Silica Nanostructures Research Articles

Preparation of Mesoporous Silica Nanostructure Functionalized With Hydrobenzoin Substituted Phthalocyanine and Its Catalytic Performance in Benzyl Alcohol Oxidation

ABSTRACTIn this study, a new mesoporous silica nanostructure functionalized with hydrobenzoin substituted cobalt (II) phthalocyanine (MCM‐41‐CoPc) was prepared by grafting first 3‐chloropropyltriethoxysilane (CPTES) and then peripherally hydrobenzoin substituted cobalt (II) phthalocyanine (CoPc) onto mesoporous silica nanomaterial (MCM‐41). The structural properties of heterogeneous catalyst MCM‐41‐CoPc were elucidated by FT‐IR, XRD, TEM, EDS, TGA, solid‐state UV–Vis and N2 sorption analyses. The catalytic performance of MCM‐41‐CoPc was investigated in the oxidation of benzyl alcohol to benzaldehyde. To find the best catalytic conditions for aldehyde selectivity, the effect of the different parameters such as temperature, reaction time, oxidant, solvent, amount of the substrate, and oxidant on the catalytic activity of MCM‐41‐CoPc was investigated in detail. The selective oxidation of benzyl alcohol to benzaldehyde in the presence of MCM‐41‐CoPc was achieved with high aldehyde selectivity (98%) and moderate conversion (57%). The reusability of MCM‐41‐CoPc was tested in three consecutive cycle and no catalytic activity loss was observed. Additionally, it has been determined that the product selectivity can be controlled depending on the type of reaction solvent. When ethyl acetate was used as the solvent, 98.5% conversion rate and 96% benzoic acid selectivity were obtained.

Endoxylanase Immobilized Nanoporous Silica for the Production of Xylooligosaccharides: Equilibrium Kinetics, Thermodynamic Studies, and Enzyme Characteristics

AbstractNanoporous structured silica materials, namely f‐SiO2, SBA‐15, IITM‐41, and MCM‐41 were employed as the matrices for immobilizing endoxylanase by adsorption method. The equilibrium kinetics, activation energy, and thermodynamic parameters associated with endoxylanase adsorption were investigated. Our findings revealed a two‐phase adsorption mechanism: an initial phase featuring rapid adsorption rates, succeeded by a slower phase wherein adsorption gradually progressed until equilibrium was attained. Analysis of the adsorption kinetic data indicated a better fit with the pseudo‐second‐order model, suggesting chemisorption and highlighting its temperature dependency. The calculated activation energy (Ea) values fell within the range of physisorption, indicating the involvement of both types of adsorption processes. Thermodynamic assessments confirmed that the adsorption reactions were spontaneous, feasible, and endothermic. Notably, the immobilization process did not change the optimum pH of the enzyme, while the optimum temperature shifted slightly. Furthermore, immobilized enzymes show a higher reaction rate (Vmax) than the soluble XynC. All immobilized xylanases produced xylobiose (X2) to xylohexose (X6) by hydrolyzing the xylan substrate. Recycling studies showed that up to 80 % of the yield was retained after seven cycles of reuse. Our study demonstrates the potential of nanostructured silica as an effective immobilization matrix for enzymes of industrial significance.

Diatoms in Focus: Chemically Doped Biosilica for Customized Nanomaterials.

Diatoms are photosynthetic microalgae widely diffused around the globe and well adapted to thrive in diverse environments. Their success is closely related to the nanostructured biosilica shell (frustule) that serves as exoskeleton. Said structures have attracted great attention, thanks to their hierarchically ordered network of micro- and nanopores. Frustules display high specific surface, mechanical resistance and photonic properties, useful for the design of functional and complex materials, with applications including sensing, biomedicine, optoelectronics and energy storage and conversion. Current technology allows to alter the chemical composition of extracted frustules with a diverse array of elements, via chemical and biochemical strategies, without compromising their valuable morphology. We started our research on diatoms from the viewpoint of material scientists, envisaging the possibilities of these nanostructured silica shells as a general platform to obtain functional materials for several applications via chemical functionalization. Our first paper in the field was published in ChemPlusChem ten years ago. Ten years later, in this Perspective, we gather the most recent and relevant functional materials derived from diatom biosilica to show the growth and diversification that this field is currently experiencing, and the key role it will play in the near future.

Shedding reduction and immunity modulation in piglets with an inactivated Mycoplasma hyopneumoniae vaccine encapsulated in nanostructured SBA-15 silica

Mycoplasma (M.) hyopneumoniae is a primary etiological agent of porcine enzootic pneumonia (PEP), a disease that causes significant economic losses to pig farming worldwide. Current commercial M. hyopneumoniae vaccines induce partial protection, decline in preventing transmission of this pathogen or inducing complete immunity, evidencing the need for improving vaccines against PEP. In our study, we aimed to test the effectiveness of the SBA-15 ordered mesoporous silica nanostructured particles as an immune adjuvant of a vaccine composed of M. hyopneumoniae strain 232 proteins encapsulated in SBA-15 and administered by intramuscular route in piglets to evaluate the immune responses and immune-protection against challenge. Forty-eight 24-day-old M. hyopneumoniae-free piglets were divided into four experimental groups with different protocols, encompassing a commercial vaccine against M. hyopneumoniae, SBA-15 vaccine, SBA-15 adjuvant without antigens and a non-immunized group. All piglets were challenged with the virulent strain 232 of M. hyopneumoniae. Piglets that received the SBA-15 and commercial vaccine presented marked immune responses characterized by anti-M. hyopneumoniae IgA and IgG antibodies in serum, anti-M. hyopneumoniae IgA antibodies in nasal mucosa and showed an upregulation of IL-17 and IL-4 cytokines and downregulation of IFN-γ in lungs 35 days post-infection. Piglets immunized with SBA-15 vaccine presented a reduction of bacterial shedding compared to piglets immunized with a commercial bacterin. In addition, piglets from SBA-15 adjuvant suspension group presented increased IL-17 gene expression in the lungs without involvement of Th1 and Th2 responses after challenge. These results indicated that SBA-15 vaccine induced both humoral and cell-mediated responses in the upper respiratory tract and lungs, first site of replication and provided protection against M. hyopneumoniae infection with a homologous strain with reduction of lung lesions and bacterial shedding. Finally, these results enhance the potential use of new technologies such as nanostructured particles applied in vaccines for the pig farming industry.

Biomimetic Colored Coating toward Robust Display under Hostile Conditions.

Structural colors particularly of the angle-independent category stemming from wavelength-dependent light scattering have aroused increasing interest due to their considerable applications spanning displays and sensors to detection. Nevertheless, these colors would be heavily altered and even disappear during practical applications, which is related with the variation of refractive index mismatch by liquid wetting/infiltrating. Inspired by bird feathers, we propose a simple deposition toward the coating with angle-independent structural color and superamphiphobicity. The coating is composed of ∼200 nm-sized channel-type structures between hollow silica and air nanostructures, exhibiting a robust sapphire blue color independent of intense liquid intrusion, which duplicates the characteristics of the back feather of Eastern Bluebird. A high color saturation and superamphiphobicity of the biomimetic coating are optimized by manipulating the coating parameters or adding black substances. Excellent durability under harsh conditions endows the coating with long-term service life in various extreme environments.

Improvement of Therapeutic Effect via Inducing Non-Apoptotic Cell Death Using mRNA-Protection Nanocage.

Necroptosis, a cell death mechanism with the characteristics of both apoptosis and necrosis, is proposed as a promising therapeutic approach for cancer therapy. Induction of necroptosis for cancer therapy may be possible through the regulation of the expression of a key factor gene receptor-interacting protein kinase-3 (RIPK3) via in vitro transcription (IVT) mRNA delivery. However, mRNA is susceptible to degradation and has a low delivery efficiency, which highlights the requirement of a proper delivery vehicle for intracellular delivery. Therefore, a new mRNA delivery system based on the nanostructured silica nanoparticles, termed mRNA-protective nanocage (mPN) has been developed. High-efficiency expression of RIPK3 and induction of necroptosis is achieved through delivery of RIPK3 IVT mRNA with mPN in vitro and in vivo models. Importantly, the mPN carrying RIPK3 mRNA distributed locally in tumors upon intravascular injection, and successfully induced necroptosis and immune cell infiltration, a hallmark of necroptosis. the suppression of tumor growth in a murine cancer model, demonstrating the synergistic effect of RIPK3 mRNA- and immune cell-mediated therapy is also observed. These findings suggest the potential for anticancer therapy through necroptosis induction and provide a strategy for the development of mRNA-based nanomedicine.

Potassium silica nanostructure improved growth and nutrient uptake of sorghum plants subjected to drought stress.

Recent advancements in nanotechnology present promising opportunities for enhancing crop resilience in adverse environmental conditions. In this study, we conducted a factorial experiment to investigate the influence of potassium nanosilicate (PNS) on sorghum plants exposed to varying degrees of drought stress A randomized complete block design with three replications was employed to subject the sorghum plants to different drought conditions. The three levels of stress were designated as non-stress (NS at -0.03 MPa), moderate stress (MD at -0.6 MPa), and severe stress (SD at -1.2 MPa). The plants were administered PNS at concentrations of 0 mM (control), 3.6 mM Si, and 7.2 mM Si. As drought stress intensified, we observed significant reductions in multiple plant parameters, including height, fresh weight, dry weight, leaf number, stem diameter, cluster length, seed weight, and nutrient uptake, with the most pronounced effects observed under SD conditions. Interestingly, nitrogen (N) and potassium (K) levels exhibited an increase under drought stress and PNS application, peaking at MD, alongside Si concentrations. Notably, PNS application facilitated enhanced nutrient uptake, particularly evident in the significant increase in nitrogen concentration observed at 3.6 mM PNS. Furthermore, the application of PNS significantly enhanced the fresh weight and nutrient concentrations (notably K and Si) in sorghum seeds under drought stress, despite varying statistical significance for other nutrients. These findings shed light on the mechanisms through which PNS exerts beneficial effects on plant performance under drought stress. By elucidating the complex interactions between PNS application, drought stress, and plant physiology, this study contributes significantly to the development of sustainable agricultural practices aimed at bolstering crop resilience and productivity in water-limited environments.

Corrosion suppression and strengthening of the Al-10Zn alloy by adding silica nanorods

Aluminum alloys have been widely studied because of their current engineering applications. Due to their high strength and lightweight, cracking can easily initiate on their surface, deteriorating their overall functional and structural properties and causing environmental attacks. The current study highlights the significant influence of incorporating 1 wt% silica nanostructure in aluminum-10 zinc alloys. The characteristics of the composites were examined using Vickers hardness, tensile, and electrochemical testing (OCP, Tafel, and EIS) at various artificial aging temperatures (423, 443, and 463 K). Silica nanorods may achieve ultrafine grains, increase hardness by up to 13.8%, increase σUTS values by up to 79% at 443 K, and improve corrosion rate by up to 89.4%, surpassing Al-10 Zn bulk metallics. We demonstrate that silica nanorods contribute to the creation of a superior nanocomposite that not only limits failure events under loading but also resists corrosion. Our findings suggest that silica nanocomposite can produce unique features for use in a variety of automotive, construction, and aerospace applications. This improvement can be attributed mainly to the large surface area of nano-silica particles, which alters the Al matrix. Microstructural, mechanical, and electrochemical studies revealed that the effects of structure refinement were dependent on nano-silica.

Investigating ultrasonic dispersion of nanostructured silica for nanocomposite materials application

This article presented the results of investigating the influence of ultrasonic dispersion of nanostructured silica that has been referred to nanosilica (n-SiO2) into unsaturated polyester (UPE) resin for nanocomposite materials application. Scanning electron microscopy (SEM) method was employed to analyze the dispersion characteristics in this work. The optimally suitable ultrasonic factors have been identified including ultrasound frequency amplitude of 60%, ultrasound time of 120 minutes. Also, the bending strength measurement results of nanocomposite samples have shown that nanosilica material addition has increased significantly the mechanical properties of the nanocomposite material based on UPE resin. This also has shown the possibility of using n-SiO2 as a reinforcing agent for nanocomposite materials applications.

Synthesis of large mesoporous silica for efficient CO2 adsorption using coal gasification fine slag

Coal gasification fine slag (CGFS), a byproduct of the coal gasification process, is currently being recognized as a resource with significant potential for value addition and sustainable applications, especially in synthesizing CO2 adsorbents. The overarching challenges in this domain include the attainment of high-efficiency, environmentally benign transformation of CGFS into useful products, and the development of cost-effective adsorbent materials featuring precisely engineered pore structures. In this study, a hierarchical porous nanostructured silica material is synthesized rapidly, efficiently, and cost-effectively through acid leaching and alkaline dissolution-assisted hydrothermal treatment, employing CGFS as the precursor. The mass ratios of sodium hydroxide (NaOH) to CGFS range from 0.4 to 1, resulting in varying morphologies and adsorption properties. Specifically, the sample with the NaOH to CGFS ratio of 0.6 (CGFS-0.6) shows the best adsorption performance. The adsorption capacities are 2.87 mmol/g and 8.49 mmol/g at 20 °C with 15 % and 45 % CO2 concentration, respectively. The material is characterized by a well-developed pore structure shaped like a bouquet of flowers, with a specific surface area of 457 m2/g and pore volume reaching 2.34 cm3/g. During the hydrothermal processing, silicate/aluminosilicate entities self-organized into a Si-O-Na/Al network structure, endowing the synthesized adsorbent with optimal internal porosity and silanol functionalities. The adsorption equilibrium is achieved rapidly within 10 min, and CO2 adsorption stability remains robust across 20 successive cycles. All isothermal models of the adsorbents conform to the Sips model. This study offers a promising pathway for the value-enhanced utilization of coal-derived solid wastes.

Insights into nanostructured silica particle formation from sodium silicate using spray drying: An experimental and theoretical study

Spray drying is a widely used operational procedure utilized in diverse sectors. The current knowledge of droplet mobility processesinside the drying chamber is not fully comprehensive due to the complex nature of droplet evaporation issues. The present study used a comprehensive methodology that integrated numerical models and actual testing to investigate the drying process of droplets in the context of spray drying. The precursor material utilized in this investigation was colloidal silica. The influence of external hydrodynamic variables, such as drying temperature (473, 673, and 873 K) and carrier gas flow rate (2, 4, 6 L/min), was thoroughly investigated in connection to the dynamics of droplets and the subsequent creation of silica particles. Distinct alterations in the size and shape of the silica particles were observed due to variations in drying temperature and carrier gas flow rate. The validity of this investigation was established by the generation of two discrete particle morphologies, namely spherical particles and doughnut-shaped particles. Spherical particles were produced under reduced carrier gas flow rates of 2 L/min and lower drying chamber temperatures of 473 K. In the quantitative evaluation, the computational fluid dynamics (CFD) computations properly established the evaporation rate constant (K) and the temperature difference (ΔT) inside the droplets. Furthermore, qualitative calculations provide insight into the complex dynamics of droplet motion inside the spray chamber. The results of this study have the potential to open up new possibilities for regulating nanoparticle creation via the use of the spray drying process.

Ordered Mesoporous Silica Delivering siRNA as Cancer Nanotherapeutics: A Comprehensive Review.

Nanosized mesoporous silica has emerged as a promising flexible platform delivering siRNA for cancer treatment. This ordered mesoporous nanosized silica provides attractive features of well-defined and tunable porosity, structure, high payload, and multiple functionalizations for targeted delivery and increasing biocompatibility over other polymeric nanocarriers. Moreover, it also overcomes the lacunae associated with traditional administration of drugs. Chemically modified porous silica matrix efficiently entraps siRNA molecules and prevents their enzymatic degradation and premature release. This Review discusses the synthesis of silica using the sol-gel approach and the advantages with different silica mesostructure. Herein, the factors affecting the synthesis of silica at nanometer scale, shape, porosity and nanoparticle surface modification are also highlighted to attain the desired nanostructured silica carriers. Additional emphasis is given to chemically modified silica delivering siRNA, where the silica nanoparticle surface was modified with different chemical moieties such as amine modified with (3-aminoropyl) triethoxysilane, polyethylenimine, chitosan, poly(ethylene glycol), and cyclodextrin polymer modification to attain high therapeutic loading, improved dispersibility and biocompatibility. Upon systemic administration, ordered mesoporous nanosized silica encounters blood cells, immune cells, and organs mainly of the reticuloendothelial system (RES). Thereby, biocompatibility and biodistribution of silica based nanocarriers are deliberated to design principles for smart and efficacious nanostructured silica-siRNA carriers and their clinical trial status. This Review further reports the future scopes and challenges for developing silica nanomaterial as a promising siRNA delivery vehicle demanding FDA approval.

Formation mechanism of two-dimensional hexagonal silica on SiO2/Si substrate

Owing to their remarkable electronic properties, silica ultrathin films have been utilized as an insulating layer in nanoelectronics systems. Silica films have been epitaxially grown on different substrates using various synthesis methods. Among all fabrication approaches, chemical vapor deposition has long been an advanced method for synthesizing two-dimensional (2D) materials due to its ability to ensure precise stacking control and minimize contamination between layers. This study harnessed the potential of CVD to atomically fabricate thin layered 2D silica on a SiO2/Si substrate. Significantly, a unique combination of multiple transition metals and salt as the catalysts aided the formation of 2D silica for the first time. Salt is a crucial catalyst in promoting the evaporation of high-melting-point metal catalysts, resulting in hexagonal nucleation sites on the SiO2/Si wafer. By meticulously controlling growth parameters, a distinctive hexagonal structure was obtained. Correspondingly, this work delves into the growth mechanism of 2D silica, as evidenced by experiments involving salt alone and individual transition metals. Group VB transition metals played a prominent role in achieving the hexagonal structure compared to their group IVB counterparts. This research offers insight into the formation and growth mechanism of 2D silica, expanding the understanding of silica nanostructures.

Enhancing Antimicrobial Efficacy and Synergistic Effects of Nano-Silica-Based Combinations With Doxycycline, Metronidazole, and Ciprofloxacin Against Enterococcus faecalis Biofilms.

Enterococcus faecalisbiofilm formation within root canals poses a challenging problem in endodontics, often leading to treatment failure. To combat this issue, nanotechnology offers a promising avenue for enhancing antimicrobial efficacy. This study explores the potential synergistic effects of combining nanoscale silica particles with conventional antibiotics, including doxycycline, metronidazole, and ciprofloxacin, against E. faecalis biofilms. The unique characteristics of silica nanoparticles, such as their increased reactivity and ability to be functionalized with other compounds, make them ideal candidates for augmenting antibiotic efficacy. This research investigates the antimicrobial properties of these silica-based combinations and their potential to eliminate or inhibit E. faecalis biofilms more effectively than conventional treatments. Methodology: The methods involved the preparation of nanostructured silica particles and their combination with doxycycline, Flagyl, and ciprofloxacin at subinhibitory concentrations. These combinations were then tested against E. faecalis biofilms using the agar well diffusion technique. Preliminary results suggested that the synergistic interactions between silica nanoparticles and antibiotics can significantly enhance antimicrobial efficacy. The combined treatment exhibited superior inhibitory effects on E. faecalis compared to antibiotics or silica nanoparticles alone (P< 0.05). Conclusions: This study sheds light on the potential of nanoscale silica-based combinations to address the challenges posed by E. faecalis biofilms in endodontics. Understanding the mechanisms of synergy between nanoparticles and antibiotics can pave the way for the development of more effective and targeted strategies for root canal disinfection, ultimately improving the success rates of endodontic treatments.

The regulation of electro-optical properties and polymer morphology of polymer-dispersed liquid crystal films with silicon nanostructure

ABSTRACT In this work, the thiol modified silica nanostructures (SiO2-SH) were doped into polymer-dispersed liquid crystal (PDLC) films. The SEM was used to observe the morphology of the polymer microstructure. The electro-optical (E-O) property test was determined by a liquid crystal parameter tester. The SEM images suggested that the SiO2-SH nanoparticles can react with acrylate groups to form the polymer matrix. The saturation voltage decreased by half in the sample when the dosage of the SiO2-SH nanoparticles was 7.5 wt%, which may be due to the reduced anchoring strength of the polymer matrix incorporated with silicon nanoparticles resulting from the lower surface energy and the enhanced steric repulsions of LC droplets and polymer matrix. In addition, the preparation conditions like polymerisation temperatures and UV light intensity also effectively regulated the E-O properties and polymer microstructure of the PDLC film with silica nanostructure. Thus, the results showed that the E-O properties and the polymer morphology of PDLC films with silicon nanostructures can be effectively regulated by doping SiO2-SH nanoparticles and regulating the preparation conditions such as the polymerisation temperature and UV light intensity. This work can provide practical guidance for modulating the properties of PDLC films.

Sol–Gel Synthesis of Nanostructured Mesoporous Silica Powder and Thin Films

Mesoporous materials are special nanoporous materials containing well-defined mesochannels with a pore diameter between 2 and 50 nm. The high surface area, ordered structure, tunable pore size, and easiness of functionalization have made mesoporous silica powder and thin films interesting materials for a wide range of applications including drug delivery, absorption, separation, catalysis, energy conversion, and storage. The sol–gel process has emerged as a promising technique for the synthesis of nanostructured mesoporous silica materials as it provides the advantages of low-temperature processing and easy control of the synthesis parameters. Although it offers several advantages over other synthesis techniques, it also has the drawbacks of high sensitivity to processing conditions. Hence, this review paper aims to give critical insights into the sol–gel process, the chemistry of sol–gel silica, the formation mechanism of mesoporosity, and the effects of the reaction parameters. A good understanding of these phenomena is essential to better control and optimize the properties of the final material for specific needs and applications. Additionally, this review paper discusses the different methods applied to the synthesis of nanostructured ordered mesoporous thin film silica, including the Electrochemically Assisted Self-Assembly method of synthesis. The EASA method is a novel and promising technique for the synthesis of well-ordered and vertically aligned pore channels of mesoporous thin films as it is required for mass transport applications. Moreover, the effects of sol composition, pH, applied potential, and deposition time on the final thickness of the thin film are elaborated on in detail. Furthermore, this comprehensive review highlights the potential and opportunities for future research and development in the area to further advance and use its full potential advantages.

Multifaceted Assessment of Porous Silica Nanocomposites: Unraveling Physical, Structural, and Biological Transformations Induced by Microwave Field Modification.

In response to the persistent challenge of heavy and noble metal environmental contamination, our research explores a new idea to capture silver through porous spherical silica nanostructures. The aim was realized using microwave radiation at varying power (P = 150 or 800 W) and exposure times (t = 60 or 150 s). It led to the development of a silica surface with enhanced metal-capture capacity. The microwave-assisted silica surface modification influences the notable changes within the carrier but also enforces the crystallization process of silver nanoparticles with different morphology, structure, and chemical composition. Microwave treatment can also stimulate the formation of core-shell bioactive Ag/Ag2CO3 heterojunctions. Due to the silver nanoparticles' sphericity and silver carbonate's presence, the modified nanocomposites exhibited heightened toxicity against common microorganisms, such as E. coli and S. epidermidis. Toxicological assessments, including minimum inhibitory concentration (MIC) and half-maximal inhibitory concentration (IC50) determinations, underscored the efficacy of the nanocomposites. This research represents a significant stride in addressing pollution challenges. It shows the potential of microwave-modified silicas in the fight against environmental contamination. Microwave engineering underscores a sophisticated approach to pollution remediation and emphasizes the pivotal role of nanotechnology in shaping sustainable solutions for environmental stewardship.

Biomimetic bilayer ionic conductive photoelectronic skin based on nano-structured photonic crystal film and flexible adhesive hydrogel for dual-signal motion detection and anti-disturbance temperature monitor

The growing interest in biological skin mimicry has greatly contributed to the creation of high-performance artificial skin. Here, inspired by the optical-electrical signal co-transmission of chameleon skins, a bilayer biomimetic ion-conductive photoelectronic skin (BIPES) was constructed by compositing the mechanochromic nano-structured silica photonic crystal film with an adhesive, flexible hydrogel by a layer-by-layer design strategy. The BIPES has a highly sensitive strain response on electrical and optical signals (GF = 3.27 at 0–100 %, Δλ/Δε = 2.1 nm %–1) and temperature response (TCR = –2.27 % °C–1 at 0–50 °C). Importantly, through the temperature insensitivity of the mechanochromic film, the BIPES not only achieved dual-signal motion detection but also achieved real-time temperature monitoring excluding strain interference. This research provides new inspiration for the construction of multi-signal combined photoelectronic skins and further exploration for advanced accurate smart wearable electronics in applications, especially in health detection for patients with non-spontaneous body-trembling.

Preparation of mesoporous silica and organosilica nanostructures functionalized with C2‐symmetric diol and their catalytic performance in diethylzinc addition to aromatic aldehydes

In this study, heterogenization of C2‐symmetric (1R,2R)‐1,2‐bis(4‐(3‐(triethoxysilyl)propyl)phenyl)ethane‐1,2‐diol compound and investigation of the effect of structural arrangements of nanocatalysts on catalytic activity were carried out. For this, bissilyl derivative of (1R,2R)‐1,2‐bis(4′‐bromophenyl)‐ethane‐1,2‐diol, named as C2‐BSi, was obtained by 2‐step synthesis. Then, mesoporous silica nanocatalysts C2‐BSi@SBA‐15 and C2‐BSi@MCM‐41 were synthesized by grafting of C2‐BSi onto SBA‐15 and MCM‐41, whereas mesoporous organosilica nanocatalysts C2‐BSi‐MON‐(a) and C2‐BSi‐MON‐(b) were synthesized by co‐condenzation of C2‐BSi and tetraethyl orthosilicate (TEOS). Structure determinations of synthesized organic substances were performed by 1H, 13C NMR, Fourier transform infrared (FT‐IR), polarimeter, and mass analysis, whereas the structural properties of heterogeneous catalysts C2‐BSi@SBA‐15, C2‐BSi@MCM‐41, C2‐BSi‐MON‐(a), and C2‐BSi‐MON‐(b) were determined by FT‐IR, X‐ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), thermogravimetric analysis (TGA), and N2 sorption analyses. The catalytic activities of novel heterogenous materials were tested in the reaction of Ti‐promoted enantioselective diethylzinc addition to aromatic aldehydes. The effects of the structural arrangements of the prepared heterogeneous catalyst on the catalytic activity were examined and compared with the catalytic activity values of their homogeneous analog. According to the results, all catalysts catalyzed the reactions and afforded the corresponding products with high conversion (82–99%) but low enantioselectivity (rac‐7% ee). The conversion values in heterogeneous catalysis were higher than those in homogeneous catalysis. C2‐BSi‐MON‐(a) with the largest pore width stood out as the most effective catalyst (99% conversion, 7% ee). The findings from the catalytic activity experiments confirmed that the structural arrangement of the nanocatalysts has an effect on the performance of the catalysts in the reaction.

Facile preparation of small-sized gold nanoparticle decorated silica nanocomposites and their morphological changes in catalytic reactions

Due to the unique physicochemical properties of gold nanoparticles (AuNPs) decorated silica nanostructures (SiO2@AuNPs), they show great potential for applications in catalysis, biosensing, optical devices and medicine. It is essential to explore the catalytic effect of SiO2@AuNPs and the understanding of the essential process of catalytic reactions. We have prepared SiO2@AuNPs by loading small-sized AuNPs on surface-modified silica nanospheres. SiO2@AuNPs was used as a catalyst for the catalytic reduction of 4-nitrophenol (4-NP) in the presence of excess NaBH4, and the results showed that with the increase of the amount of catalyst from 30 to 100 μl, the corresponding rate constant K app was increased from 6.44 × 10−3 to 1.45 × 10−2 s−1, and its TOF was as high as 1.326 × 103 h−1, and the catalytic rate could still be maintained at 87% after five cycles. By analyzing the morphology and size of the SiO2 supported AuNPs before and after the catalytic reaction, it can be seen that the atoms on the surface of small-sized AuNPs supported by silica have migrated during the catalytic process, which subsequently affects the catalytic efficiency of the structure. This study proves the good catalytic effect of SiO2@AuNPs structure and lays the foundation for its wider application.