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A new type of catalyst containing magnesium oxide modified with various modifiers ranging from bromine and iodine, to interhalogen compounds, hydrohalogenic acids, and alkyl halides have been prepared using chemical vapor deposition (CVD) and wet impregnation methods. The obtained systems were characterized using a number of methods: determination of the concentration of X− ions, surface area determination, powder X-ray diffraction (PXRD), surface acid–base strength measurements, TPD of probe molecules (acetonitrile, pivalonitrile, triethylamine, and n-butylamine), TPD-MS of reaction products of methyl iodide with MgO, and Fourier transform infrared spectroscopy (FTIR). The catalysts’ activity and chemoselectivity during transfer hydrogenation from ethanol to acrolein to allyl alcohol was measured. A significant increase in the activity of modified MgO (up to 80% conversion) in the transfer hydrogenation of acrolein was found, while maintaining high chemoselectivity (>90%) to allyl alcohol. As a general conclusion, it was shown that the modification of MgO results in the suppression of strong basic sites of the oxide, with a simultaneous appearance of Brønsted acidic sites on its surface. Independently, extensive research on the reaction progress of thirty alkyl halides with MgO was also performed in order to determine its ability to neutralize chlorinated wastes.

Catalytic conversion of lignin to value-added aromatic compounds is still an open challenge, since the selective cleavage of the linkages interconnecting the aromatic molecules, especially the β-O-4 ones, is not efficiently achieved yet. Herein, novel titania-based nanostructured materials were synthesized using low-power-low-frequency ultrasound that demonstrated high efficiency for the selective cleavage of Cα-Cβ bond of β-O-4 linkages of lignin-inspired model compounds. Going a step ahead, experiments of sonophotocatalytic valorization of 2-phenoxy-1-phenylethanol were contacted for the first time, where the exposure to ultrasound leading to better conversion and selectivity towards the desired products in the case of the novel ultrasound-synthesized nano-photocatalyst. Mechanistic insights showcased that photogenerated holes are the main active species in the catalytic process. In general, this research work provides a green, effective, and cost-effective approach for the selective and efficient catalytic lignin valorization.

Selective oxidation, which is crucial in diverse chemical industries, transforms harmful chemicals into valuable compounds. Heterogeneous sonocatalysis, an emerging sustainable approach, urges in-depth exploration. In this work, we investigated N-doped or non-doped carbonaceous materials as alternatives to scarce, economically sensitive metal-based catalysts. Having synthesized diverse carbons using a hard-template technique, we subjected them to sonication at frequencies of 22, 100, 500, and 800 kHz with a 50% amplitude. Sonochemical reaction catalytic tests considerably increased the catalytic activity of C-meso (non-doped mesoporous carbon material). The scavenger test showed a radical formation when this catalyst was used. N-doped carbons did not show adequate and consistent sonoactivity for the selective oxidation of 4-Hydroxy-3,5 dimethoxybenzyl alcohol in comparison with control conditions without sonication, which might be associated with an acid–base interaction between the catalysts and the substrate and sonoactivity prohibition by piridinic nitrogen in N-doped catalysts.

A series of 20 wt.% MO2/S catalysts (where M = Ce, Mn or Zr and S = SiO2 or Al2O3) were prepared using various precursors of the active phases. The resulting catalysts were characterized using different methods (XRD, TPR and SBET). For the first time, anhydrides were used as potential starting materials for ketone synthesis. This novel reaction was performed on various aliphatic anhydrides in the presence of catalysts within a temperature range of 523–723 K. For all anhydrides, except for pivalic anhydride, the appropriate ketones were obtained with good or very good yields. The vapor-phase catalytic ketonization of esters of benzene-1,x-dicarboxylic acids (x = 2, 3 or 4) with acetic acid were studied in the range of 673–723 K in order to obtain 1,x-diacetylbenzenes. Their yields strongly increased with an increase in the x value (0, 8 and 43% for x = 2, 3 and 4, respectively). The presence of acetophenone as a side product was always noted. In the case of ω-phenylalkanoic acids, their vapor-phase ketonization with acetic acid led to the formation of appropriate ketones with 47–49% yields. Much lower yields of ketones (3–19%) were obtained for acids and ethyl esters containing heterocycle substituents (with O or S atoms) and/or vinyl groups. In the reaction between ethyl 4-nitrophenylacetate and acetic acid, only the products of ester decomposition (p-toluidine and p-nitrotoluene) were determined.

The research for “green” and economically feasible approaches such as (photo)catalysis especially for biomass valorization such as selective oxidation of biomass derived compounds like aromatic alcohols to corresponding aldehyde by avoiding the harsh reaction conditions and the addition of reagents concentrate the focus of attention the last years. Hence, design and development of novel photocatalyst for the partial selective oxidation is highly desirable. In this research work, ultrasonication of different frequencies (22, 40, 80 kHz) and different amplitudes was utilized as synthesis tool in order to obtain novel materials by precipitation method. The synthesized samples were characterized by using different techniques such as N2 sorption, TEM, XPS, XRD, thermal analysis, and diffuse reflectance spectroscopy. The synthesized sample by using low ultrasound frequency (22 kHz) and amplitude showed a mixed morphological and structural nature consisting of asymmetric 1-dimensional (nanorods-like), layered nano-structures and not well-defined areas, leading to elevate for metal oxide specific surface areas up to 155 m2/g. The observed 1-D nanostructures have diamentions in the range of 20–60 nm. This sample revealed the highest photo-oxidation efficiency for the selective conversion of two biomass-derived, and more specifically lignin-inspired model compounds, benzyl alcohol and cinnamyl alcohol to benzaldehyde and cinnamyl aldehyde, respectively, and hence the highest yield towards the desired aldehydes. The selective photo-oxidation activity was retained even after 5 photocatalytic cycles, while no leaching of Ti was recorded.

The designing and synthesis of novel photocatalysts are the most important parts, with TiO2-based materials to be consider as prosperous candidates for the selective photo-oxidation of aromatic alcohol. Herein, we established an ultrasound-assisted (500 kHz) precipitation synthetic protocol which led to titanate nanorods of 30 nm maximum length, decorated with nanoclusters of size 1–3 nm. The physicochemical features of the synthesized catalysts were characterized by various techniques. The 1-D nanomaterial obtained at low ultrasound power revealed highest yield towards selective photo-oxidation of benzyl alcohol to benzaldehyde comparing to the material synthesized at higher ultrasound power, in silent, and the commercial TiO2-P25.

In this study, magnesium nitrate, chloride or sulphate were used in the synthesis of Mg(OH)2, the precursor of MgO. It was found that the counter ion strongly influences the purity of the Mg(OH)2, as well as the specific surface area of the obtained MgO. The latter is also strongly influenced by the calcination temperature. The choice of the precipitating agent can lead to the introduction of K+ or Na+ ions and hence NH3 (aq) is the best choice. A multistep precipitation procedure of Mg(OH)2 was proposed to lower the concentration of typical impurities (Fe, Ni and Mn) found in commercial p.a. purity Mg(NO3)2. The effect of the number of portions of water used for washing of Mg(OH)2 on the purity of the final product has also been investigated in detail. The stages of formation of grains of Mg(OH)2 and their subsequent thermal decomposition was described together with determination of the introduction of new impurities into the material. Large scale (1500 g) preparation of Mg(OH)2 with an improved purity was performed and described. Therefore, this study explains what measures should be taken to obtain pure magnesia catalysts and is a valuable resource for catalytic research in which magnesia is used.

The challenge of improving the activity of TiO2 by modifying it with metals and using it for targeted applications in microreactor environments is an active area of research. Recently, microreactors have emerged as successful candidates for many photocatalytic reactions, especially for the selective oxidation process. The current work introduces ultrasound-assisted catalyst deposition on the inner walls of a perfluoro-alkoxy alkane (PFA) microtube under mild conditions. We report Cu-Au/TiO2 and Fe-Au/TiO2 nanoparticles synthesized using the sol–gel method. The obtained photocatalysts were thoroughly characterized by UV–Vis diffuse-reflectance spectroscopy (DRS), high-resolution scanning electron microscopy (HR-SEM), high-resolution transmission electron microscopy (HR-TEM), X-ray diffraction analysis (XRD), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and N2 physisorption. The photocatalytic activity under UV (375 nm) and visible light (515 nm) was estimated by the oxidation of lignin-based model aromatic alcohols in batch and fluoropolymer-based flow systems. The bimetallic catalyst exhibited improved photocatalytic selective oxidation. Herein, four aromatic alcohols were individually investigated and compared. In our experiments, the alcohols containing hydroxy and methoxy groups (coniferyl and vanillin alcohol) showed high conversion (93% and 52%, respectively) with 8% and 17% selectivity towards their respective aldehydes, with the formation of other side products. The results offer an insight into ligand-to-metal charge transfer (LMCT) complex formation, which was found to be the main reason for the activity of synthesized catalysts under visible light.