Search Results (33)

The development of non-noble metal catalysts provides a cost-effective and sustainable route for glucose oxidation to gluconic acid. In this study, a series of catalysts based on inexpensive transition metals (Cr, Cu, Ni, Fe) and/or Au were synthesized using siliceous supports (SiO₂ and MCM-41) and systematically evaluated. The aim was to partially or fully replace noble metals with lower-cost alternatives, while maintaining high catalytic performance. Comprehensive characterization—including ICP-AES for composition, N₂ adsorption–desorption for porosity, XRD for structure, H₂-TPR for reducibility, and NH₃-TPD for acidity—was conducted to establish structure–property relationships. Among the tested catalysts, Ni- and Fe-based systems exhibited superior stability, with NiO/SiO₂ achieving gluconic acid yields comparable to Au. The bimetallic Au–Ni/SiO₂ catalyst displayed enhanced metal–support interactions and minimal leaching (<2%), while Au–Fe/SiO₂ improved selectivity, yielding up to 23% gluconic acid, surpassing 5Fe/SiO₂ (18%) and 0.3Au/SiO₂ (15%), albeit with lower stability. These results highlight the potential of low-cost transition-metal and bimetallic catalysts as efficient and economically viable systems for selective glucose oxidation, providing insights for rational catalyst design in sustainable carbohydrate valorization. Full article

The ongoing miniaturization of semiconductor devices necessitates continuous advancements in lithographic processes, which are critical for high-precision circuit formation. To prevent substrate damage during the etching step, a spin-on hardmask (SOH) layer is often introduced between the photoresist (PR) and the substrate. However, residual metal ions in SOH solutions can adversely affect integrated circuit performance, underscoring the need for efficient and chemically compatible removal strategies. This study investigates the adsorption of metal ions (Al³⁺, Cr³⁺, Cu²⁺, Fe³⁺, Ni²⁺, and Ti⁴⁺) from SOH solutions using mesoporous silica materials—MCM-41 and SBA-15—functionalized with various groups (–OH, –NH₂, –SH, and –CH₃). Adsorption performance was evaluated under solvent-only, monomer-containing, and polymer-containing conditions. Among the tested materials, amine-functionalized mesoporous silica exhibited the highest adsorption efficiency, with SBA-15-NH₂ showing relatively effective and uniform performance in polymer-containing systems. Isotherm analysis supported a monolayer chemical adsorption mechanism, suggesting the significance of surface functional groups in the adsorption process. These findings demonstrate the potential of functionalized mesoporous silica as a promising candidate for trace metal ion removal in semiconductor manufacturing, offering enhanced yield and improved process reliability. Full article

This work shows a sustainable methodology for the synthesis of biogenic materials designed for the removal and photodegradation of rhodamine B (RhB), a highly dangerous environmental pollutant that induces reproductive toxicity. The classical synthesis of MCM-41-ordered mesoporous materials was modified using biocompatible rice husk as the silica template. Iron was incorporated and the so-prepared biogenic photocatalysts were characterized by X-ray diffraction, N₂ adsorption–desorption isotherms, transmission electron microscopy, diffuse reflectance UV-Vis, surface pH, cyclic voltammetry, and Fourier transform infrared spectral analysis of pyridine adsorption. The photocatalytic performance of the materials was evaluated following the removal by adsorption and the photon-driven degradation of RhB. The adsorption capacity and photocatalytic activity of the biogenic materials were correlated with their properties, including iron content, texture, surface content, and electrochemical properties. The best biogenic material boosted the degradation rates of RhB under UV irradiation up to 4.7 and 2.2 times greater than the direct photolysis and the benchmark semiconductor TiO₂-P25. It can be concluded that the use of rice husks for the synthesis of biogenic Fe-modified mesoporous materials is a promising strategy for wastewater treatment applications, particularly in the removal of highly toxic organic dyes. Full article

Nanopowders of hydroxyapatite (HA) and Fe-substituted hydroxyapatite (HAFe) were synthesized by wet precipitation on either MCM-41 (a synthetic, mesoporous aluminosilicate material) or an aluminum-containing MCM-41 (AlMCM) support. According to X-ray diffraction data, all of the synthesized materials are composite powders consisting of amorphous silicate and an HA phase with low crystallinity. The presence of aluminum and iron in the structure of the powders resulted in further amorphization. The obtained samples showed high specific surface areas (SSAs), ranging from 162.3 to 186.6 m²/g for MCM-41-HA and from 112.6 to 127.2 m²/g for AlMCM-HA. The hysteresis loops were found to be of type H3, indicating the formation of slit-like pores in the intercrystalline space, as confirmed by transmission electron microscopy, which revealed the presence of lamellar and flake-like particles. Catalytic activity tests showed that the conversion of dibenzothiophene depended on the iron concentration in the material and the acidity of the support. To further improve the catalytic activity of the materials, they were impregnated with molybdenum compounds. Active molybdenum peroxo complexes formed under these conditions enabled 100% conversion of dibenzothiophene. To our knowledge, this is the first study on the influence of MCM-41-HA- or AlMCM-HA-based materials on dibenzothiophene conversion via oxidative desulfurization using hydrogen peroxide as an oxidant. Full article

Innovative nano fertilizers based on nanoparticles present great potential for agriculture since they can stimulate growth and development in different crops. However, the efficiency of nanoparticles directly depends on their physicochemical characteristics, such as composition, shape, size, and the type of plant species. In this work, a material formed by mesoporous silica and iron oxide (Fe₃O₄@MCM-48) was synthesized and used as a nano fertilizer for tomato crop. Materials with different percentages of iron (10, 20, 30, 40, and 50% by weight) were applied to study the effect of the amount of iron in the plants and compared with MCM-48 without iron and ferric chloride hexahydrate. Using X-ray diffraction (XRD), it was possible to identify the phases present in the system, and with Transmission Electron Microscopy (TEM), it was observed that the material is made up of a matrix of MCM-48 with embedded Fe₃O₄ nanoparticles with a size of 5 nm. Also, the results show that all treatments with nano fertilizers increased the content of photosynthetic pigments and carotenoids in leaves. The use of nano fertilizers can be a viable option to improve the crop growth and efficiency of nutrient use in plants. Full article

In the presented work, titanosilicate with the MWW structure (Ti-MWW) was hydrothermally synthesized using boron and titanium precursors, with piperidine as a structure-directing agent. The resulting layered zeolite precursor, with a Si/Ti molar ratio of 50, was treated in an HNO₃ solution to remove extraframework Ti and B species. The acid-modified zeolite was functionalized with transition metal cations (Cu²⁺, Fe²⁺, Mn²⁺) and trinuclear oligocations (Fe(3) and Mn(3)). The application of this catalytic system is supported by the presence of titanium in the catalytic support structure—similar to a commercial system, V₂O₅–TiO₂. The obtained samples were characterized with respect to their structure (P-XRD, DRIFT), textural parameters (low-temperature N₂ sorption), surface acidity (NH₃-TPD), transition metal content (ICP-OES) and form (UV–vis DRS) as well as catalyst’s reducibility (H₂-TPR). Ti-MWW zeolite samples modified with transition metals were evaluated as catalysts for the selective catalytic reduction of NO with ammonia (NH₃-SCR). The effective temperature range for the NO conversion varied depending on the type of active phase used to functionalize the porous support. The catalytic performance was influenced by transition metal content, its form, and accessibility for reactants as well as interactions between the active phase and titanium-containing support. Among the catalysts tested, the copper-modified Ti-MWW zeolite showed the most promising results, maintaining 90% NO conversion rates across a relatively broad temperature range from 200 to 325 °C. This catalyst meets the requirements of modern NH₃-SCR installations, which aim to operate in the low-temperature region, below 250 °C. Full article

Thermochemical recycling of plastics in the presence of catalysts is often employed to facilitate the degradation of polymers. The choice of the catalyst is polymer-oriented, while its selection becomes more difficult in the case of polymeric blends. The present investigation studies the catalytic pyrolysis of polymers abundant in waste electric and electronic equipment (WEEE), including poly(acrylonitrile-butadiene-styrene) (ABS), high-impact polystyrene (HIPS) and poly(bisphenol-A carbonate) (PC), along with their blends with polypropylene (PP) and poly(vinyl chloride) (PVC). The aim is to study the kinetic mechanism and estimate the catalysts’ effect on the activation energy of the degradation. The chosen catalysts were Fe₂O₃ for ABS, Al-MCM-41 for HIPS, Al₂O₃ for PC, CaO for Blend A (comprising ABS, HIPS, PC and PP) and silicalite for Blend B (comprising ABS, HIPS, PC, PP and PVC). Thermogravimetric experiments were performed in a N₂ atmosphere at several heating rates. Information on the degradation mechanism (degradation steps, initial and final degradation temperature, etc.) was attained. It was found that for pure (co)polymers, the catalytic degradation occurred in one-step, whereas in the case of the blends, two steps were required. For the estimation of the activation energy of those degradations, isoconversional kinetic models (integral and differential) were employed. In all cases, the catalysts used were efficient in reducing the estimated E_α, compared to the values of E_α obtained from conventional pyrolysis. Full article

The catalytic decomposition of CH₄ to H₂ and carbon nanotubes (CNTs) was investigated regarding Pt(1)-Fe(30)/MCM-41 and Fe(30)/MCM-41 using a fixed-bed flow reactor under an atmosphere. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), transmission electron microscope (TEM), and Raman spectroscopy were used to characterize the behavior of Pt(1)-Fe(30)/MCM-41 and Fe(30)/MCM-41. The hydrogen yield of Pt(1)-Fe(30)/MCM-41 was 3.2 times higher than that of Fe(30)/MCM-41. When 1 wt% of Pt was added to Fe(30)/MCM-41(Mobil Composition of Matter No. 41), the atomic percentage of Fe2p increased from 13.39% to 16.14% and the core Fe2p_1/2 electron levels of Fe⁰ and Fe²⁺ chemically shifted to lower energies (0.2 eV and 0.1 eV, respectively) than those of Fe(30)/MCM-41. The Fe, Pt, Si, and O nanoparticles were uniformly distributed on the catalyst surface, and the average iron particle sizes of the Pt(1)-Fe(30)/MCM-41 and Fe(30)/MCM-41 were about 33.4 nm and 58.5 nm, respectively. This is attributed to the uniform distribution of the nano-sized iron particles on the MCM-41 surface, which was due to the suitable metal-carrier interaction (SMCI) between Fe, Pt, and MCM-41 and the high reduction degree of Fe due to the spillover effect of H₂ from Pt to Fe. Pt(1)-Fe(30)/MCM-41 produced multiwalled CNTs and bamboo-shaped CNTs with high crystallinity and graphitization degree using the tip-growth mechanism, with an I_D/I_G ratio of 0.93 and a C(101)/C(002) ratio of 0.64. Full article

Tetracycline (TC) is a common antibiotic; when untreated TC enters the environment, it will cause a negative impact on the human body through the food chain. In the present study, MnO₂/MCM-41@Fe₃O₄ (FeMnMCM) prepared using a hydrothermal and redox method and Camellia oleifera shell-activated carbon (COFAC) prepared through alkali activation were encapsulated using alginate (ALG) and calcium chloride as a cross-linking matrix to give the composite beads COFAC–FeMnMCM–ALG. The resultant COFAC–FeMnMCM–ALG composite beads were then carefully characterized, showing a high immobilization of MnO₂/MCM-41@Fe₃O₄, with porous COFAC as an effective bioadsorbent for enriching the pollutants in the treated samples. These bead catalysts were subsequently applied to the oxidative degradation of TC in a Fenton oxidation system. Several parameters affecting the degradation were investigated, including the H₂O₂ concentration, catalyst dosage, initial TC concentration, and temperature. A very high catalytic activity towards the degradation of TC was demonstrated. The electron paramagnetic resonance (EPR) and quenching results showed that ·OH and ·O₂⁻ were generated in the system, with ·OH as the main radical species. In addition, the COFAC–FeMnMCM–ALG catalyst exhibited excellent recyclability/reusability. We conclude that the as-prepared COFAC–FeMnMCM–ALG composite beads, which integrate MnO₂ and Fe₃O₄ with bioadsorbents, provide a new idea for the design of catalysts for advanced oxidation processes (AOPs) and have great potential in the Fenton oxidation system to degrade toxic pollutants. Full article

Two series of MCM-36 zeolites intercalated with various pillars and modified with iron were synthesized, analyzed with respect to their physicochemical properties, and tested as catalysts for the NH₃-SCR process. It was found that the characteristic MWW morphology of MCM-36 can be obtained successfully using silica, alumina, and iron oxide as pillars. Additionally, one-pot synthesis of the material with iron resulted in the incorporation of monomeric Fe³⁺ species into the framework positions. The results of catalytic tests revealed that the one-pot synthesized sample intercalated with silica and alumina was the most efficient catalyst of NO reduction, exhibiting ca. 100% activity at 250 °C. The outstanding performance of the material was attributed to the abundance of Lewis acid sites and the beneficial influence of alumina on the distribution of iron species in the zeolite. In contrast, the active centers originating from the Fe₂O₃ pillars improved the NO conversion in the high-temperature range. Nevertheless, the aggregated particles of the metal oxide limited the access of the reacting molecules to the inner structure of the catalyst, which affected the overall activity and promoted the formation of N₂O above 300 °C. Full article

The aim of the present study was to obtain a hydrogel-based film as a carrier for the sustained and controlled release of vancomycin, an antibiotic commonly used in various types of infections. Considering the high-water solubility of vancomycin (>50 mg/mL) and the aqueous medium underlying the exudates, a prolonged release of vancomycin from an MCM-41 carrier was sought. The present work focused on the synthesis of malic acid coated magnetite (Fe₃O₄/malic) by co-precipitation, synthesis of MCM-41 by a sol-gel method and loading of MCM-41 with vancomycin, and their use in alginate films for wound dressing. The nanoparticles obtained were physically mixed and embedded in the alginate gel. Prior to incorporation, the nanoparticles were characterized by XRD, FT-IR and FT-Raman spectroscopy, TGA-DSC and DLS. The films were prepared by a simple casting method and were further cross-linked and examined for possible heterogeneities by means of FT-IR microscopy and SEM. The degree of swelling and the water vapor transmission rate were determined, considering their potential use as wound dressings. The obtained films show morpho-structural homogeneity, sustained release over 48 h and a strong synergistic enhancement of the antimicrobial activity as a consequence of the hybrid nature of these films. The antimicrobial efficacy was tested against S. aureus, two strains of E. faecalis (including vancomycin-resistant Enterococcus, VRE) and C. albicans. The incorporation of magnetite was also considered as an external triggering component in case the films were used as a magneto-responsive smart dressing to stimulate vancomycin diffusion. Full article

The catalytic performance of Fe-catalysts in selective catalytic reduction of nitrogen oxides with ammonia (NH₃-SCR) strongly depends on the nature of iron sites. Therefore, we aimed to prepare and investigate the catalytic potential of Fe-MCM-22 with various Si/Fe molar ratios in NH₃-SCR. The samples were prepared by the one-pot synthesis method to provide high dispersion of iron and reduce the number of synthesis steps. We have found that the sample with the lowest concentration of Fe exhibited the highest catalytic activity of ca. 100% at 175 °C, due to the abundance of well-dispersed isolated iron species. The decrease of Si/Fe limited the formation of microporous structure and resulted in partial amorphization, formation of iron oxide clusters, and emission of N₂O during the catalytic reaction. However, an optimal concentration of Fe_xO_y oligomers contributed to the decomposition of nitrous oxide within 250–400 °C. Moreover, the acidic character of the catalysts was not a key factor determining the high conversion of NO. Additionally, we conducted NH₃-SCR catalytic tests over the samples after poisoning with sulfur dioxide (SO₂). We observed that SO₂ affected the catalytic performance mainly in the low-temperature region, due to the deposition of thermally unstable ammonium sulfates. Full article

Mesoporous silica of MCM-41 type with spherical morphology was modified with copper, iron, or manganese as well as pairs of these metals by template ion-exchange (TIE) method. The obtained samples were characterized with respect to their structure (XRD), morphology (SEM-EDS), textural parameters (low-temperature N₂ sorption), surface acidity (NH₃-TPD), transition metal loadings (ICP-OES), their deposited forms (UV-vis DRS) and reducibility (H₂-TPR). The catalytic performance of monometallic and bimetallic samples in the selective catalytic reduction of NO with ammonia (NH₃-SCR) was tested. The best catalytic results presented a bimetallic copper-manganese sample, which was significantly more active than the mechanical mixture of monometallic copper and manganese catalysts. The synergistic cooperation of manganese and copper species is possibly related to charge relocation between them, resulting in activation of the catalyst in oxidation of NO to NO₂, which is necessary for the fast NH₃-SCR reaction. Full article

The application of layered zeolites of MWW topology in environmental catalysis has attracted growing attention in recent years; however, only a few studies have explored their performance in selective catalytic reduction with ammonia (NH₃-SCR). Thus, our work describes, for the first time, the one-pot synthesis of Fe-modified NH₃-SCR catalysts supported on MCM-22, MCM-36, and ITQ-2. The calculated chemical composition of the materials was Si/Al of 30 and 5 wt.% of Fe. The reported results indicated a correlation between the arrangement of MWW layers and the form of iron in the zeolitic structure. We have observed that one-pot synthesis resulted in high dispersion of Fe³⁺ sites, which significantly enhanced low-temperature activity and prevented N₂O generation during the reaction. All of the investigated samples exhibited almost 100% NO conversion at 250 °C. The most satisfactory activity was exhibited by Fe-modified MCM-36, since 50% of NO reduction was obtained at 150 °C for this catalyst. This effect can be explained by the abundance of isolated Fe³⁺ species, which are active in low-temperature NH₃-SCR. Additionally, SiO₂ pillars present in MCM-36 provided an additional surface for the deposition of the active phase. Full article

Noble metal catalysts currently dominate the landscape of chemical synthesis, but cheaper and less toxic derivatives are recently emerging as more sustainable solutions. Iron is among the possible alternative metals due to its biocompatibility and exceptional versatility. Nowadays, iron catalysts work essentially in homogeneous conditions, while heterogeneous catalysts would be better performing and more desirable systems for a broad industrial application. In this review, approaches for heterogenization of iron catalysts reported in the literature within the last two decades are summarized, and utility and critical points are discussed. The immobilization on silica of bis(arylimine)pyridyl iron complexes, good catalysts in the polymerization of olefins, is the first useful heterogeneous strategy described. Microporous molecular sieves also proved to be good iron catalyst carriers, able to provide confined geometries where olefin polymerization can occur. Same immobilizing supports (e.g., MCM-41 and MCM-48) are suitable for anchoring iron-based catalysts for styrene, cyclohexene and cyclohexane oxidation. Another excellent example is the anchoring to a Merrifield resin of an Fe^II-anthranilic acid complex, active in the catalytic reaction of urea with alcohols and amines for the synthesis of carbamates and N-substituted ureas, respectively. A SILP (Supported Ionic Liquid Phase) catalytic system has been successfully employed for the heterogenization of a chemoselective iron catalyst active in aldehyde hydrogenation. Finally, Fe^III ions supported on polyvinylpyridine grafted chitosan made a useful heterogeneous catalytic system for C–H bond activation. Full article