Solvent-free cross aldol condensation of aldehydes and ketones over SrMo1-xNixO3-δ perovskite nanocrystals as heterogeneous catalysts.

Aldol condensation is arguably one of the most fascinating reactions that leads to the formation of C-C bonds. Its use in the pharmaceutical industry to synthesis complex drugs from simple aldehydes and ketones has become of paramount importance. Although this is one reaction that has lured a lot of attention, not enough has been explored in heterogeneous catalysis. In this work we have successfully synthesized multicationic perovskites via the soft-template method and characterized them thoroughly. The synthesized perovskite nanocrystals were found to have small SBET however their catalytic application in the conversion of benzaldehyde (BAL) in the aldol condensation with diethyl ketone (DEK) was found to be astonishing. The synthesis was confirmed using many techniques, from determining the oxidation states of the materials using XPS. This gave access to determine the coordination of the metals in the perovskite lattice and also qualitatively assess the oxygen environments that exist. The oxygen vacancies and SBET were used to assess the activity of the perovskite catalysts in the cross-aldol condensation reaction. The optimal conditions for this aldol condensation were found to be 120 °C after 25 h with no solvent using SrMo0.5Ni0.5O3-δ inorganic perovskite which had the highest amount of oxygen vacant sites which gave a conversion of 88 % and an 82 % selectivity towards the desired cross-aldol condensation product. The use of dimethylformamide (DMF) for this reaction is discouraged as it reacts with BAL to produce a higher amide.

One-Step Synthesis of a Mn-Doped Fe2O3/GO Core-Shell Nanocomposite and Its Application for the Adsorption of Levofloxacin in Aqueous Solution.

This study describes for the first time the synthesis, characterization, and application of a MnFe2O3/GO core-shell nanocomposite as an adsorbent for the removal of levofloxacin (Lev) from real water samples. The formation of the proposed nanocomposite was confirmed using various characterization techniques. The structural techniques revealed a 20 nm average particle size of the MnFe2O3/GO core-shell nanocomposite, with a surface area of 70.7 m2 g-1, as shown by the BET results. The most influential parameters (adsorbent dosage, stirring rate, and Lev pH) that affected the adsorption process were optimized using the response surface methodology (RSM) based on a central composite design. The optimum conditions were 0.007 g, 2, and 7 for adsorbent dosage, stirring rate, and Lev pH, respectively. The adsorption behavior of Lev on the MnFe2O3/GO core-shell nanocomposite was examined using isotherm models, kinetics, and thermodynamics. The kinetic models demonstrated that the adsorption process was controlled by both intraparticle and outer diffusion. Furthermore, the results obtained revealed that the adsorption of Lev on MnFe2O3/GO was dominated by electrostatic interactions. Moreover, Dubinin-Radushkevich and Temkin isotherms confirmed that the sorption mechanism was dominated by electrostatic interactions, while Langmuir and Sips models confirmed a monolayer adsorption process. The maximum adsorption capacity of Lev onto the MnFe2O3/GO adsorbent was found to be 129.9 mg g-1. Furthermore, the thermodynamic data revealed that the adsorption system was spontaneous and exothermic. The synthesized MnFe2O3/GO core-shell nanocomposite showed significant recyclability and regenerability properties up to five adsorption-desorption cycles. As a proof of concept, the performance of the prepared adsorbent was evaluated for laboratory-scale purification of spiked real water samples. The prepared adsorbent significantly reduced the concentration of Lev in the real water samples and the removal efficiency ranged from 86 to 97%.

Molybdenum-modified mesoporous SiO2 as an efficient Lewis acid catalyst for the acetylation of alcohols.

A suitable, expeditious and well-organized approach for the acetylation of alcohols with acetic anhydride in the presence of 5%MoO3-SiO2 as an optimum environmentally benign heterogeneous catalyst was developed. The high surface area obtained for 5%MoO3-SiO2, 101 m2 g-1 compared to other catalysts, 22, 23, and 44 m2 g-1 for 5%WO3-ZrO2, 5%WO3-SiO2, and 5%MoO3-ZrO2, respectively, appears to be the driving force for better catalytic activity. Amongst the two dopants used, molybdenum oxide is the better dopant compared to its tungsten oxide counterpart. High yields of up to 86% were obtained with MoO3 doping while WO3 containing catalysts did not show any activity. Other reaction parameters such as reactor stirring speed, and solvent variation were studied and revealed that the optimum stirring speed is 400 rpm and cyclohexane is the best solvent. Thus, the utilization of affordable and nontoxic materials, short reaction times, reusability, and producibility of excellent yields of the desired products are the advantages of this procedure.

Palladium(II) Immobilized on Metal-Organic Frameworks for Catalytic Conversion of Carbon Dioxide to Formate.

In this work, we report the design of a two-dimensional (2D) isostructural metal-organic framework containing Pd(II) active sites, using a bipyridyl dicarboxylate linker (Mg(bpdc)(DMF)2PdCl2]n (Pd@Mg:JMS-2) and [Mn(bpdc)(DMF)2PdCl2]n(Pd@Mn:JMS-2)). The activated MOFs Pd@Mg:JMS-2a and Pd@Mn:JMS-2a were evaluated as heterogeneous catalysts for the hydrogenation of carbon dioxide (CO2) to formate. Under optimal conditions, the MOFs exhibited impressive catalytic activity with formate turnover numbers of 7272 and 9808 for Pd@Mg:JMS-2a and Pd@Mn:JMS-2a, respectively, after 24 h. These catalysts exhibited higher catalytic activity when compared to its homogeneous counterpart that was used as a linker during MOF synthesis. Post-experimental characterization showed that the structural integrity of the MOFs was not altered after catalysis. This work demonstrates that the catalytic activity of homogeneous systems can be enhanced under heterogeneous conditions by anchoring them on MOFs.

Inorganic Perovskite-Induced Synergy on Highly Selective Pd-Catalyzed Hydrogenation of Cinnamaldehyde.

The transformation of various organic molecules into value-added chemicals has been driven by the success in development of highly active catalytic systems. Heterogeneous catalysts have found use in many industrial processes by virtue of their ease of separation and high activities in various reactions. However, many processes employing heterogeneous catalysts in the transformation of organic molecules suffer significantly when it comes to product selectivity. Herein, we report on the synthesis of highly selective palladium nanoparticle (Pd NP)-containing catalysts. The heterogeneous catalysts reported herein consist of active mixed-metal oxides, in the form of perovskites as catalysts, and as catalytic supports for Pd NPs. The activity of pure perovskites when applied as catalysts in the hydrogenation of cinnamaldehyde is 3 factors lower compared with Pd NPs immobilized on them. However, considering the fact that perovskites achieved percentage conversions between 18 and 25% in a short period of time makes them perfect candidates to replace platinum group metals in the future. In addition to being earmarked as the future of catalysis, perovskites induced a synergistic effect on the conversion of the substrate compared to when Pd NPs are immobilized on the silica support. Furthermore, these catalysts are 100% selective to hydrocinnamaldehyde and stable for up to five catalytic cycles. With regard to reusability of the catalysts, Pd/LaFeO3 was used as a benchmark catalyst and revealed the need for surface restructuring of the catalyst for optimum activity.

Synergistic Effects of Gold-Palladium Nanoalloys and Reducible Supports on the Catalytic Reduction of 4-Nitrophenol.

Herein we report on the catalytic activity of mesoporous nickel, iron, cerium, cobalt, and manganese oxides prepared using KIT-6 as a hard template via evaporation-assisted precipitation. The mesoporous metal oxides (MMOs) were characterized and used as heterogeneous catalysts in the reduction of 4-nitrophenol (4-Nip) by sodium borohydride (BH4-). Furthermore, polyamidoamide (PAMAM) dendrimers were used to synthesize gold-palladium nanoalloy particles. The size of AuPd/PAMAM was found to be 3.5 ± 0.8 nm in diameter before being immobilized on the aforementioned mesoporous metal oxides and used as catalysts in the reduction of 4-Nip. Prior to catalytic evaluation, the reduction profiles of the mesoporous metal oxides were investigated by hydrogen-temperature-programmed reduction (H2-TPR) and showed that mesoporous metal oxides can be easily reduced at lower temperatures and that the immobilization of gold-palladium nanoalloy particles lowers their reduction temperatures. Mesoporous cobalt and manganese oxides showed catalytic activity toward 4-Nip reduction, and the activity was enhanced after immobilization of the gold-palladium nanoalloys. Isolation of nanoparticles activity was achieved by immobilization of the gold-palladium nanoalloys on the inert silica support. From this we postulated an electron relay mechanism for the reduction of 4-nitrophenol. With the use of power rate law we showed that 4-Nip reduction follows pseudo-first-order kinetics.