Keggin-Type Heteropoly Salts as Bifunctional Catalysts in Aerobic Baeyer-Villiger Oxidation

The cobalt, manganese, and iron salts of tungstophosphoric or molybdophosphoric acid with growing content of metals were applied for the first time as catalysts in the Baeyer-Villiger (BV) oxidation of cyclohexanone to ε-caprolactone with molecular oxygen. The catalysts were characterized with Fourier transform infrared spectroscopy (FTIR), X-ray fluorescence (XRF), and ethanol decomposition reaction. Introduction of transition metals into the heteropoly structure increases the activity of resulting heteropoly salts in comparison with parent heteropolyacids. It was shown that the most active catalysts are salts of the heteropoly salts with one metal atom introduced and one proton left (HMPX) type, (where M = Co, Fe, Mn, and X = W, Mo) with the metal to proton ratio equal one. Among all of the studied catalysts, the highest catalytic activity was observed for HCoPW. The effect indicates that both the acidic and redox properties are required to achieve the best performance. The Baeyer-Villiger (BV) oxidation mechanism proposed identifies the participation of heteropoly compounds in three steps of the investigated reaction: oxidation of aldehyde to peracid (redox function), activation of carbonyl group (Lewis acidity), and decomposition of the Criegee adduct to ε-caprolactone (Brønsted acidity)

Synthesis of Nanocrystalline Mg-Al Hydrotalcites in the Presence of Starch—the Effect on Structure and Composition

The study describes the synthesis of Mg-Al hydrotalcite (Ht) with the use of starch as a structure controlling biotemplate. Syntheses were carried out at room temperature, by co-precipitation at pH = 10. The investigated synthesis parameters included the nature of the precipitating agent (NaOH/Na2CO3 or NH3aq/(NH4)2CO3), the nature of starch (potato, corn and cassava), the method of starch addition to reagents, the method of drying and the effect of washing. The materials were examined with X-ray diffraction, scanning electron microscopy/energy dispersive X-ray spectroscopy and infrared spectroscopy. The data show that synthesis of Ht materials in the presence of starch, with use of the ammonia-based precipitant, enabled preparation of nanocrystalline Ht with very fine (<50 nm) particle size. All investigated starches had a similar effect on the crystallinity and the grain size of Ht precipitates. Ht with the smallest nanocrystals was obtained when starch was present in all solutions used for synthesis, and the final product subjected to freeze drying. Washing with water was found to enhance recrystallization and exchange of nitrates for carbonates. Infrared spectra showed that an interaction exists between the biopolymer template and the Ht particles, resulting in a higher degree of order within the Ht-adhering starch component

Fine Crystalline Mg-Al Hydrotalcites as Catalysts for Baeyer-Villiger Oxidation of Cyclohexanone with H2O2

The catalytic activity of Mg-Al hydrotalcite (HT) materials in base-catalyzed reactions is known to be promoted by the low crystallinity of the HT solid. In the present work, two routes enabling the preparation of finely crystalline Mg-Al HT materials were explored: (1) the inverse microemulsion technique, and (2) co-precipitation in the presence of starch. Carbonate, chloride and bromide forms of HT were prepared, examined with X-ray diffraction, scanning electron microscopy/energy dispersive X-ray spectroscopy and infrared spectroscopy, and used as catalysts in the Baeyer–Villiger oxidation of cyclohexanone to ε-caprolactone with a H2O2/acetonitrile system. The bromide forms proved significantly less active than the chlorides and carbonates, as they promoted nonselective consumption of H2O2. The fine crystalline materials were more active than the more crystalline HT references obtained by conventional co-precipitation. Catalysts prepared by inverse microemulsion were less crystalline and more active than the starch-templated ones, but suffered stronger deactivation by the acidic reaction environment. Alkalization of the reaction medium with NaHCO3 stabilized the HT materials and increased the ε-caprolactone yield, which became comparable for both types of fine crystalline catalysts—thus pointing to the synthesis involving a simple and cheap starch templating approach as being a particularly attractive one

Physicochemical and catalytic properties of hybrid catalysts derived from 12-molybdophosphoric acid and montmorillonites

The hybrid catalysts derived from 12-molybdophosphoric acid (H3PMo12O40 denoted as HPMo) and montmorillonite (Na, H-exchanged montmorillonites derived from Polish bentonite denoted as Na-Mt, H-Mt and commercially available K10 montmorillonite denoted as Mt-K10) were prepared by conventional and modified impregnation routes. Conventional procedure based on the incipient wetness impregnation method involved stirring of the aqueous dispersion of HPMo and montmorillonite, followed by drying at elevated temperature. Modified preparation method employed ultrasonication as a means of the dispersion homogenization, followed by freeze-drying. Such prepared catalysts were characterized by means of powder X-ray diffraction (XRD), scanning electron microscopy (SEM), nitrogen sorption, electron spin resonance (ESR), Fourier transform infrared (FT-IR), ultraviolet–visible (UV–vis) and 31P solid-state magic-angle-spinning nuclear magnetic resonance (MAS-NMR) spectroscopy. Acidic/redox properties of HPMo/montmorillonite systems were evaluated by catalytic conversion of ethanol and pyridine sorption. The hybrid catalysts consist of two catalytically active components. In contrast to montmorillonite, especially acid-treated montmorillonite, which has mainly acidic sites, HPMo species in the final hybrid catalysts may offer both acidic and redox catalytic functions. Spreading HPMo on the surface of montmorillonites results in enhancement in the redox reactivity as a consequence of exposing the redox sites (Mo-containing species). The use of Na-Mt leads to the catalysts with dominating redox function as the acidic sites (coming from HPMo) may be obscured by replacement of protons by sodium ions coming from Na-Mt. In addition, the catalyst prepared by modified impregnation shows higher redox reactivity than that prepared by conventional impregnation

The Synthesis of Cu–Mn–Al Mixed-Oxide Combustion Catalysts by Co-Precipitation in the Presence of Starch: A Comparison of NaOH with Organic Precipitants

Cu–Mn mixed oxides are well known as active combustion catalysts. The common method for their synthesis is based on co-precipitation, with NaOH as a precipitant, and is burdened with the possibility of introducing undesired Na contamination. This work describes the use of two organic bases, tetrabutylammonium hydroxide and choline hydroxide, as precipitating agents in a novel alkali-free route for Cu–Mn–Al catalyst synthesis. To obtain fine crystalline precursors, which are considered advantageous for the preparation of active catalysts, co-precipitation was carried out in the presence of starch gel. Reference materials prepared with NaOH in the absence of starch were also obtained. Mixed oxides were produced by calcination at 450 °C. The precursors contained MnCO3 doped with Cu and Al, and an admixture of amorphous phases. Those prepared in the presence of starch were less crystalline and retained biopolymer residues. The combustion of these residues during calcination enhanced the formation of larger amounts of the Cu1.5Mn1.5O4 spinel phase, with better crystallinity in comparison to catalysts prepared from conventionally synthesized precursors. Tests of toluene combustion demonstrated that the catalysts prepared with starch performed better than those obtained in starch-free syntheses, and that the mixed oxides obtained by the alkali-free route were more active than catalysts prepared with NaOH. Catalytic data are discussed in terms of property–performance relationships

The Synthesis of Cu–Mn–Al Mixed-Oxide Combustion Catalysts by Co-Precipitation in the Presence of Starch: A Comparison of NaOH with Organic Precipitants

Cu–Mn mixed oxides are well known as active combustion catalysts. The common method for their synthesis is based on co-precipitation, with NaOH as a precipitant, and is burdened with the possibility of introducing undesired Na contamination. This work describes the use of two organic bases, tetrabutylammonium hydroxide and choline hydroxide, as precipitating agents in a novel alkali-free route for Cu–Mn–Al catalyst synthesis. To obtain fine crystalline precursors, which are considered advantageous for the preparation of active catalysts, co-precipitation was carried out in the presence of starch gel. Reference materials prepared with NaOH in the absence of starch were also obtained. Mixed oxides were produced by calcination at 450 °C. The precursors contained MnCO3 doped with Cu and Al, and an admixture of amorphous phases. Those prepared in the presence of starch were less crystalline and retained biopolymer residues. The combustion of these residues during calcination enhanced the formation of larger amounts of the Cu1.5Mn1.5O4 spinel phase, with better crystallinity in comparison to catalysts prepared from conventionally synthesized precursors. Tests of toluene combustion demonstrated that the catalysts prepared with starch performed better than those obtained in starch-free syntheses, and that the mixed oxides obtained by the alkali-free route were more active than catalysts prepared with NaOH. Catalytic data are discussed in terms of property–performance relationships