Hydrodechlorination of 4-Chlorophenol on Pd-Fe Catalysts on Mesoporous ZrO2SiO2 Support

A mesoporous support based on silica and zirconia (ZS) was used to prepare monometallic 1 wt% Pd/ZS, 10 wt% Fe/ZS, and bimetallic FePd/ZS catalysts. The catalysts were characterized by TPR-H2, XRD, SEM-EDS, TEM, AAS, and DRIFT spectroscopy of adsorbed CO after H2 reduction in situ and tested in hydrodechlorination of environmental pollutant 4-chlorophelol in aqueous solution at 30 °C. The bimetallic catalyst demonstrated an excellent activity, selectivity to phenol and stability in 10 consecutive runs. FePd/ZS has exceptional reducibility due to the high dispersion of palladium and strong interaction between FeOx and palladium, confirmed by TPR-H2, DRIFT spectroscopy, XRD, and TEM. Its reduction occurs during short-time treatment with hydrogen in an aqueous solution at RT. The Pd/ZS was more resistant to reduction but can be activated by aqueous phenol solution and H2. The study by DRIFT spectroscopy of CO adsorbed on Pd/ZS reduced in harsh (H2, 330 °C), medium (H2, 200 °C) and mild conditions (H2 + aqueous solution of phenol) helped to identify the reasons of the reducing action of phenol solution. It was found that phenol provided fast transformation of Pd+ to Pd0. Pd/ZS also can serve as an active and stable catalyst for 4-PhCl transformation to phenol after proper reduction

Effect of gold electronic state on the catalytic performance of nano gold catalysts in n-octanol oxidation

UIDB/50006/2020 project VIU-RSCBMT-65/2019 project 18-29-24037 (Russia) MINECO project CTQ2017-86170-R (Spain)This study aims to identify the role of the various electronic states of gold in the catalytic behavior of Au/MxOy/TiO2 (where MxOy are Fe2O3 or MgO) for the liquid phase oxidation of n-octanol, under mild conditions. For this purpose, Au/MxOy/TiO2 catalysts were prepared by deposition-precipitation with urea, varying the gold content (0.5 or 4 wt.%) and pretreatment conditions (H2 or O2), and characterized by low temperature nitrogen adsorption-desorption, X-ray powder diffraction (XRD), energy dispersive spectroscopy (EDX), scanning transmission electron microscopy-high angle annular dark field (STEM HAADF), diffuse reflectance Fourier transform infrared (DRIFT) spectroscopy of CO adsorption, temperature-programmable desorption (TPD) of ammonia and carbon dioxide, and X-ray photoelectron spectroscopy (XPS). Three states of gold were identified on the surface of the catalysts, Au0, Au1+ and Au3+, and their ratio determined the catalysts performance. Based on a comparison of catalytic and spectroscopic results, it may be concluded that Au+ was the active site state, while Au0 had negative effect, due to a partial blocking of Au0 by solvent. Au3+ also inhibited the oxidation process, due to the strong adsorption of the solvent and/or water formed during the reaction. Density functional theory (DFT) simulations confirmed these suggestions. The dependence of selectivity on the ratio of Brønsted acid centers to Brønsted basic centers was revealed.publishersversionpublishe

The Role of the Activator Additives Introduction Method in the Cold Sintering Process of ZnO Ceramics: CSP/SPS Approach

The great prospects for introducing the cold sintering process (CSP) into industry determine the importance of finding approaches to reduce the processing time and mechanical pressure required to obtain dense ceramics using CSP. The introducing zinc acetate into the initial ZnO powder of methods, such as impregnation, thermovapor autoclave treatment (TVT), and direct injection of an aqueous solution into a die followed by cold sintering process using a spark plasma sintering unit, was studied. The effect of the introduction methods on the density and grain size of sintered ceramics was analyzed using SEM, dynamic light scattering, IR spectroscopy, and XRD. The impregnation method provides sintered samples with high relative density (over 0.90) and significant grain growth when sintered at 250 °C with a high heating rate of 100 °C/min, under a uniaxial pressure of 80 MPa in a vacuum, and a short isothermic dwell time (5 min). The TVT and aqueous solution direct injection methods showed lower relative densities (0.87 and 0.76, respectively) of CSP ZnO samples. Finally, the development of ideas about the processes occurring in an aqueous medium with CSP and TVT, which are subject to mechanical pressure, is presented

Oxidation of a wood extractive betulin to biologically active oxo-derivatives using supported gold catalysts

Betulin is transformed into its oxo-derivatives by liquid-phase oxidation over Au catalysts in mild conditions

Novel Complex Titanium NASICON-Type Phosphates as Acidic Catalysts for Ethanol Dehydration

The conversion of ethanol towards ethylene and diethyl ether in the presence of catalysts requires special consideration from the perspective of green chemistry. Ethanol dehydration was studied on a complex titanium phosphate MAlTiP (M0.5(1+x)AlxTi2-x(PO4)3 with M = Ni, Mn (x = 0; 0.2)) catalysts, alongside a NASICON-type structure synthesized by the sol–gel method. The initial catalysts were characterized by N2 gas sorption, SEM, XRD and spectroscopic methods (Raman and DRIFT of adsorbed CO and C6H6). The results revealed that all catalysts exhibited high activity and selectivity at 300–420 °C. The conversion of ethanol increases with the reaction temperature, reaching 67–80% at 420 °C. The MnAlTiP exhibited the highest ethylene selectivity among other catalysts, with 87% at 420 °C. The aluminum modification improved the acid properties of the catalysts, due to the appearance of Lewis acid sites (LAS) and the strength moderate Brønsted acid sites (BAS). It was shown that the activity of complex phosphates in ethanol dehydration increases with the strength of the Brønsted acid sites (BAS)

Novel Complex Titanium NASICON-Type Phosphates as Acidic Catalysts for Ethanol Dehydration

The conversion of ethanol towards ethylene and diethyl ether in the presence of catalysts requires special consideration from the perspective of green chemistry. Ethanol dehydration was studied on a complex titanium phosphate MAlTiP (M0.5(1+x)AlxTi2-x(PO4)3 with M = Ni, Mn (x = 0; 0.2)) catalysts, alongside a NASICON-type structure synthesized by the sol–gel method. The initial catalysts were characterized by N2 gas sorption, SEM, XRD and spectroscopic methods (Raman and DRIFT of adsorbed CO and C6H6). The results revealed that all catalysts exhibited high activity and selectivity at 300–420 °C. The conversion of ethanol increases with the reaction temperature, reaching 67–80% at 420 °C. The MnAlTiP exhibited the highest ethylene selectivity among other catalysts, with 87% at 420 °C. The aluminum modification improved the acid properties of the catalysts, due to the appearance of Lewis acid sites (LAS) and the strength moderate Brønsted acid sites (BAS). It was shown that the activity of complex phosphates in ethanol dehydration increases with the strength of the Brønsted acid sites (BAS)