Surface Studies and Nature of Active Sites of Supported Heteropolyacids as Catalysts in Methanol Dehydration

1994 ◽  
Vol 59 (4) ◽  
pp. 820-832 ◽  
Author(s):  
Amin Anwar ◽  
Ali Abdel-Ghaffar ◽  
Sameh Aboul-Fotouh ◽  
Ebeid Fikry

Different amounts of molybdo- and tungstophosphoric acids were supported on α-Al2O3 to get information about their surface and catalytic properties. The surface study revealed that surface area, total pore volume and the mean pore radius decreased as the acid content increased. X-Ray diffraction analysis showed that there is no interaction between the acid and α-Al2O3. Using a continuous flow system, methanol transformation was carried out under atmospheric pressure. Some experiments were made to determine the nature of active centers and reaction mechanism.

1996 ◽  
Vol 61 (8) ◽  
pp. 1131-1140 ◽  
Author(s):  
Abd El-Aziz Ahmed Said

Vanadium oxide catalysts doped or mixed with 1-50 mole % Fe3+ ions were prepared. The structure of the original samples and those calcined from 200 up to 500 °C were characterized by TG, DTA, IR and X-ray diffraction. The SBET values and texture of the solid catalysts were investigated. The catalytic dehydration-dehydrogenation of isopropanol was carried out at 200 °C using a flow system. The results obtained showed an observable decrease in the activity of V2O5 on the addition of Fe3+ ions. Moreover, Fe2V4O13 is the more active and selective catalyst than FeVO4 spinels. The results were correlated with the active sites created on the catalyst surface.


1993 ◽  
Vol 58 (7) ◽  
pp. 1591-1599 ◽  
Author(s):  
Abd El-Aziz A. Said

Molybdenum oxide catalyst doped or mixed with (1 - 50) mole % Fe3+ ions were prepared. The structure of the original samples and the samples calcined at 400 °C were characterized using DTA, X-ray diffraction and IR spectra. Measurements of the electrical conductivity of calcined samples with and without isopropyl alcohol revealed that the conductance increases on increasing the content of Fe3+ ions up to 50 mole %. The activation energies of charge carriers were determined in presence and absence of the alcohol. The catalytic dehydration of isopropyl alcohol was carried out at 250 °C using a flow system. The results obtained showed that the doped or mixed catalysts are active and selective towards propene formation. However, the catalyst containing 40 mole % Fe3+ ions exhibited the highest activity and selectivity. Correlations were attempted to the catalyst composition with their electronic and catalytic properties. Probable mechanism for the dehydration process is proposed in terms of surface active sites.


2019 ◽  
Vol 19 (6) ◽  
pp. 3210-3217
Author(s):  
Jing Yang ◽  
Wang-Qing Fan ◽  
Ruihua Mu ◽  
Yamei Zhao

A novel Pd/SiO2 inorganic–organic composite material was developed for the selective separation of H2 from a mixture of H2 and CO2. Its thermal stability and microstructure calcined under N2 atmosphere were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy and N2 sorption–desorption measurements. Pd element in Pd/SiO2 gel material exists in PdCl2 form, calcination at 350 °C can result in the complete transformation of Pd2+ to metallic Pd0. With the increase of calcination temperature, the hydrophobic Si–CH3 bands decreased in intensity. The residue of Pd/SiO2 material calcined at 800 °C was mainly composed of Si–O–Si, metallic Pd0, CSi4 and some elemental C0. The mean pore size, BET specific surface area and total pore volume of the as-prepared Pd/SiO2 material calcined at 350 °C was about 2.26 nm, 417.35 m2 g−1 and 0.288 m3 g−1, respectively. The mean H2 and CO2 permeances of the corresponding Pd/SiO2 membrane were 9.90×10−6 and 9.10×10−7 mol m−2 Pa−1 s−1, respectively, when operating at 200 °C and a pressure difference of 0.3 MPa. After the steam exposure at 200 °C for 168 h, the H2 permeance decreased by 3.23% while the H2/CO2 permselectivity increased by 2.50%.


1997 ◽  
Vol 15 (8) ◽  
pp. 593-607 ◽  
Author(s):  
A. Abd. El-Aal ◽  
A.M. Ghozza ◽  
G.A. El-Shobaky

The surface characteristics, viz., the specific surface area SBET, the total pore volume Vp and the mean pore radius r̄, of NiO and Fe2O3 were determined from N2 adsorption isotherms conducted at −196°C for the different adsorbents preheated in air at temperatures in the range 300–800°C. The catalytic activities exhibited in CO oxidation by O2 on the various solids were investigated at temperatures varying between 150°C and 400°C. The effect of heating the NiO and Fe2O3 solids in CO and O2 atmospheres at 175–275°C on their catalytic activities was also studied. The results showed that increasing the calcination temperature in the range 300–800°C resulted in a progressive decrease in the SBET value of NiO and Fe2O3. The computed values of the apparent activation energy for the sintering of the oxides were 71 and 92 kJ/mol, respectively. The sintering of NiO and Fe2O3 took place mainly via a particle adhesion mechanism. The catalytic activity of NiO decreased progressively on increasing its calcination temperature from 300°C to 800°C, due to a decrease in its SBET value and the progressive removal of excess O2 which was present as non-stoichiometric NiO. This treatment also decreased the catalytic activity of Fe2O3. The decrease was, however, more pronounced when the temperature increased from 300°C to 400°C which was a result of the crystallization of the ferric oxide into the α-Fe2O3 phase. An increase in the calcination temperature for both oxides from 300°C to 800°C did not modify the mechanism of oxidation of CO by O2 over the various solids but rather changed the concentration of catalytically active sites. Heating NiO and Fe2O3 in CO and O2 atmospheres at 175–275°C modified their catalytic activities, with Fe2O3 being influenced to a greater extent than NiO.


2012 ◽  
Vol 524-527 ◽  
pp. 876-882 ◽  
Author(s):  
Chun Guang Pan ◽  
Hong Zhu Ma

Two catalysts, SO42-/activated clay (SAC) and SO42-/Fe2O3 activated clay (SFAC) were obtained by activated clay with or without Fe2O3 loading then treated with H2SO4. The acidity of the catalysts were measured by temperature-programmed desorption of ammonia (NH3-TPD), and the results confirm that the SFAC catalyst has higher acid strength than SAC catalyst. Other techniques such as X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET), and energy dispersive X-ray spectroscopy (EDXS) were also employed to characterize the structure of catalysts. Its catalytic properties in desulfurization reaction from the simulated coking benzene by alkylation method was also investigated under mild conditions (353 K and atmospheric pressure), the thiophene removal efficiency can reach 42% for SAC catalyst and 99% for SFAC catalyst, respectively.


Author(s):  
William F. Tivol ◽  
Murray Vernon King ◽  
D. F. Parsons

Feasibility of isomorphous substitution in electron diffraction is supported by a calculation of the mean alteration of the electron-diffraction structure factors for hemoglobin crystals caused by substituting two mercury atoms per molecule, following Green, Ingram & Perutz, but with allowance for the proportionality of f to Z3/4 for electron diffraction. This yields a mean net change in F of 12.5%, as contrasted with 22.8% for x-ray diffraction.Use of the hydration chamber in electron diffraction opens prospects for examining many proteins that yield only very thin crystals not suitable for x-ray diffraction. Examination in the wet state avoids treatments that could cause translocation of the heavy-atom labels or distortion of the crystal. Combined with low-fluence techniques, it enables study of the protein in a state as close to native as possible.We have undertaken a study of crystals of rat hemoglobin by electron diffraction in the wet state. Rat hemoglobin offers a certain advantage for hydration-chamber work over other hemoglobins in that it can be crystallized from distilled water instead of salt solutions.


Materials ◽  
2021 ◽  
Vol 14 (10) ◽  
pp. 2623
Author(s):  
Monika Wójcik-Bania ◽  
Jakub Matusik

Polymer–clay mineral composites are an important class of materials with various applications in the industry. Despite interesting properties of polysiloxanes, such matrices were rarely used in combination with clay minerals. Thus, for the first time, a systematic study was designed to investigate the cross-linking efficiency of polysiloxane networks in the presence of 2 wt % of organo-montmorillonite. Montmorillonite (Mt) was intercalated with six quaternary ammonium salts of the cation structure [(CH3)2R’NR]+, where R = C12, C14, C16, and R’ = methyl or benzyl substituent. The intercalation efficiency was examined by X-ray diffraction, CHN elemental analysis, and Fourier transform infrared (FTIR) spectroscopy. Textural studies have shown that the application of freezing in liquid nitrogen and freeze-drying after the intercalation increases the specific surface area and the total pore volume of organo-Mt. The polymer matrix was a poly(methylhydrosiloxane) cross-linked with two linear vinylsiloxanes of different siloxane chain lengths between end functional groups. X-ray diffraction and transmission electron microscopy studies have shown that the increase in d-spacing of organo-Mt and the benzyl substituent influence the degree of nanofillers’ exfoliation in the nanocomposites. The increase in the degree of organo-Mt exfoliation reduces the efficiency of hydrosilylation reaction monitored by FTIR. This was due to physical hindrance induced by exfoliated Mt particles.


2021 ◽  
Vol 56 (19) ◽  
pp. 11237-11247 ◽  
Author(s):  
Johannes Pötschke ◽  
Manisha Dahal ◽  
Mathias Herrmann ◽  
Anne Vornberger ◽  
Björn Matthey ◽  
...  

AbstractDense (Hf, Ta, Nb, Ti, V)C- and (Ta, Nb, Ti, V, W)C-based high-entropy carbides (HEC) were produced by three different sintering techniques: gas pressure sintering/sinter–HIP at 1900 °C and 100 bar Ar, vacuum sintering at 2250 °C and 0.001 bar as well as SPS/FAST at 2000 °C and 60 MPa pressure. The relative density varied from 97.9 to 100%, with SPS producing 100% dense samples with both compositions. Grain size measurements showed that the substitution of Hf with W leads to an increase in the mean grain size of 5–10 times the size of the (Hf, Ta, Nb, Ti, V,)C samples. Vacuum-sintered samples showed uniform grain size distribution regardless of composition. EDS mapping revealed the formation of a solid solution with no intermetallic phases or element clustering. X-ray diffraction analysis showed the structure of mostly single-phase cubic high-entropy carbides. Hardness measurements revealed that (Hf, Ta, Nb, Ti, V)C samples possess higher hardness values than (Ta, Nb, Ti, V, W)C samples.


2009 ◽  
Vol 73 (6) ◽  
pp. 1027-1032 ◽  
Author(s):  
F. Nestola ◽  
A. Guastoni ◽  
L. Bindi ◽  
L. Secco

AbstractDalnegroite, ideally Tl4Pb2(As12Sb8)Σ20S34, is a new mineral from Lengenbach, Binntal, Switzerland. It occurs as anhedral to subhedral grains up to 200 μm across, closely associated with realgar, pyrite, Sb-rich seligmanite in a gangue of dolomite. Dalnegroite is opaque with a submetallic lustre and shows a brownish-red streak. It is brittle; the Vickers hardness (VHN25) is 87 kg mm-2(range: 69—101) (Mohs hardness ∼3—3½). In reflected light, dalnegroite is highly bireflectant and weakly pleochroic, from white to a slightly greenish-grey. In cross-polarized light, it is highly anisotropic with bluish to green rotation tints and red internal reflections.According to chemical and X-ray diffraction data, dalnegroite appears to be isotypic with chabournéite, Tl5-xPb2x(Sb,As)21-xS34. It is triclinic, probable space groupP1, witha= 16.217(7) Å,b= 42.544(9) Å,c= 8.557(4) Å, α = 95.72(4)°, β = 90.25(4)°, γ = 96.78(4)°,V= 5832(4) Å3,Z= 4.The nine strongest powder-diffraction lines [d(Å) (I/I0) (hkl)] are: 3.927 (100) (10 0); 3.775 (45) (22); 3.685 (45) (60); 3.620 (50) (440); 3.124 (50) (2); 2.929 (60) (42); 2.850 (70) (42); 2.579 (45) (02); 2.097 (60) (024). The mean of 11 electron microprobe analyses gave elemental concentrations as follows: Pb 10.09(1) wt.%, Tl 20.36(1), Sb 23.95(1), As 21.33(8), S 26.16(8), totalling 101.95 wt.%, corresponding to Tl4.15Pb2.03(As11.86Sb8.20)S34. The new mineral is named for Alberto Dal Negro, Professor in Mineralogy and Crystallography at the University of Padova since 1976.


1998 ◽  
Vol 16 (4) ◽  
pp. 285-293 ◽  
Author(s):  
M.R. Mostafa ◽  
F.Sh. Ahmed

Co3(PO4)2, AlPO4 and the binary system Co3(PO4)2-AlPO4 with different compositions were prepared by the coprecipitation method. The structural properties of these samples were determined using XRD, DTA and FT-IR techniques. The textural properties were determined from the adsorption of nitrogen at 77 K. The surface acidity was measured by a calorimetric titration method. The samples were tested as catalysts in the dehydration of ethanol and isopropanol using a pulse microcatalytic technique. The data obtained from XRD and FT-IR indicate the amorphous structures of the prepared catalysts. An increase in Co3(PO4)2 content led to a decrease in the surface area and in the total pore volume and an increase in the mean pore radius. The surface acidity of the catalyst depends on the chemical composition; the surface acidity increased with an increase in the AlPO4 content. The dehydration temperature and the distribution of acid sites are important parameters in determining the selectivity and activity of the catalyst.


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