scholarly journals Studies of the Acidity and Ionic Conductivity of Silica-Supported Heteropoly Compounds. I. The Dehydration oft-Butyl Alcohol over Heteropoly Compound Catalysts

1989 ◽  
Vol 62 (10) ◽  
pp. 3195-3201 ◽  
Author(s):  
Reiji Ohtsuka ◽  
Yoshio Morioka ◽  
Jun-ichi Kobayashi
2019 ◽  
Vol 60 (11) ◽  
pp. 85-92
Author(s):  
Nikita A. Panurin ◽  
◽  
Natalya Yu. Isaeva ◽  
Ekaterina B. Markova ◽  
Tatiana F. Sheshko ◽  
...  

Carrying out heterogeneous acid catalysis with the use of heteropoly compounds has received considerable attention due to the great economic and environmental benefits. In spite of this, its industrial application is limited as there are difficulties in catalyst regeneration (settling) caused by its relatively low thermal stability. The aim of present work was to search and select catalysts related to the class of heteropoly compounds for propane cracking, to test the selectivity of the prosses as well as to discuss possible approaches for solving the problem of catalyst deactivation, that can contribute to achieve stable characteristics of solid heteropoly catalysts. Among these approaches are: the development of new catalysts with high thermal stability, the modification of catalysts to promote coke combustion, the inhibition of coke formation on heteropoly compound catalysts during the process, carrying out the reactions in supercritical media and also the cascade reactions using a multifunctional heteropoly catalyst. The obtained catalyst was also studied by physicochemical methods to get deep knowledge about which features of these compounds influence on the catalytic activity. A highly active and selective catalyst for ammonium octomolybdenocobaltate(II) ammonium (NH4)2[Co(H2O)4]2[Mo8O27]∙6H2O was synthesized for cracking associated petroleum gases. The qualitative, quantitative, and structural composition as well as the specific surface area of the obtained catalyst was established by the methods of X-ray diffraction, X-ray phase and fluorescence analysis. It was revealed that ammonium octomolybdenocobaltate(II) crystallizes in a triclinic syngony with cell parameters: а = 8.6292(9) Å b = 9.4795(10) Å c = 12.2071(13) Å α = 104.326(2)° β = 109.910(2)° γ = 100.820(2)°.


2010 ◽  
Vol 1279 ◽  
Author(s):  
Svetlana A. Tungatarova

AbstractDynamics of structural transformation of supported heteropoly compound was investigated by IR-spectroscopy, XRD, TPR, and TPO methods. The 15-30 wt.% H3PMo12O40 and H3PV2Mo10O40, supported on SiO2 catalysts were investigated in process under various conditions by interaction with O2 (air) in the presence of water vapor, H2, alkane in TPR regime, O2 in TPO regime (298-1273K) and H2O (298, 923K). The rank of reversible structural conversion of supported heteropoly compounds was established under influence of temperatureand medium. These new findings of reversible structural cycle explains the stability of the 12th series Mo heteropoly compounds supported on Si-containing carrier at high temperatures (873-1073K) which is close to the actual operation temperatures of the partial oxidation reactions and oxidative dehydrogenation of alkanes.


2020 ◽  
Author(s):  
Saneyuki Ohno ◽  
Tim Bernges ◽  
Johannes Buchheim ◽  
Marc Duchardt ◽  
Anna-Katharina Hatz ◽  
...  

<p>Owing to highly conductive solid ionic conductors, all-solid-state batteries attract significant attention as promising next-generation energy storage devices. A lot of research is invested in the search and optimization of solid electrolytes with higher ionic conductivity. However, a systematic study of an <i>interlaboratory reproducibility</i> of measured ionic conductivities and activation energies is missing, making the comparison of absolute values in literature challenging. In this study, we perform an uncertainty evaluation via a Round Robin approach using different Li-argyrodites exhibiting orders of magnitude different ionic conductivities as reference materials. Identical samples are distributed to different research laboratories and the conductivities and activation barriers are measured by impedance spectroscopy. The results show large ranges of up to 4.5 mScm<sup>-1</sup> in the measured total ionic conductivity (1.3 – 5.8 mScm<sup>-1</sup> for the highest conducting sample, relative standard deviation 35 – 50% across all samples) and up to 128 meV for the activation barriers (198 – 326 meV, relative standard deviation 5 – 15%, across all samples), presenting the necessity of a more rigorous methodology including further collaborations within the community and multiplicate measurements.</p>


2020 ◽  
Author(s):  
Theodosios Famprikis ◽  
O. Ulas Kudu ◽  
James Dawson ◽  
Pieremanuele Canepa ◽  
François Fauth ◽  
...  

<div> <p>Fast-ion conductors are critical to the development of solid-state batteries. The effects of mechanochemical synthesis that lead to increased ionic conductivity in an archetypical sodium-ion conductor Na<sub>3</sub>PS<sub>4</sub> are not fully understood. We present here a comprehensive analysis based on diffraction (Bragg, pair distribution function), spectroscopy (impedance, Raman, NMR, INS) and <i>ab-initio</i> simulations aimed at elucidating the synthesis-property relationships in Na<sub>3</sub>PS<sub>4</sub>. We consolidate previously reported interpretations about the local structure of ball-milled samples, underlining the sodium disorder and showing that a local tetragonal framework more accurately describes the structure than the originally proposed cubic one. Through variable-pressure impedance spectroscopy measurements, we report for the first time the activation volume for Na<sup>+</sup> migration in Na<sub>3</sub>PS<sub>4</sub>, which is ~30% higher for the ball-milled samples. Moreover, we show that the effect of ball-milling on increasing the ionic conductivity of Na<sub>3</sub>PS<sub>4</sub> to ~10<sup>-4</sup> S/cm can be reproduced by applying external pressure on a sample from conventional high temperature ceramic synthesis. We conclude that the key effects of mechanochemical synthesis on the properties of solid electrolytes can be analyzed and understood in terms of pressure, strain and activation volume.</p> </div>


2019 ◽  
Author(s):  
Till Fuchs ◽  
Sean Culver ◽  
Paul Till ◽  
Wolfgang Zeier

<p>The sodium-ion conducting family of Na<sub>3</sub><i>Pn</i>S<sub>4</sub>, with <i>Pn</i> = P, Sb, have gained interest for the use in solid-state batteries due to their high ionic conductivity. However, significant improvements to the conductivity have been hampered by the lack of aliovalent dopants that can introduce vacancies into the structure. Inspired by the need for vacancy introduction into Na<sub>3</sub><i>Pn</i>S<sub>4</sub>, the solid solutions with WS<sub>4</sub><sup>2-</sup> introduction are explored. The influence of the substitution with WS<sub>4</sub><sup>2-</sup> for PS<sub>4</sub><sup>3-</sup> and SbS<sub>4</sub><sup>3-</sup>, respectively, is monitored using a combination of X-ray diffraction, Raman and impedance spectroscopy. With increasing vacancy concentration improvements resulting in a very high ionic conductivity of 13 ± 3 mS·cm<sup>-1</sup> for Na<sub>2.9</sub>P<sub>0.9</sub>W<sub>0.1</sub>S<sub>4</sub> and 41 ± 8 mS·cm<sup>-1</sup> for Na<sub>2.9</sub>Sb<sub>0.9</sub>W<sub>0.1</sub>S<sub>4</sub> can be observed. This work acts as a stepping-stone towards further engineering of ionic conductors using vacancy-injection via aliovalent substituents.</p>


2019 ◽  
Author(s):  
Till Fuchs ◽  
Sean Culver ◽  
Paul Till ◽  
Wolfgang Zeier

<p>The sodium-ion conducting family of Na<sub>3</sub><i>Pn</i>S<sub>4</sub>, with <i>Pn</i> = P, Sb, have gained interest for the use in solid-state batteries due to their high ionic conductivity. However, significant improvements to the conductivity have been hampered by the lack of aliovalent dopants that can introduce vacancies into the structure. Inspired by the need for vacancy introduction into Na<sub>3</sub><i>Pn</i>S<sub>4</sub>, the solid solutions with WS<sub>4</sub><sup>2-</sup> introduction are explored. The influence of the substitution with WS<sub>4</sub><sup>2-</sup> for PS<sub>4</sub><sup>3-</sup> and SbS<sub>4</sub><sup>3-</sup>, respectively, is monitored using a combination of X-ray diffraction, Raman and impedance spectroscopy. With increasing vacancy concentration improvements resulting in a very high ionic conductivity of 13 ± 3 mS·cm<sup>-1</sup> for Na<sub>2.9</sub>P<sub>0.9</sub>W<sub>0.1</sub>S<sub>4</sub> and 41 ± 8 mS·cm<sup>-1</sup> for Na<sub>2.9</sub>Sb<sub>0.9</sub>W<sub>0.1</sub>S<sub>4</sub> can be observed. This work acts as a stepping-stone towards further engineering of ionic conductors using vacancy-injection via aliovalent substituents.</p>


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