Studies of New Iridium Catalysts Supported on Modified Silicalite-1—Their Structure and Hydrogenating Properties

This paper investigates the catalytic properties of the iridium catalysts supported on modified silicalite-1. Post-synthesis modification of silicalite-1, with solutions of ammonium compounds (NH₄F and NH₄OH), appeared to be an efficient method to generate the acidic sites in starting support. The modification of support led not only to changes in its acidity but also its porosity—formation of additional micro- and mesopores. The novel materials were used as supports for iridium. The iridium catalysts (1 wt.% Ir) were characterized by N₂ adsorption/desorption measurements, temperature-programmed reduction with hydrogen (TPR-H₂), H₂ chemisorption, transmission electron microscopy (TEM), temperature-programmed desorption of ammonia (TPD-NH₃), X-ray photoelectron spectroscopy (XPS) and tested in the hydrogenation of toluene reaction. The catalytic activity of iridium supported on silicalite-1 treated with NH₄OH (higher porosity of support, better dispersion of active phase) was much higher than that of Ir supported on unmodified and modified with NH₄F silicalite-1.     

Constructing Biopolymer-Inorganic Nanocomposite through a Biomimetic Mineralization Process for Enzyme Immobilization

Inspired by biosilicification, biomimetic polymer-silica nanocomposite has aroused a lot of interest from the viewpoints of both scientific research and technological applications. In this study, a novel dual functional polymer, NH₂-Alginate, is synthesized through an oxidation-amination-reduction process. The “catalysis function” ensures the as-prepared NH₂-Alginate inducing biomimetic mineralization of silica from low concentration precursor (Na₂SiO₃), and the “template function” cause microscopic phase separation in aqueous solution. The diameter of resultant NH₂-Alginate micelles in aqueous solution distributed from 100 nm to 1.5 μm, and is influenced by the synthetic process of NH₂-Alginate. The size and morphology of obtained NH₂-Alginate/silica nanocomposite are correlated with the micelles. NH₂-Alginate/silica nanocomposite was subsequently utilized to immobilize β-Glucuronidase (GUS). The harsh condition tolerance and long-term storage stability of the immobilized GUS are notably improved due to the buffering effect of NH₂-Alginate and cage effect of silica matrix.     

Structures,Bonding and Sensor Properties of Some Alkaline o-Phthalatocuprates

Comprehensive study of the structure and bonding of disodium, dipotassium and diammonium di-o-phthalatocuprates(II) dihydrates has been undertaken. The crystal structure of ammonium o-phthalatocuprate has been determined. The identity of structures of phthalatocuprate chains in potassium and ammonium salts has been revealed. Vibrational spectra of all three compounds have been recorded, and the assignment of vibrational bands has been made. Force field calculations have shown a minor effect of outer-sphere cations (Na⁺, K⁺, NH₄⁺) on both intraligand (C-O) and metal–ligand bond strengths. Synthesized compounds have been tested as electrochemical sensors on D-glucose, dopamine and paracetamol. Their sensitivity to analytes varied in the order of Na⁺ > K⁺ > NH₄⁺. This effect has been explained by the more pronounced steric hindrance of copper ions in potassium and ammonium salts.     

Butanol Dehydration over V2O5-TiO2/MCM-41 Catalysts Prepared via Liquid Phase Atomic Layer Deposition

MCM-41 was used as a support and, by using atomic layer deposition (ALD) in the liquid phase, a catalyst was prepared by consecutively loading titanium oxide and vanadium oxide to the support. This research analyzes the effect of the loading amount of vanadium oxide on the acidic characteristics and catalytic performance in the dehydration of butanol. The physical and chemical characteristics of the TiO₂-V₂O₅/MCM-41 catalysts were analyzed using XRF, BET, NH₃-TPD, XRD, Py-IR, and XPS. The dehydration reaction of butanol was performed in a fixed bed reactor. For the samples with vanadium oxide loaded to TiO₂/MCM-41 sample using the liquid phase ALD method, it was possible to increase the loading amount until the amount of vanadium oxide reached 12.1 wt %. It was confirmed that the structural properties of the mesoporous silica were retained well after titanium oxide and vanadium loading. The NH₃-TPD and Py-IR results indicated that weak acid sites were produced over the TiO₂/MCM-41 samples, which is attributed to the generation of Lewis acid sites. The highest activity of the V₂O₅(12.1)-TiO₂/MCM-41 catalyst in 2-butanol dehydration is ascribed to it having the highest number of Lewis acid sites, as well as the highest vanadium dispersion.     

Optimization of Pickling Solution for Improving the Phosphatability of Advanced High-Strength Steels

This study investigated the optimum pickling conditions for improving the phosphatability of advanced high-strength steel (AHSS) using surface analysis and electrochemical measurements. To remove the SiO₂ that forms on the surface of AHSS, 30 wt.% NH₄HF₂ was added to the pickling solution, resulting in a significant reduction in the amount of SiO₂ remaining on the surface of the AHSS. The phosphatability was improved remarkably using HNO₃ concentrations higher than 13% in the pickling solution. Furthermore, phosphate crystals became finer after pickling with a HNO₃-based solution rather than a HCl-based solution. Electrochemical impedance spectroscopy (EIS) data indicated that the corrosion resistance of AHSS subjected to HNO₃-based pickling was higher than that of AHSS subjected to HCl-based pickling. Fluorine compounds, which were involved in the phosphate treatment process, were only formed on the surface of steel in HNO₃-based solutions. The F compounds reacted with the phosphate solution to increase the pH of the bulk solution, which greatly improved the phosphatability. The phosphatability was better under HNO₃-based conditions than a HCl-based condition due to the fineness of the phosphate structure and the increased surface roughness.     

Stability Study of the Irradiated Poly(lactic acid)/Styrene Isoprene Styrene Reinforced with Silica Nanoparticles

In this paper, the stability improvement of poly(lactic acid) (PLA)/styrene-isoprene block copolymer (SIS) loaded with silica nanoparticles is characterized. The protection efficiency in the material of thermal stability is mainly studied by means of high accurate isothermal and nonisothermal chemiluminescence procedures. The oxidation induction times obtained in the isothermal CL determinations increase from 45 min to 312 min as the polymer is free of silica or the filler loading is about 10%, respectively. The nonisothermal measurements reveal the values of onset oxidation temperatures with about 15% when the concentration of SiO₂ particles is enhanced from none to 10%. The curing assay and Charlesby–Pinner representation as well as the modifications that occurred in the FTIR carbonyl band at 1745 cm⁻¹ are appropriate proofs for the delay of oxidation in hybrid samples. The improved efficiency of silica during the accelerated degradation of PLA/SIS 30/n-SiO₂ composites is demonstrated by means of the increased values of activation energy in correlation with the augmentation of silica loading. While the pristine material is modified by the addition of 10% silica nanoparticles, the activation energy grows from 55 kJ mol⁻¹ to 74 kJ mol⁻¹ for nonirradiated samples and from 47 kJ mol⁻¹ to 76 kJ mol⁻¹ for γ-processed material at 25 kGy. The stabilizer features are associated with silica nanoparticles due to the protection of fragments generated by the scission of hydrocarbon structure of SIS, the minor component, whose degradation fragments are early converted into hydroperoxides rather than influencing depolymerization in the PLA phase. The reduction of the transmission values concerning the growing reinforcement is evidence of the capacity of SiO₂ to minimize the changes in polymers subjected to high energy sterilization. The silica loading of 10 wt% may be considered a proper solution for attaining an extended lifespan under the accelerated degradation caused by the intense transfer of energy, such as radiation processing on the polymer hybrid.     

Spherical Silica Modified with Magnesium and Ruthenium—Synthesis,Characterization and Catalytic Properties

The design of different bimetallic catalysts is an important area of catalytic research in the context of their possible applications in the cascade processes, meeting the requirements of the so-called green chemistry. In this study, such catalysts were obtained by the incorporation of magnesium species into spherical silica, which was in the next step covered with porous silica and modified with ruthenium species. The structure and chemical composition of the materials obtained were determined by XRD measurements, low temperature N₂ adsorption/desorption, SEM, ICP-OES and XPS methods. The catalytic activities of materials obtained were tested in 2-propanol decomposition and hydrogenation of levulinic acid. The results obtained confirmed the successful coverage of nanospheres with porous silica. A much higher concentration of ruthenium species was found on the surface of the catalysts than in their bulk. The opposite relationship was observed for magnesium species. The modification of nanospheres with silica had a positive effect on the catalytic activity of the materials obtained. For the most active sample, i.e., Ru/NS/3Mg/NS, 49% of levulinic acid conversion in its hydrogenation process was reported with γ-valerolactone as the only product.     

Impedance and Dielectric Properties of PVC:NH4I Solid Polymer Electrolytes (SPEs): Steps toward the Fabrication of SPEs with High Resistivity

In the present article, a simple technique is provided for the fabrication of a polymer electrolyte system composed of polyvinyl chloride (PVC) and doped with varying content of ammonium iodide (NH₄I) salt using solution-casting methodology. The influences of NH₄I on the structural, electrochemical, and electrical properties of PVC have been investigated using X-ray diffraction, electrochemical impedance spectroscopy (EIS), and dielectric properties. The X-ray study reveals the amorphous nature of the polymer–salt complex. The EIS measurement revealed an ionic conductivity of 5.57 × 10⁻¹⁰ S/cm for the electrolyte containing 10 wt.% of salt. Our hypothesis is provided, which demonstrated the likelihood of designing highly resistive solid electrolytes using the concept of a polymer electrolyte. Here, the results showed that the resistivity of the studied samples is not dramatically decreased with increasing NH₄I. Bode plots distinguish the decrease in resistance or impedance with increasing salt contents. Dielectric measurements revealed a decrease in the dielectric constant with the increase of NH₄I content in the PVC polymer. The relaxation time and dielectric properties of the electrolytes confirmed their non-Debye type behavior. This pattern has been validated by the existence of an incomplete semicircle in the Argand plot. Insulation materials with low ε_r have found widespread applications in electronic devices due to the reduction in delay, power dissipation, and crosstalk. In addition, an investigation of real and imaginary parts of electric modulus leads to the minimized electrode polarization being reached.     

Recovery of Platinum Group Metals from Spent Automotive Catalysts Using Lithium Salts and Hydrochloric Acid

The recovery of platinum group metals (PGMs) from waste materials involves dissolving the waste in an aqueous solution. However, since PGMs are precious metals, their dissolution requires strong oxidizing agents such as chlorine gas and aqua regia. In this study, we aimed to recover PGMs via the calcination of spent automotive catalysts (autocatalysts) with Li salts based on the concept of “spent autocatalyst + waste lithium-ion batteries” and leaching with only HCl. The results suggest that, when Li₂CO₃ was used, the Pt content was fully leached, while 94.9% and 97.5% of Rh and Pd, respectively, were leached using HCl addition. Even when LiF, which is a decomposition product of the electrolytic solution (LiPF₆), was used as the Li salt model, the PGM leaching rate did not significantly change. In addition, we studied the immobilization of fluorine on cordierite (2MgO·2Al₂O₃·5SiO₂), which is a matrix component of autocatalysts. Through the calcination of LiF in the presence of cordierite, we found that cordierite thermally decomposed, and fluorine was immobilized as MgF₂.     

SBA-15 with Crystalline Walls Produced via Thermal Treatment with the Alkali and Alkali Earth Metal Ions

Crystalline walled SBA-15 with large pore size were prepared using alkali and alkali earth metal ions (Na⁺, Li⁺, K⁺ and Ca²⁺). For this work, the ratios of alkali metal ions (Si/metal ion) ranged from 2.1 to 80, while the temperatures tested ranged from 500 to 700 °C. The SBA-15 prepared with Si/Na⁺ ratios ranging from 2.1 to 40 at 700 °C exhibited both cristobalite and quartz SiO₂ structures in pore walls. When the Na⁺ amount increased (i.e., Si/Na increased from 80 to 40), the pore size was increased remarkably but the surface area and pore volume of the metal ion-based SBA-15 were decreased. When the SBA-15 prepared with Li⁺, K⁺ and Ca²⁺ ions (Si/metal ion = 40) was thermally treated at 700 °C, the crystalline SiO₂ of quartz structure with large pore diameter (i.e., 802.5 Å) was observed for Ca⁺² ion-based SBA-15, while no crystalline SiO₂ structures were observed in pore walls for both the K⁺ and Li⁺ ions treated SBA-15. The crystalline SiO₂ structures may be formed by the rearrangement of silica matrix when alkali or alkali earth metal ions are inserted into silica matrix at elevated temperature.     

Multiple Intermolecular Interaction to Improve the Abrasion Resistance and Wet Skid Resistance of Eucommia Ulmoides Gum/Styrene Butadiene Rubber Composite

A rubber composite was prepared by using methyltriethoxysilane (MTES) to modify silica (SiO₂) and epoxidized eucommia ulmoides gum (EEUG) as rubber additives to endow silica with excellent dispersion and interfacial compatibility under the action of processing shear. The results showed that compared with the unmodified silica-reinforced rubber composite (SiO₂/EUG/SBR), the bound rubber content of MTES-SiO₂/EEUG/EUG/SBR was increased by 184%, and its tensile strength, modulus at 100% strain, modulus at 300% strain, and tear strength increased by 42.1%, 88.5%, 130.8%, and 39.9%, respectively. The Akron abrasion volume of the MTES-SiO₂/EEUG/EUG/SBR composite decreased by 50.9%, and the wet friction coefficient increased by 43.2%. The wear resistance and wet skid resistance of the rubber composite were significantly improved.     

Biomimetic Growth of Hydroxyapatite on SiO2 Microspheres to Improve Its Biocompatibility and Gentamicin Loading Capacity

The interest in multifunctional biomaterials to be implanted are also able to release drugs that reduce pain and inflammation or prevent a possible infection has increased. Bioactive materials such as silica (SiO₂) containing surface silanol groups contribute to the nucleation and growth of hydroxyapatite (HAp) in a physiological environment. Regarding biocompatibility, the spherical shape of particles is the desirable one, since it does not cause mechanical damage to the cell membrane. In this work, the synthesis of SiO₂ microspheres was performed by the modified Stöber method and they were used for the biomimetic growth of HAp on their surface. The effect of the type of surfactant (sodium dodecyl sulphate (SDS), cetyltrimethylammonium bromide (CTAB), and polyethylene glycol (PEG)), and heat treatment on the morphology and size of SiO₂ particles was investigated. Monodisperse, spherical-shaped SiO₂ microparticles with an average particle size of 179 nm, were obtained when using PEG (SiO₂-PEG). The biomimetic growth of HAp was performed on this sample to improve its biocompatibility and drug-loading capacity using gentamicin as a model drug. Biomimetic growth of HAp was confirmed by FTIR-ATR, SEM-EDX and TEM techniques. SiO₂-PEG/HAp sample had a better biocompatibility in vitro and gentamicin loading capacity than SiO₂-PEG sample.     

“Low Cost” Pore Expanded SBA-15 Functionalized with Amine Groups Applied to CO2 Adsorption

The CO₂ adsorption capacity of different functionalized mesoporous silicas of the SBA-15 type was investigated and the influence of textural properties and the effect of the silicon source on the CO₂ uptake studied. Several adsorbents based on SBA-15 were synthesized using sodium silicate as silicon source, replacing the commonly used tetraethyl orthosilicate (TEOS). Thus, we synthesized three couples of supports, two at room temperature (RT, RT-F), two hydrothermal (HT, HT-F) and two hydrothermal with addition of swelling agent (1,3,5-triisopropylbenzene) (TiPB, TiPB-F). Within each couple, one of the materials was synthesized with ammonium fluoride (NH₄F). The supports were functionalized via grafting 3-aminopropyltriethoxysilane (APTES) and via impregnation with polyethylenimine ethylenediamine branched (PEI). The adsorption behavior of the pure materials was described well by the Langmuir model, whereas for the amine-silicas, a Dualsite Langmuir model was applied, which allowed us to qualify and quantify two different adsorption sites. Among the materials synthesized, only the SBA-15 synthesized at room temperatures (RT) improved its properties as an adsorbent with the addition of fluoride when the silicas were functionalized with APTES. The most promising result was the TiPB-F/50PEI silica which at 75 °C and 1 bar CO₂ captured 2.21 mmol/g.     

Polyamine-Promoted Growth of One-Dimensional Nanostructure-Based Silica and Its Feature in Catalyst Design

Crystalline linear polyethyleneimine (LPEI) is a fascinating polymer that can be used as a catalyst, template and scaffold in order to direct the formation of silica with controllable compositions and spatial structures under mild conditions. Considering the crystallization and assembly of LPEI is temperature-dependent, we adopted different accelerated cooling processes of a hot aqueous solution of LPEI in order to modulate the LPEI crystalline aggregates. We then used them in the hydrolytic condensation of alkoxysilane. A series of silica with nanofibrils, nanotubes and nanowire-based structures were achieved simply by the LPEI aggregates which were pre-formed in defined cooling processes. These specific one-dimensional nanoscale structures assembled into microscale fibers-, sheet- and platelet-like coalescences. Furthermore, the deposition kinetics was also researched by the combination of other characterizations (e.g., pH measurement, ²⁹Si MAS NMR). As a preliminary application, the hybrids of LPEI@SiO₂ were used not only as an agent for reducing PtCl₄²⁻ into Pt but also as host for loading Pt nanoparticles. The Pt-loaded silica showed good catalytic properties in the reduction of Rhodamine B by dimethylaminoborane (DMAB).     

Towards Efficient Acidic Catalysts via Optimization of SO3H-Organosilane Immobilization on SBA-15 under Increased Pressure: Potential Applications in Gas and Liquid Phase Reactions

In this paper, the optimization of the synthesis of catalysts based on acidic mesoporous silica of the SBA-15 type by post-synthesis immobilization of 3-(trihydroxysilyl)-1-propanesulfonic acid (TPS) under increased pressure up to 20 bar is reported. Sample structures and composition were examined by XRD measurement, low-temperature N₂ adsorption/desorption and elemental analysis. The catalytic activities of the materials obtained were determined in both gas and liquid phase processes, i.e., by esterification of acetic acid and glycerol dehydration, respectively. The optimum pressure for modification leading to the highest number of acidic sites was found to be 10 bar. The final material was very active and stable in liquid phase processes; however, the stability in the gas-phase process was unsatisfactory due to the loss of sulphonic species from the catalyst surface.     

Growth of Anodic Layers on 304L Stainless Steel Using Fluoride Free Electrolytes and Their Electrochemical Behavior in Chloride Solution

Anodic layers have been grown on 304L stainless steel (304L SS) using two kinds of fluoride-free organic electrolytes. The replacement of NH₄F for NaAlO₂ or Na₂SiO₃ in the glycerol solution and the influence of the H₂O concentration have been examined. The obtained anodic layers were characterized by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and potentiodynamic polarization tests. Here, it was found that, although the anodic layers fabricated within the NaAlO₂-electrolyte and high H₂O concentrations presented limited adherence to the substrate, the anodizing in the Na₂SiO₃-electrolyte and low H₂O concentrations allowed the growth oxide layers, and even a type of ordered morphology was observed. Furthermore, the electrochemical tests in chloride solution determined low chemical stability and active behavior of oxide layers grown in NaAlO₂-electrolyte. In contrast, the corrosion resistance was improved approximately one order of magnitude compared to the non-anodized 304L SS substrate for the anodizing treatment in glycerol, 0.05 M Na₂SiO₃, and 1.7 vol% H₂O at 20 mA/cm² for 6 min. Thus, this anodizing condition offers insight into the sustainable growth of oxide layers with potential anti-corrosion properties.     

Morphology and Properties of Poly(2,6-dimethyl-1,4-phenylene oxide)/Polyamide 11 Hybrid Nanocomposites: Effect of Silica Surface Modification

Poly(2,6-dimethyl-1,4-phenylene oxide)/polyamide 11 (PPO/PA11 80/20) blend filled with neat (SiO₂) or modified silica having amine functional groups (A-SiO₂) was melt mixing in a twin-screw extruder. The silica was prepared by the sol–gel process. SEM shows that, with increasing A-SiO₂ content from 1 to 5 wt.%, the morphology of PPO/PA11blend changed from droplet matrix to co-continuous with phase inversion. The phase inversion was also observed for 5 wt.% of neat silica, but the droplet-matrix structure was retained. The overall rheological and mechanical properties improvement of the A-SiO₂-filled composites in comparison with the unfilled blend and neat silica counterpart was drastic, especially in terms of viscosity and stiffness. A-SiO₂ improved PPO and PA11 miscibility and reduced the crystallinity of PA11, without affecting the T_c, owing to the compatibilization effect. On the other hand, neat silica slightly increased the crystallinity of PA11 and decreased the crystallization temperature of PA11 and the glass transition temperature of PPO as a result of its plasticization.     

Insertion Compounds of 2H-TaS(2).NH(3)

A new method of intercalating metals into layer compounds has been developed using electrolytic generation from the salt solution in ammonia. The results suggest that metals that are soluble in ammonia will form a homogeneous metal-ammonia intercalate layer, NH₃·M_x, when x is less than the limiting solubility of M in NH₃. The superconducting transition temperature (T_c) was found to increase as the c-axis expansion [2δ = c(TaS₂·NH₃·M_x) - c(2H-TaS₂)] decreased when M = lithium, sodium, and potassium. Of all the alkali metals, potassium gave the most stable compounds and the highest T_c, 4.7°K.     

Nutrients Recovery from Dairy Wastewater by Struvite Precipitation Combined with Ammonium Sorption on Clinoptilolite

Struvite precipitation from Wastewater involves an excess of ammonium to create a supersaturated initial solution. The remaining fraction can be a threat to the environment. This work combined struvite precipitation and ammonium sorption using natural zeolite to decrease the ammonium level in the effluent. Two approaches of estimation of feed sample doses were used. One consisted of gradient experiments for ammonium precipitation to the asymptotic level and was combined with clinoptilolite to lower the ammonium level in the effluent. This approach used doses of 0.05:1.51:0.61:1 of Ca:Mg:NH₄⁺:PO₄³⁻ mole ratios, respectively. In contrast, three level design with narrowed NH₄⁺:PO₄³⁻ range reached 0.25:1.51:0.8:1 for Ca:Mg:NH₄⁺:PO₄³⁻ mole ratios. The addition of zeolite decreased effluent ammonium concentration. In both ways, the P and N recoveries were higher than 94% and 72%, respectively. The complexity of the precipitation mixture decreased the ammonium sorption capacity (Q_e) of clinoptilolite from Q_e of 0.52 to 0.10 meq∙g⁻¹ in single and complex solutions, respectively. Thermodynamically, the addition of 1.5 % of clinoptilolite changed the struvite precipitation spontaneity from ∆G of −5.87 to −5.42 kJ·mol⁻¹ and from 9.66 to 9.56 kJ·mol⁻¹ for gradient and three level experimental procedures, respectively. Thus, clinoptilolite demonstrated a positive effect on the struvite precipitation process and its environmental impact.     

The Effect of Sibunit Carbon Surface Modification with Diazonium Tosylate Salts of Pd and Pd-Au Catalysts on Furfural Hydrogenation

Herein, we investigated the effect of the support modification (Sibunit carbon) with diazonium salts of Pd and Pd-Au catalysts on furfural hydrogenation under 5 bars of H₂ and 50 °C. To this end, the surface of Sibunit (Cp) was modified with butyl (Cp-Butyl), carboxyl (Cp-COOH) and amino groups (Cp-NH₂) using corresponding diazonium salts. The catalysts were synthesized by the sol immobilization method. The catalysts as well as the corresponding supports were characterized by Fourier transform infrared spectroscopy, N₂ adsorption-desorption, inductively coupled plasma atomic emission spectroscopy, high resolution transmission electron microscopy, energy dispersive spectroscopy, X-ray diffraction, Hammet indicator method and X-ray photoelectron spectroscopy. The analysis of the results allowed us to determine the crucial influence of surface chemistry on the catalytic behavior of the studied catalysts, especially regarding selectivity. At the same time, the structural, textural, electronic and acid–base properties of the catalysts were practically unaffected. Thus, it can be assumed that the modification of Sibunit with various functional groups leads to changes in the hydrophobic/hydrophilic and/or electrostatic properties of the surface, which influenced the selectivity of the process.