Search Results (67)

This work studies the effect of mesostructured silica–zirconia–tungstophosphoric acid (SiO₂-ZrO₂-TPA) composites used as catalysts in the synthesis of nifedipine by the Hantzsch methodology. The selectivity for nifedipine is determined, along with that of secondary products that may form depending on the reaction conditions. The materials were synthesized via the sol–gel method and characterized by N₂ adsorption–desorption isotherms, infrared spectroscopy (FT-IR), ³¹P solid-state nuclear magnetic resonance (NMR-MAS), X-ray diffraction (XRD), thermogravimetric analysis (TGA), X-ray photoelectron spectra (XPS), and potentiometric titration. The characterization results from the XPS spectra showed that as the Si/Zr ratio drops, the Si-O-Si signal size decreases, while the Zr-O signal size increases. Characterization by titration indicated that an increase in the total acidity of the material, resulting from support modification with tungstophosphoric acid (H₃PW₁₂O₄₀, TPA), enhances the reaction yield. The catalytic activity in the solvent-free Hantzsch reaction was evaluated under thermal heating and microwave irradiation. The experiments conducted at 80 °C achieved a maximum yield of 57% after 4 h of reaction using the Si20Zr80TPA30 catalyst (50 mg), while by microwave heating, the yield significantly improved, reaching 77% in only 1 h of reaction. This catalyst exhibited stability and reusability without significant loss of activity up to the third cycle. Depending on the type of material and the reaction conditions, it is possible to modify the selectivity of the reaction, obtaining a 1,2-dihydropyridine isomeric to nifedipine. Reaction intermediates and other minor secondary products that may be formed in the process were also evaluated. Full article

Nanotopography refers to the intricate surface characteristics of materials at the sub-micron (<1000 nm) and nanometer (<100 nm) scales. These topographical surface features significantly influence the physical, chemical, and biological properties of biomaterials, affecting their interactions with cells and surrounding tissues. The development of nanostructured surfaces of polymeric nanocomposites has garnered increasing attention in the fields of tissue engineering and regenerative medicine due to their ability to modulate cellular responses and enhance tissue regeneration. Various top-down and bottom-up techniques, including nanolithography, etching, deposition, laser ablation, template-assisted synthesis, and nanografting techniques, are employed to create structured surfaces on biomaterials. Additionally, nanotopographies can be fabricated using polymeric nanocomposites, with or without the integration of organic and inorganic nanomaterials, through advanced methods such as using electrospinning, layer-by-layer (LbL) assembly, sol–gel processing, in situ polymerization, 3D printing, template-assisted methods, and spin coating. The surface topography of polymeric nanocomposite scaffolds can be tailored through the incorporation of organic nanomaterials (e.g., chitosan, dextran, alginate, collagen, polydopamine, cellulose, polypyrrole) and inorganic nanomaterials (e.g., silver, gold, titania, silica, zirconia, iron oxide). The choice of fabrication technique depends on the desired surface features, material properties, and specific biomedical applications. Nanotopographical modifications on biomaterials’ surface play a crucial role in regulating cell behavior, including adhesion, proliferation, differentiation, and migration, which are critical for tissue engineering and repair. For effective tissue regeneration, it is imperative that scaffolds closely mimic the native extracellular matrix (ECM), providing a mechanical framework and topographical cues that replicate matrix elasticity and nanoscale surface features. This ECM biomimicry is vital for responding to biochemical signaling cues, orchestrating cellular functions, metabolic processes, and subsequent tissue organization. The integration of nanotopography within scaffold matrices has emerged as a pivotal regulator in the development of next-generation biomaterials designed to regulate cellular responses for enhanced tissue repair and organization. Additionally, these scaffolds with specific surface topographies, such as grooves (linear channels that guide cell alignment), pillars (protrusions), holes/pits/dots (depressions), fibrous structures (mimicking ECM fibers), and tubular arrays (array of tubular structures), are crucial for regulating cell behavior and promoting tissue repair. This review presents recent advances in the fabrication methodologies used to engineer nanotopographical microenvironments in polymeric nanocomposite tissue scaffolds through the incorporation of nanomaterials and biomolecular functionalization. Furthermore, it discusses how these modifications influence cellular interactions and tissue regeneration. Finally, the review highlights the challenges and future perspectives in nanomaterial-mediated fabrication of nanotopographical polymeric scaffolds for tissue engineering and regenerative medicine. Full article

The use of tomato plant residues (i.e., stems, leaves, etc.) as a substrate for catalytic pyrolysis of biomass was investigated. A comprehensive study was conducted to investigate the impact of catalysts on the performance of different pyrolysis fractions (i.e., gas, biosolid, waxes, and bioliquid) as well as the distribution of products within the bioliquid. The catalysts employed in this study were derived from two distinct types of zirconia. The first type was synthesized by a conventional sol-gel method, while the second type was prepared with a modified method aimed at improving the presence of mesopores. This modification involved the incorporation of Pluronic 123. These materials were designated ZrO₂ and ZrO₂P25, respectively. Both types of zirconia were used as supports for tungstophosphoric acid (H₃PW₁₂O₄₀, TPA), a heteropolyacid with a Keggin structure, in the preparation of catalysts with strong acid sites. The results demonstrated that the bioliquid yield of the non-catalytic fast pyrolysis of tomato plant waste was approximately 23% and that the obtained bioliquid contained a wide variety of molecules, which were detected and quantified by GC-MS. In the presence of the catalysts, both the bioliquid yield and the distribution of bioliquid products were substantially modified. Furthermore, the possible sugar degradation pathways leading to the formation of the molecules present in the pyrolytic bioliquids were thoroughly examined. The results obtained from this study indicate that the physicochemical characteristics of the catalysts, specifically their pore size and acidity, have a significant impact on the selectivity of the catalytic processes towards valuable molecules, including anhydro-sugars and furanic derivatives such as furfural and furfuryl alcohol. Full article

ZrO₂, TiO₂, ZrO₂-TiO₂, and TiO₂-ZrO₂ were successfully prepared using the sol–gel method and fully characterized to check their physico-chemical features. X-ray diffraction showed the co-existence of monoclinic and tetragonal ZrO₂ in addition to the Anatase phase for TiO₂. The formation of mixed oxides led to a reduction in the band gap values and a modification of the textural characteristics, while the XPS evidenced an oxygen vacancy-rich surface. The ability of the synthesized materials to eliminate drug contaminants was checked using Sulfamethoxazole (SMX) as a model molecule under UV and BLUE-LED irradiation. The materials’ potential to decrease wastewater toxicity was also studied. The best photocatalyst was TiO₂-ZrO₂ with 76 and 100% conversion under visible and UV irradiation, respectively. Full article

Background: Our previous study found that the addition of pentavalent cations like niobium (Nb) to yttria-stabilized zirconia increased fracture toughness but also raised the coefficient of thermal expansion (CTE), and opacity also increased undesirably. A new surface treatment is required to boost fracture toughness without altering CTE or translucency. Methods: The surfaces of pre-sintered 3 mol% yttria-stabilized tetragonal zirconia polycrystal (3Y-TZP) and 4.2 mol% yttria-stabilized partially stabilized zirconia (4.2Y-PSZ) were treated with a Nb sol solution containing Nb₂O₅ nanoparticles. After drying and sintering, a high-Nb-content surface layer formed with a depth of approximately 1 mm. Results: The Nb content in this surface layer matched that of a bulk material with 1 mol% Nb₂O₅. The tetragonality of the surface zirconia increased, enhancing the surface fracture toughness without changing the CTE or translucency. Conclusions: Adding Nb near the surface improved the fracture toughness without affecting the CTE or translucency. This method could strengthen zirconia prostheses, allowing more reliable dental restorations. Full article

The presented manuscript demonstrates the effect of the thickness of a zinc alloy sublayer on the corrosion resistance and stability of three types of bi-layer systems composed of Co- or Ni-modified zinc coatings (both as sublayers) and a top sol–gel ZrO₂ film in a 5% NaCl solution. In order to obtain more detailed information, the alloy sublayers were electrodeposited with three different thicknesses (1, 5 and 10 µm, respectively) on a low-carbon steel substrate. Three consecutive dip-coated ZrO₂ sol–gel layers were deposited thereafter on the individual zinc alloy sublayers. For comparison, an ordinary electrodeposited zinc coating was obtained and investigated. The aim of this study was to evaluate the effect of the thickness of the zinc-based sublayer on the protective characteristics of the bi-layer systems. The surface morphology features and the phase composition of the latter systems were examined using scanning electron microscopy (SEM), atomic force microscopy (AFM), water contact angle (WCA) measurements and X-ray diffraction (XRD) analyses. The corrosion stability was evaluated by means of potentiodynamic polarization (PDP) curves and polarization resistance (Rp) measurements. The zirconia finish layers possessed an amorphous, dense and hydrophobic nature, while the sublayers were multicrystalline. The results confirmed the increased corrosion resistance of the protective system, which contains electrodeposited sublayer of Zn-Co alloy with a 10 µm thickness in a corrosive test medium. Full article

Hydrogen atoms can enter into metallic materials through penetration and diffusion, leading to the degradation of the mechanical properties of the materials, and the application of hydrogen barrier coatings is an effective means to alleviate this problem. Zirconia coatings (ZrO₂) have been widely studied as a common hydrogen barrier coating, but zirconia undergoes a crystalline transition with temperature change, which can lead to volumetric changes in the coating and thus cause problems such as cracking and peeling of the coating. In this work, ZrO₂ coating was prepared on a Q235 matrix using a sol-gel method, while yttria-stabilized zirconia (YSZ) coatings with different contents of rare earth elements were prepared in order to alleviate a series of problems caused by the crystal form transformation of ZrO₂. The coating performances were evaluated by the electrochemical hydrogen penetration test, pencil hardness test, scratch test, and high-temperature oxidation test. The results show that yttrium can improve the stability of the high-temperature phase of ZrO₂, alleviating the cracking problem of the coating due to the volume change triggered by the crystalline transition; improve the consistency of the coating; and refine the grain size of the oxide. The performance of YSZ coating was strongly influenced by the yttria doping mass, and the coating with 10 wt% yttria doping had the best hydrogen barrier performance, the best antioxidant performance, and the largest adhesion. Compared with the matrix, the steady-state hydrogen current density of the YSZ coating decreased by 72.3%, the antioxidant performance was improved by 65.8%, and the ZrO₂ coating hardness and adhesion levels were B and 4B, respectively, while YSZ coating hardness and adhesion were upgraded to 2H and 5B. With the further increase in yttrium doping mass, the hardness of the coating continued to improve, but the defects of the coating increased, resulting in a decrease in the hydrogen barrier performance, antioxidant performance, and adhesion. In this work, the various performances of ZrO₂ coating were significantly improved by doping with the rare earth element, which provides a reference for further development and application of oxide coatings. Full article

Barium zirconate (BaZrO₃, BZO), which exhibits superior mechanical, thermal, and chemical stability, has been widely used in many applications. In dentistry, BZO is used as a radiopacifier in mineral trioxide aggregates (MTAs) for endodontic filling applications. In the present study, BZO was prepared using the sol–gel process, followed by calcination at 700–1000 °C. The calcined BZO powders were investigated using X-ray diffraction and scanning electron microscopy. Thereafter, MTA-like cements with the addition of calcined BZO powder were evaluated to determine the optimal composition based on radiopacity, diametral tensile strength (DTS), and setting times. The experimental results showed that calcined BZO exhibited a majority BZO phase with minor zirconia crystals. The crystallinity, the percentage, and the average crystalline size of BZO increased with the increasing calcination temperature. The optimal MTA-like cement was obtained by adding 20% of the 700 °C-calcined BZO powder. The initial and final setting times were 25 and 32 min, respectively. They were significantly shorter than those (70 and 56 min, respectively) prepared with commercial BZO powder. It exhibited a radiopacity of 3.60 ± 0.22 mmAl and a DTS of 3.02 ± 0.18 MPa. After 28 days of simulated oral environment storage, the radiopacity and DTS decreased to 3.36 ± 0.53 mmAl and 2.84 ± 0.27 MPa, respectively. This suggests that 700 °C-calcined BZO powder has potential as a novel radiopacifier for MTAs. Full article

The development of direct dimethyl ether (DME) solid oxide fuel cells (SOFCs) has several drawbacks, due to the low catalytic activity and carbon deposition of conventional Ni–zirconia-based anodes. In the present study, the insertion of 2.0 wt.% Ru-Ce_0.7Zr_0.3O_2−δ (ruthenium–zirconium-doped ceria, Ru-CZO) as an anode catalyst layer (ACL) is proposed to be a promising solution. For this purpose, the CZO powder was prepared by the sol–gel synthesis method, and subsequently, nanoparticles of Ru (1.0–2.0 wt.%) were synthesized by the impregnation method and calcination. The catalyst powder was characterized by BET-specific surface area, X-ray diffraction (XRD), field emission scanning electron microscopy with an energy-dispersive spectroscopy detector (FESEM-EDS), and transmission electron microscopy (TEM) techniques. Afterward, the catalytic activity of Ru-CZO catalyst was studied using DME partial oxidation. Finally, button anode-supported SOFCs with Ru-CZO ACL were prepared, depositing Ru-CZO onto the anode support and using an annealing process. The effect of ACL on the electrochemical performance of cells was investigated under a DME and air mixture at 750 °C. The results showed a high dispersion of Ru in the CZO solid solution, which provided a complete DME conversion and high yields of H₂ and CO at 750 °C. As a result, 2.0 wt.% Ru-CZO ACL enhanced the cell performance by more than 20% at 750 °C. The post-test analysis of cells with ACL proved a remarkable resistance of Ru-CZO ACL to carbon deposition compared to the reference cell, evidencing the potential application of Ru-CZO as a catalyst as well as an ACL for direct DME SOFCs. Full article

Bioethanol, which is currently produced commercially from a growing variety of renewable biomass and waste sources, is an appealing feedstock for the production of fuels and chemicals. The literature clearly shows that bioethanol is a versatile building block to be used in biorefineries. The ethanol conversion using several catalysts with acidic, basic, and redox characteristics results in a diverse assortment of high-value bioproducts. High-acidity tungsten zirconia-based catalysts are stated to compete with traditional zeolitic catalysts and can be employed in the dehydration of ethanol to ethylene, but for a low reaction temperature acetic acid is formed, which causes corrosion issues. WO₃-ZrO₂ (W/Zr = 1, atomic) catalysts modified with MoO₃ were prepared by a sol-gel-like procedure and tested in a gas phase ethanol conversion in the presence of air. The citrate derived xerogels were annealed at 853 K for 12 h, allowing low surface area (<10 m²/g) materials with a Mo-W mixed-oxide-rich surface over tetragonal nanostructured zirconia. Catalysts with MoO3-loading produced mainly acetaldehyde, instead of ethylene, as a result of the high reducibility of Mo⁶⁺ when compared to W⁶⁺. During the reaction, the Mo⁶⁺ becomes partially reduced, but Mo⁶⁺/Mo⁵⁺ species are still active for methanol conversion with increased ethylene selectivity due to the high acidity of tetrahedral MO_X species formed during the reaction. Adding water to ethanol, to simulate bioethanol, only leads to a slight inhibition in ethanol conversion over the MoO₃/(WO₃-ZrO₂) catalysts. The results show that molybdenum oxide deposited on tungstated zirconia catalyst is active, with low sensitivity to water, for the valorization of bioethanol into high-value chemicals, such as ethylene and acetaldehyde, and whose selectivity can be tuned by changing the amount of MoO₃ that is loaded. The MoO₃/(WO₃-ZrO₂) catalysts prepared show catalytic behavior similar to that of noble metal-based catalysts reported in the literature for the dehydrogenation of bioethanol in high-value chemicals. Full article

The properties of a catalyst support are closely related to the catalyst activity, yet the focus is often placed on the active species, with little attention given to the support properties. In this work, we specifically investigated the changes in support properties after the addition of P, as well as their impact on catalyst activity when used for catalyst preparation. We prepared the CeO₂-ZrO₂-P₂O₅-Al₂O₃ (CeZrPAl) composite oxides using the sol–gel, impregnation, and mechanical mixing methods, and characterized the support properties using techniques such as XRD, XPS, SEM-EDS, N₂ adsorption–desorption, and Raman spectra. The results showed that the support prepared using the sol–gel method can exhibit a more stable phase structure, larger surface area, higher adsorption capacity for oxygen species, and greater oxygen storage capacity. The addition of an appropriate amount of P is necessary. On the one hand, the crystallization and growth of CePO₄ can lead to a decrease in the Ce content in the cubic phase ceria–zirconia solid solution, resulting in a phase separation of the ceria–zirconia solid solution. On the other hand, CePO₄ can lock some of the Ce³⁺/Ce⁴⁺ redox pairs, leading to a reduction in the adsorption of oxygen species and a decrease in the oxygen storage capacity of the CeZrPAl composite oxides. The research results indicated that the optimal P addition is 6 wt.% in the support. Therefore, we prepared a Pd/CeZrPAl catalyst using CeZrAl with 6 wt.% P₂O₅ as the support and conducted the catalytic oxidation of C₃H₈. Compared with the support without P added, the catalyst activity of the support loaded with P was significantly improved. The fresh and aged (1000 °C/5 h) catalysts decreased by 20 °C and 5 °C in T₅₀ (C₃H₈ conversion temperature of 50%), and by 81 °C and 15 °C in T₉₀ (C₃H₈ conversion temperature of 90%), respectively. Full article

Dental surgery needs a biocompatible implant design that can ensure both osseointegration and soft tissue integration. This study aims to investigate the behavior of a hydroxyapatite-based coating, specifically designed to be deposited onto a zirconia substrate that was intentionally made porous through additive manufacturing for the purpose of reducing the cost of material. Layers were made via sol–gel dip coating by immersing the porous substrates into solutions of hydroxyapatite that were mixed with polyethyleneimine to improve the adhesion of hydroxyapatite to the substrate. The microstructure was determined by using X-ray diffraction, which showed the adhesion of hydroxyapatite; and atomic force microscopy was used to highlight the homogeneity of the coating repartition. Thermogravimetric analysis, differential scanning calorimetry, and Fourier transform infrared spectroscopy showed successful, selective removal of the polymer and a preserved hydroxyapatite coating. Finally, scanning electron microscopy pictures of the printed zirconia ceramics, which were obtained through the digital light processing additive manufacturing method, revealed that the mixed coating leads to a thicker, more uniform layer in comparison with a pure hydroxyapatite coating. Therefore, homogeneous coatings can be added to porous zirconia by combining polyethyleneimine with hydroxyapatite. This result has implications for improving global access to dental care. Full article

Zirconia–silica monolithic catalysts with hierarchical micro/macroporous structure were obtained in a sol-gel process combined with phase separation using inorganic salts, i.e., oxychloride, oxynitrate and sulphate, as a zirconium source. It was found that the use of zirconium oxychloride and prehydrolysis of tetraethoxysilane (TEOS) resulted in materials characterized by a well-developed continuous structure of macropores with a diameter of ca. 10 μm. For zirconium oxynitrate and sulfate modified materials, the prehydrolysis hardly affected the macropore size. The micropores with a diameter of 1.5 nm in the skeleton of all materials provided a large surface area of 550–590 m²/g. A high dispersion of zirconia in the silica skeleton in all studied materials was shown. However, the largest surface concentration of Lewis and Brönsted acid sites was found in the monolith synthesized with zirconium oxychloride. The monoliths were used as a core for continuous-flow microreactors and high catalytic activity was confirmed in the deacetalization of benzylaldehyde dimethyl acetal. The process was characterized by a high efficiency at low temperature, i.e., 35 °C. Full article

This work presents the enhanced corrosion resistance of newly developed two-layer composite coatings deposited on low-carbon steel: electrodeposited zinc alloy coatings (Zn–Ni with 10 wt.% Ni (ZN) or Zn–Co with 3 wt.% Co (ZC), respectively) and a top ZrO₂ sol–gel layer. Surface morphology peculiarities and anti-corrosion characteristics were examined using scanning electron microscopy (SEM), energy dispersive spectroscopy (EDX), atomic force microscopy (AFM), water contact angle (WCA) measurements, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) analyses, potentiodynamic polarization (PDP) curves, corrosion potential (Ecorr), polarization resistance (Rp) measurements (for a prolonged period of 25 days) and open-circuit potential (OCP). The results were compared with the corrosion peculiarities of usual zinc coating. The zirconia top coatings in both systems were amorphous and dense, possessing hydrophobic nature. The experimental data revealed an increased corrosion resistance and protective ability of the ZC system in comparison to that of ZN due to its smooth, homogeneous surface and the presence of poorly crystallized oxides (ZnO and Co₃O₄), both later playing the role of a barrier for corrosive agents. Full article

This work is dedicated to the study of the effect of the synthesis conditions (drying and calcination) of sulfated zirconia on the final catalytic behavior of bifunctional composite catalysts prepared by the physical mixing of the sulfated zirconia (methanol dehydration catalyst) with Cu/ZnO/Al₂O₃ (CZA; methanol synthesis catalyst). The main objective was to optimize the CZA-ZrO₂/SO₄²⁻ composite catalyst for its use in the direct production of dimethyl ether (DME) from syngas. Sulfated zirconia aerogel (AZS) and xerogel (XZS) were prepared using the sol–gel method using different solvent evacuation conditions and calcination temperatures, while the Cu-ZnO(Al) catalyst was synthesized using the coprecipitation procedure. The effectivity of CZA-ZrO₂/SO₄²⁻ composite catalysts for the direct production of dimethyl ether (DME) from syngas was evaluated in a flow reactor at 250 °C and 30 bar total pressure. The characterization of the sulfated zirconia aerogels and xerogels using different techniques showed that the mesoporous aerogel (AZS_0.5300) exhibited the best textural and acidic properties due to the gel drying under supercritical conditions and calcination at 300 °C. As a result, the composite catalyst CZA-AZS_0.5300 exhibited seven times higher DME production than its xerogel-containing counterpart (364 vs. 52 μmol_DME·min⁻¹·g_cat⁻¹). This was attributed to its well-matched metal surface, mesoporous structure, optimal crystallite size and, most importantly, its higher acidity. Full article