CO_(2)in the plastic deformation process,which can be intercalated into the hollow mesoporous silica nanospheres with anisotropic stresses and induces the rearrangement of Si-O bonds and transformation of ring structures.This work suggests a novel approach to engineer high-performance nano-silica glass components for numerous optical and photonic devices under mild condition.

Thickening progression mechanism of silica fume-oil well cement composite system at high temperatures

This work studied the thickening progression mechanism of the silica fume-oil well cement composite system at high temperatures(110-180.C)in order to provide a theoretical guidance for the rational application of silica fume in the cementing engineering.Results showed that silica fume seldom affected the thickening progression of oil well cement slurry at 110-120.C,but when temperature reached above130.C,it would aggravate the bulging degree of thickening curves and significantly extend the thickening time,meanwhile causing the abnormal“temperature-based thickening time reversal”and“dosage-based thickening time reversal”phenomena in the range of 130-160.C and 170-180.C respectively.At 130-160.C,the thickening time of oil well cement slurry was mainly associated with the generation rate of calcium hydroxide(CH)crystal.The introduced silica fume would be attracted to the cement minerals'surface that were hydrating to produce CH and agglomerate together to form an“adsorptive barrier”to hinder further hydration of the inner cement minerals.This“adsorptive barrier”effect strengthened with the rising temperature which extended the thickening time and caused the occurrence of the“temperature-based thickening time reversal”phenomenon.At 170-180.C,the pozzolanic activity of silica fume significantly enhanced and considerable amount of C-S-H was generated,thus the“temperature-based thickening time reversal”vanished and the“dosage-based thickening time reversal”was presented.

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.

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.

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.

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.

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%.

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.

Highly Efficient Heavy-Metal-Ion Removal from Shellfish Processing Liquid with Low Protein and Polysaccharide Loss by Hybrid Mesoporous Silica Diol-APDC-SBA15

Heavy metal ions in shellfish products are harmful to human health,and their removal with low nutrient loss remains challenging.Herein,a new type of mesoporous silica(SBA15),modified internally with ammonium pyrrolidine dithiocarbamate(APDC)and externally with alkyl-diol groups,which was named as Diol-APDC-SBA15,was successfully developed and characterized by powder X-ray diffraction patterns,nitrogen adsorption,and Fourier transform infrared spectroscopy.The solutions with lead,chromium,cadmium,and copper were used to investigate the adsorption capacity of Diol-APDC-SBA15.Diol-APDC-SBA15 was adopted to remove heavy metals from cooking liquids of clams(Ruditapes philippinarum),hydrolysate liquids of oysters(Ostrea gigas Thunberg),and polysaccharide solution from the cooking liquid of R.philippinarum.The efficiencies of removing heavy metal ions and the loss rates of proteins and polysaccharides were examined.The results showed that the adsorption capacities of Diol-APDCSBA15 for Pb,Cr,Cd,and Cu in standard heavy-metal solutions were 161.4,166.1,29.6,and 60.2mgg^(−1),respectively.The removal efficiency of Diol-APDC-SBA15 for Pb in the three shellfish processing liquids ranged from 60.5%to 99.6%.The Cr removal efficiency was above 99.9%in the oyster hydrolysate liquid.Meanwhile,the percentages of polysaccharide loss were 5.5%and 3.7%in the cooking liquid of clam and polysaccharide solution,respectively,and the protein loss was 1.2%in the oyster hydrolysate liquid.Therefore,the Diol-APDC-SBA15 material exhibits a great potential application in the removal of heavy metals from shellfish processing liquids with low losses of proteins and polysaccharides.

Fabrication of chitosan/silica hybrid coating on AZ31 Mg alloy for orthopaedic applications

Biocompatible conversion of chitosan and chitosan/silica hybrid coating were prepared to enhance the biocompatibility and corrosion resistance of biodegradable AZ31 Mg alloy. The coatings were optimized and analysed with potentiodynamic polarization, SEM, ATR-IR and XPS studies. Potentiodynamic polarization studies, revealed that the coatings exhibited high corrosion resistance. The surface morphology of the Ch-3/Si coating showed small globular rough structure. The presence of functional groups was confirmed by ATR-IR. For a better understanding of chitosan/silica hybrid coating, the chemical states were examined by XPS studies. The in-vitro bioactivity of the coated samples was evaluated in Earle’s solution, which formed a dense layer of coral-like structure and calcium-deficient apatite with less stoichiometric ratio than the hydroxyapatite. In-vitro cell culture studies exhibited a good cell proliferation rate and the fabricated Ch-3/Si coating was found to be non-hemolytic. The bacterial studies proved that Ch-3/Si coating possessed inherent antibacterial activity.

The Adsorption of Pb(II)Using Silica Gel Synthesized from Chemical Bottle Waste:Optimization Using Box-Behnken Design

The adsorption of Pb(II)on silica gel synthesized from chemical glass bottle waste has been studied.The effect of independent variables(adsorbent dose,initial concentration of Pb(II),contact time,and pH)on the Pb(II)removal from water was evaluated and optimized using the Response Surface Methodology(RSM).Under optimized conditions(adsorbent dose:20 mg;contact time:30 min;initial Pb(II)concentration:120 mg.L^(−1);and pH:8),the removal of Pb(II)was 99.77%.The adsorption equilibrium data obtained from the batch experiment were investigated using different isotherm models.The Langmuir isotherm model fits the experimental data.This shows that the surface of the silica gel synthesized from chemical bottles waste was covered by a Pb(II)monolayer.XRF analysis showed that the synthesized silica gel had a SiO_(2) content of 75.63%.Amorphous silica was observed from XRD analysis.SEM-EDX characterization showed that Pb was adsorbed on the silica gel surface.SEM analysis showed that silica gel has irregular particles with a surface area of 297.08 m2.g^(−1) with a pore radius of 15.74 nm calculated from BET analysis.

Silica Gel from Chemical Glass Bottle Waste as Adsorbent for Methylene Blue:Optimization Using BBD

This research focuses on the effective removal of methylene blue dye using silica gel synthesized from chemical glass bottle waste as an environmentally friendly and cost-effective adsorbent.The adsorption process was optimized using Box-Behnken Design(BBD)and Response Surface Methodology(RSM)to investigate the influence of pH(6;8 and 10),contact time(15;30 and 45 min),adsorbent mass(30;50 and 70 mg),and initial concentration(20;50 and 80 mg/L)of the adsorbate on the adsorption efficiency.The BBD was conducted using Google Colaboratory software,which encompassed 27 experiments with randomly assigned combinations.The silica gel synthesized from chemical glass bottle was characterized by XRD,FTIR,SEM-EDX and TEM.The adsorption result was measured by spectrophotometer UV-Vis.The optimized conditions resulted in a remarkable methylene blue removal efficiency of 99.41%.Characterization of the silica gel demonstrated amorphous morphology and prominent absorption bands characteristic of silica.The Langmuir isotherm model best described the adsorption behavior,revealing chemisorption with a monolayer coverage of methylene blue on the adsorbent surface,and a maximum adsorption capacity of 82.02 mg/g.Additionally,the pseudo-second-order kinetics model indicated a chemisorption mechanism during the adsorption process.The findings highlight the potential of silica gel from chemical glass bottle waste as a promising adsorbent for wastewater treatment,offering economic and environmental benefits.Further investigations can explore its scalability,regenerability,and reusability for industrial-scale applications.