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The pure and palladium doped 12-tungstophosphoric acid - H3PW12O40 (HPW) and its cesium salts CsxH3-xPW12O40 (x = 1, 2, 2.25 and 2.5) were prepared and characterized by thermal analysis, FTIR, XRD, BET and XPS methods. In this paper were determined the optimal reaction temperature and the effect of palladium on the coke content during the dehydration of ethanol in the temperature range of 200−350 °C. Above 300 °C, a strong deactivation of the catalysts was caused by coke formation. The catalytic tests demonstrate that by supporting the HPW and PdyPW (y = 0.15, 0.2 and 0.25) on mesoporous molecular sieve SBA-15 the catalytic activity in ethanol dehydration reaction was improved. Palladium doping of HPW/SBA-15 significantly decreases the formation of coke deposit. The formation of coke during the ethanol dehydration does not affect the Keggin structure which led us to conclude that such catalysts can be regenerated in air and regain their catalytic activity for a short time.

Thermogravimetric analysis (TGA) was used to evaluate the thermal stability and the amount of coke deposition resulting from the deactivation of catalysts during ethanol dehydration reaction in a fixed bed continuous flow reactor. In this study, a series of catalysts containing 30% of Pd doped and pure 12-tungstophosphoric acid and its insoluble Cs2.5H0.5PW12O40 salt supported on SBA-15 were prepared. The catalytic efficiency of ethanol dehydration reaction was also evaluated. Two types of coke are identified from the TPO (Temperature programmed oxidation) profiles and assigned to the coke precursor and hard coke, respectively. The results indicate that cesium salts reduced the formation of hard coke. The amount of total coke formed was significantly reduced by supporting the catalysts on mesoporous SBA-15 molecular sieves.

Some heteropoly salts – mesoporous silica composites were prepared from Co salt of molybdophosphoric acid CoHPMo 12 O 40 (CoHPM) by supporting on mesoporous silica in different concentrations (20–40 wt% CoHPM) of active phase. The acidity of composites was studied by the adsorption of ammonia and its temperature programmed desorption – TPD using thermogravimetry. The evolved gases during the adsorption–desorption of ammonia on CoPM-silica composites were identified by online mass spectrometry coupled with thermal gravimetry technique. The elemental concentrations based on the relative area of XPS spectra components for Co 2p, Mo 3d, Si 2p and O 1s were obtained for the surface of CoHPM/silica. The dehydration of ethanol was used to probe the catalytic properties of the CoHPM samples incorporated on the silica matrix. The main reaction products obtained on acid (dehydration) catalytic centres were ethylene and diethyl ether, besides acetaldehyde which was obtained on redox (dehydrogenation) catalytic centres. It is shown that silica – supported catalysts, appeared to be more active than bulk CoHPM catalyst in dehydration and dehydrogenation reactions. The higher values of dehydration and reaction products formation are obtained with the lowest loading (20 wt% CoHPM) and as a consequence the highest dispersion of active phase. The ethanol conversion and the carbon selectivity to the primary compounds were investigated during time on stream in order to study the stability and regenerability of supported catalysts.

A series of heteropolyacids–mesoporous silica composites were prepared from nickel salt of molybdophosphoric acid Ni1HPMo12O40 (NiHPM) by supporting on SBA-15 mesoporous silica in different concentrations of active phase. The structure and texture of these NiHPM/SBA-15 composites were studied by XRD, FT-IR and micro-Raman spectroscopy, nitrogen physisorption at 77 K, UV–Vis–DRS and SEM–EDX. The effect of the support on thermal stability was investigated by TG-DTG, DTA and DSC methods. By impregnation of Ni salt on mesoporous silica the thermal stability of the Keggin structure increases in comparison with its parent bulk heteropolyacid. From XRD at small angles could be observed that NiHPM/SBA-15 composites with low surface coverage preserve the mesopore structure of silica, with well dispersed NiHPM on the surface of the pore walls for SBA-15. The adsorption of ammonia and its temperature programmed desorption using thermogravimetry were studied for acidity evaluation. The total acidity of the weak and strong acidic sites of NiHPM/SBA-15 composites is obviously increases in comparison with bulk Ni salt. The main products observed in the evolved gases during desorption of NH3 were NH3, CO2 and NO/NO2.

The salts of the H 3 PW 12 O 40 (H 3 PW) with Cs counter cation were prepared and characterized by thermal analysis, IR, XRD, BET, XPS LEIS and SEM methods. The samples are denoted as Cs x H 3 − x PW 12 O 40 ( x = 1, 2, 2.25, 2.5 and 3). The catalytic activity of the compounds prepared with various cesium/Keggin unit ratios was tested in ethanol conversion by pulse reaction technique. The change of catalytic activity vs. pulse number was explained by formation of strong adsorbed species on catalysts. A microstructure model of the Cs x H 3 − x PW 12 O 40 containing spherical aggregates, which consist of Cs 3 PW 12 O 40 crystallites core coated with H 3 PW 12 O 40 layers, was proposed on the basis of the structural–textural properties and their catalytic performances in ethanol conversion. The model explains the abrupt increase of the specific surface area for x > 2 and also the highest selectivity for C 4 hydrocarbons on Cs 2.5 H 0.5 PW 12 O 40 due to its special microstructure: a H 3 PW monolayer embedding a core of Cs 3 PW. The Cs concentrations on the Cs x H 3 − x PW 12 O 40 surface were determined by XPS and were found less than expected based on their chemical composition, but which correspond to the proposed model of microstructure.

Two new Schiff base ligands 1 and 2 (where 1 = 4-(2-hydroxybenzilidenamino)-phenyl-4-(decyloxy)-2-(pent-4-enyloxy)benzoate, 2 = 4-(4-(decyloxy)-2-hydroxybenziliden amino)-phenyl-4-(decyloxy)-2-(pent-4-enyloxy)benzoate) and their copper (Cu)(II) complexes have been synthesised and characterised. The derivatives were fully characterised structurally, and their mesomorphic behaviour was investigated by polarised optical microscopyand differential scanning calorimetry. The structure of Cu(II) complex having 1 as ligand (3) was determined by X-ray diffraction. The Schiff base ligands exhibit enantiotropic nematic phases, the Cu(II) complex 4 shows monotropic nematic phase behaviour, while compound 3 does not show mesomorphism.