Search Results (79)

Catalysis plays a pivotal role in green chemistry practices, particularly in reducing waste generated during chemical synthesis. Decatungstate (DT) emerges as a potent photocatalyst for Type I oxidations, exhibiting remarkable resilience to oxygen quenching, a characteristic that sets it apart from other excited triplet state photocatalysts. While homogeneous DT catalysis demonstrates effectiveness, its solubility poses challenges for its separation and recycling. To address these limitations, we focus on the development and comparison of heterogeneous DT photocatalysts, aiming to optimize their yield, recovery, and reusability. We synthesized tetrabutylammonium decatungstate (TBADT)-supported catalysts using silica, alumina, titanium dioxide, and glass wool and characterized them using diffuse reflectance measurements. Subsequently, we evaluated their photocatalytic performance by monitoring the oxidation of 1-phenylethanol and cyclohexanol under UVA irradiation. Our findings reveal that TBADT@silica emerges as the most effective catalyst, achieving approximately 20% conversion of cyclohexanol and 50% conversion of 1-phenylethanol with good reusability. Interestingly, we observed that 3-aminopropyl-triethoxysilane (APTES) treatment, intended to enhance DT anchoring, unexpectedly quenches the ³DT* triplet state, reducing catalytic activity. This unexpected finding underscores the importance of careful consideration in designing robust and recyclable heterogeneous decatungstate catalysts. Our research contributes significantly to the advancement of heterogeneous photocatalysis, paving the way for future applications in flow photochemistry. Further, we share a Python code (Google 3.12.11) to correct spectra obtained in Cary spectrometers. Full article

A series of half-titanocenes containing different trialkylsilyl para-phenoxy substituents, Cp*TiCl₂(O-2,6-ⁱPr₂-4-R-C₆H₂) [Cp* = C₅Me₅; R = Si(n-Bu)₃ (5), SiMe₂(n-C₈H₁₇) (6), SiMe₂(t-Bu) (7)], were prepared and identified. Catalytic activity in ethylene polymerization by Cp*TiCl₂(O-2,6-ⁱPr₂-4-R-C₆H₂) [R = H (1), SiMe₃ (2), SiEt₃ (3), Si(i-Pr)₃ (4), 5–7]–MAO (methylaluminoxane) catalysts increased in the following order (in toluene at 25 °C, ethylene 4 atm): R = H (1) < SiMe₃ (2), SiEt₃ (3), Si(i-Pr)₃ (4) < SiMe₂(t-Bu) (7) < SiMe₂(n-C₈H₁₇) (6) < Si(n-Bu)₃ (5, activity = 6.56 × 10⁴ kg-PE/mol-Ti·h). The results thus suggest that the introduction of an alkyl group into a silyl substituent led to an increase in activity. The activities of 5 were affected by the Al/Ti molar ratio (amount of MAO charged), and the highest activity (7.00 × 10⁵ kg-PE/mol-Ti·h) was observed under optimized conditions at 50 °C, whereas the activity decreased at 80 °C. In ethylene copolymerization with 1-dodecene, the Si(n-Bu)₃ analog (5) exhibited remarkable catalytic activity (4.32 × 10⁶ kg-polymer/mol-Ti·h at 25 °C), which was higher than those of the reported catalysts (1–3), affording poly(ethylene-co-1-dodecene)s with efficient comonomer incorporation as observed in 3 [r_E = 3.77 (5) vs. 3.58 (3)]. Full article

Titanium, the second most abundant and one of the cheapest, non-toxic transition metals in the Earth’s crust, is highly favorable for catalytic applications due to its widespread availability, low cost, low toxicity, and well-documented biocompatibility. However, because of its high affinity for oxygen and inherent Lewis acidity, titanium complexes generally exhibit lower tolerance toward various functional groups compared with complexes of later transition metals. The incorporation of cyclopentadienyl ligands significantly enhances the structural tunability of these complexes in their 3D configuration. By modifying the ligand framework, it is possible to fine-tune the Lewis acidity of the central titanium atom as well as the lability and binding characteristics of the ligands. This strategy enables precise control over the catalytic performance of titanocene complexes. The main body of this review provides an overview of recent advances in titanocene catalysis within the field of chemical synthesis since 2019. It includes illustrative examples that demonstrate the substrate scope and practical applications of titanocene catalysts in the synthesis of complex organic molecules and natural products. Finally, the review outlines current research opportunities and strategic directions for future developments in titanocene-based catalysis. Full article

Anodised metal matrices represent a versatile and multifunctional platform for the development of advanced materials with tunable physicochemical properties. Through electrochemical oxidation processes—commonly referred to as anodisation—metals such as aluminium, titanium, niobium, zinc and tantalum can be transformed into structured oxide layers with defined porosity, thickness and surface morphology. These methods enable the fabrication of ordered nanoporous arrays, nanotubes and nanowires, depending on the process parameters and the type of metal. The review introduces and outlines the various anodisation techniques and parameters. This is crucial, since each individual metal requires specified optimal conditions to obtain a stable anodised oxide layer. This review provides an overview of recent advances in the design and application of anodised metal substrates, with the focus on their role as functional platforms in catalysis, sensing, energy storage and biomedical engineering. Special attention is given to post-anodisation surface modification strategies, such as chemical functionalisation, thin-film deposition and molecular-level integration, which significantly expand the utility of these materials. The review also highlights the challenges, limitations and future perspectives of anodising technologies, aiming to guide the rational design of next-generation devices based on engineered oxide architectures. Full article

Background: Carbohydrate-derived chiral ligands are promising tools in asymmetric catalysis due to their structural diversity, chirality, and availability. However, ligands based on galactose or sorbose have been scarcely explored in the enantioselective addition of dialkylzinc reagents to aldehydes. Methods: A series of chiral diols and β-amino alcohols was synthesized from methyl D-glucopyranoside, methyl D-galactopyranoside, and D-fructose. These ligands were tested in the titanium tetraisopropoxide-promoted enantioselective addition of diethylzinc to aromatic and aliphatic aldehydes. Results: Several ligands, particularly those with a D-fructopyranose backbone, exhibited excellent catalytic activity, with conversion rates up to 100% and enantioselectivities up to 96% ee. Notably, this study reports for the first time the use of β-amino alcohols derived from fructose and sorbose in this transformation. Conclusions: Carbohydrate-based ligands represent effective, inexpensive, and structurally versatile scaffolds for developing highly enantioselective catalysts, expanding the utility of sugars in asymmetric organometallic reactions. Full article

To investigate the application potential of amorphous transition metal chalcogenides in catalysis, this study successfully synthesized amorphous molybdenum telluride (MoTe_x) materials and systematically explored their structural characteristics, compositional modulation, and catalytic performance. Experimental results indicate that the synthesized amorphous system consists of particles of approximately 200–300 nm in size. This distinct microstructure facilitates the exposure of abundant active sites and enhances physical adsorption capacity. The amorphous MoTe₂/MoTe₃ catalysts achieve an approximately 30%/40% degradation of methylene blue (MB) within 90 min, demonstrating significantly enhanced photocatalytic efficiency compared to that of crystalline MoTe₂ (≈20% degradation under identical conditions). Furthermore, when integrated with titanium dioxide (TiO₂), the composite exhibits exceptional co-catalytic performance, achieving a 90% degradation of MB within 90 min under visible-light irradiation, representing a catalytic efficiency improvement exceeding 160% compared to the results for pristine TiO₂. Furthermore, through comparative analysis of the catalytic behavior and microstructural variations between amorphous MoTe₃ (a-MoTe₃) and MoTe₂ (a-MoTe₂), we observed that the catalytic activity of molybdenum tellurides exhibits a weak correlation with the tellurium content, with co-catalytic efficacy jointly governed by the density of the active sites and the physical adsorption properties. This research provides new methods and insights for the study and improvement of catalytic performance in chalcogenide materials. Full article

For the efficient operation of various TiO₂-based devices, it is important to understand the patterns of electric charge transport. In the present paper TiO₂-C-Cu nanocomposites were synthesized by the electrochemical method. The band gap energy Eg of all systems was found to be approximately the same, 3.2 eV. Both copper ions replacing titanium ions and copper ions within the CuO phase were detected. The modification of TiO₂-C nanotubes by copper led to a significant increase in conductivity and photocurrent, which may be associated with the formation of new donor states (Ti³⁺ centers) creating levels in the band gap of TiO₂-C-Cu. The characteristics of charge carrier transport (including photocurrent) in TiO₂-C-Cu materials were revealed for the first time. The conductivity at DC and at low frequencies of AC is due to the movement of electrons along the conduction zone, whereas at high frequencies there is a hopping mechanism of conduction. The acquired original results testify to the potential usage of TiO₂-C-Cu nanocomposites in the field of catalysis and photoelectrochemistry. Full article

Chiral ansa-η⁵-complexes of transition metals have shown remarkable efficacy in organometallic synthesis and catalysis. Additionally, enantiomerically pure ansa-complexes hold promise for the development of novel chiral materials and pharmaceuticals. The discovery and synthesis of a diverse range of group IVB and IIIB metal complexes represents a significant milestone in the advancement of stereoselective catalytic methods for constructing metal-C, C-C, C-H, and C-heteroatom bonds. The synthesis of enantiomerically pure metallocenes can be accomplished through several strategies: utilizing optically active precursors of η⁵-ligands, separation of diastereomers of complexes with enantiomerically pure agents, and synthesis via the stereocontrolled reactions of enantiomerically pure σ-complexes with prochiral anions of η⁵-ligands. This review focuses on the analysis of various nuances of the synthesis of enantiomerically pure ansa-η⁵-complexes of titanium and lanthanum families. Their applicability as effective catalysts in asymmetric carbomagnesiation, carbo- and cycloalumination, oligo- and polymerization, Diels–Alder cycloaddition, reactions of zirconaaziridines, cyclization, hydrosilylation, hydrogenation, hydroamination, and other processes are highlighted as well. Full article

Antibiotic residues in the marine environment pose a serious threat to ecosystems and human health, and there is an urgent need to develop efficient and selective pollution control technologies. Molecular imprinting technology (MIT) provides a new idea for antibiotic pollution control with its specific recognition and targeted removal ability. However, traditional titanium dioxide (TiO₂) photocatalysts have limited degradation efficiency and lack of selectivity for low concentrations of antibiotics. This paper reviews the preparation strategy and modification means of molecularly imprinted TiO₂ (MI-TiO₂) and its composites and systematically explores its application mechanism and performance advantages in marine antibiotic wastewater treatment. It was shown that MI-TiO₂ significantly enhanced the selective degradation efficiency of antibiotics such as tetracyclines and sulfonamides through the enrichment of target pollutants by specifically imprinted cavities, combined with the efficient generation of photocatalytic reactive oxygen species (ROS). In addition, emerging technologies such as magnetic/electric field-assisted catalysis and photothermal synergistic effect further optimized the recoverability and stability of the catalysts. This paper provides theoretical support for the practical application of MI-TiO₂ in complex marine pollution systems and looks forward to its future development in the field of environmental remediation. Full article

As a carbon-neutral and renewable raw material, cellulose can be transformed into biomass fuels to reduce the dependence on fossil fuels and carbon dioxide emissions. In view of harsh reaction conditions, low selectivity of product, and easy deactivation of the catalyst, this study studied the use of photothermal catalytic technology to convert cellulose into bio-oil rich in levulinic acid. It was discovered that a synergistic effect between heating and photocatalysis is present in cellulose degradation. Different metals were loaded on carbon nanotubes doped with titanium dioxide to prepare different photothermal catalysts, and their catalytic effects on cellulose were compared. It was found that TiO₂-CNT loaded with platinum metal exhibited the highest catalytic performance. By adopting Pt/TiO₂-CNT as the catalyst, the conversion rate of bio-oil reached 99.44%, and the selectivity of LA reached 44.41% at 220 °C for 3 h. As the photothermal catalysis increased the H/C ratio and decreased the O/C ratio of the liquid product, the calorific value reached 21.01 MJ/kg. This study can promote the further industrial application of lignocellulose to prepare fuel oil and decrease the environmental pollution caused by the massive consumption of fossil fuels. Full article

The chemical conversion of plastic waste has been considered an important subject in terms of the circular economy, and the chemical recycling and upcycling of poly(ethylene terephthalate) (PET) has been considered one of the most important subjects. In this study, the depolymerization of PET with n-hexylamine, n-octylamine, and 3-amino-1-propanol has been explored in the presence of Cp*TiCl₃ (Cp* = C₅Me₅). The reactions of PET with n-hexylamine and n-octylamine at 130 °C afforded the corresponding N,N′-di(n-alkyl) terephthalamides in high yields (>90%), and Cp*TiCl₃ plays a role as the catalyst to facilitate the conversion in exclusive selectivity. The reaction of PET with 3-amino-1-propanol proceeded at 100 °C even in the absence of the Ti catalyst, affording N,N′-bis(3-hydroxy) terephthalamides in high yields. A unique contrast has been demonstrated between the depolymerization of PET by transesterification with alcohol and by aminolysis; the depolymerizations with these amines proceeded without the aid of a catalyst. Full article

Research on converting methane to hydrogen has gained more attention due to the availability of methane reserves and the global focus on sustainable and environmentally friendly energy sources. The decomposition of methane through catalysis (CDM) has excellent potential to produce clean hydrogen and valuable carbon products. However, developing catalysts that are both active and stable is a highly challenging area of research. Using titanium isopropoxide as a precursor and different loadings of TiO₂ (10 wt.%, 20 wt.%, and 30 wt.%), alumina has been coated with TiO₂ in a single-step hydrothermal synthesis procedure. These synthesized materials are examined as possible support materials for CDM; different wt.% of iron is loaded onto the synthesized support material using a co-precipitation method to enhance the methane conversion via a decomposition reaction. The result shows that the 20 wt.% Fe/20 wt.% Ti-Al (20Fe/20Ti-Al) catalyst demonstrates remarkable stability and exhibits superior performance, reaching a conversion rate of methane of 94% with hydrogen production of 84% after 4 h. The outstanding performance is primarily due to the moderate interaction between the support and the active metal, as well as the presence of the rutile phase. The 20Fe/30Ti-Al catalyst exhibited lower activity than the other catalysts, achieving a methane conversion of 85% and hydrogen production of 79% during the reaction. Raman and XRD analysis revealed that all the catalysts generated graphitic carbon, with the 20Fe/20Ti-Al catalyst specifically producing single-walled carbon nanotubes. Full article

Contaminated drinking water is a major health hazard in large urban areas as well as remote communities. Several pollutants detected in rivers and lakes are hormone disruptors that are harmful to consumers as well as aquatic life. In this contribution, we present a new material, synthesized using novel green technologies, designed for solar- or LED-driven degradation of pollutants. This material is based on a glass fiber support, loaded with black TiO₂, a modified form of TiO₂ with strong visible light absorption and without any toxic metal or non-metal dopants. This photocatalyst is fully compatible with flow applications. The effectiveness of the catalyst is demonstrated with crocin and 17β-estradiol, the former being a natural carotenoid used as a screening tool and the latter being a common hormonal disruptor. Our work shows that under visible light illumination, our supported black TiO₂ can degrade these water contaminants with greater efficiency than conventional TiO₂. We envision that our findings can contribute to the production of inexpensive, large-scale solar or LED-based water decontamination systems that could be rapidly deployed to sites in need. Operation of such systems would require minimal training and could be monitored remotely. In addition to the catalyst’s non-toxicity and inflow compatibility, the material also has a long shelf life and is easy and inexpensive to produce, making it an attractive candidate for developing water treatment devices. Full article

Nano metal oxides (NMOs), with their unique physico-chemical properties and low toxicity, have become a focus of research in heterogeneous catalysis. Their distinct characteristics, which can be tailored based on size and structure, make them highly efficient catalysts. NMOs have the potential to significantly contribute to the degradation of numerous environmental pollutants through photolytic decomposition. This work comprehensively analyzes the synthesis, catalytic performance, and applications of photocatalytically active metal oxides, specifically titanium, zinc, copper, iron, silver, tin, and tungsten oxides. The primary objective is to demonstrate how the effectiveness of photocatalytic processes can be enhanced and optimized by incorporating metals, non-metals, and metalloids into their structure and forming heterostructures. Furthermore, the aim is to understand the underlying process of photocatalytic oxidation thoroughly. Photocatalysis, a promising approach in advanced oxidation processes, has garnered significant interest in these fields. Full article

The traditional catalytic oxidation of carbon monoxide (CO) using metal oxide catalysts often requires either high temperatures (thermocatalysis) or ultraviolet light (UV) excitation (photocatalysis), limiting practical applications under ambient conditions. Our research aimed to develop a catalytic system capable of oxidizing CO to CO₂ at room temperature and in the dark. Using the Strong Metal–Support Interaction (SMSI) methodology, several titanium oxide (TiO₂)-complexed metals were prepared (Ag, Au, Pd, and Pt). The highest catalytic efficiency of CO oxidation at room temperature was demonstrated for the TiO₂-Pt complex. Therefore, this complex was further examined structurally and functionally. Two modes of operation were addressed. The first involved applying the catalytic system to remove CO from an individual’s environment (environmental system), while the second involved the installation of the catalysis chamber as a part of a personal protection unit (e.g., a mask). The catalytic activity exhibited a significant reduction in CO levels in both the environmental and personal protection scenarios. The practical application of the system was demonstrated through efficient CO oxidation in air emitted from a controlled fire experiment conducted in collaboration with the Israel Fire and Rescue Authority. Full article