On the mechanism of alkyne hydrogenation catalyzed by Ga-doped ceria

2019 ◽  
Vol 375 ◽  
pp. 410-418 ◽  
Author(s):  
Shulan Zhou ◽  
Liye Gao ◽  
Fenfei Wei ◽  
Sen Lin ◽  
Hua Guo
Author(s):  
Tarini Prasad Mishra ◽  
Christian Lenser ◽  
Rishi Raj ◽  
Olivier Guillon ◽  
Martin Bram

Coatings ◽  
2021 ◽  
Vol 11 (6) ◽  
pp. 724
Author(s):  
Sara Massardo ◽  
Alessandro Cingolani ◽  
Cristina Artini

Rare earth-doped ceria thin films are currently thoroughly studied to be used in miniaturized solid oxide cells, memristive devices and gas sensors. The employment in such different application fields derives from the most remarkable property of this material, namely ionic conductivity, occurring through the mobility of oxygen ions above a certain threshold temperature. This feature is in turn limited by the association of defects, which hinders the movement of ions through the lattice. In addition to these issues, ionic conductivity in thin films is dominated by the presence of the film/substrate interface, where a strain can arise as a consequence of lattice mismatch. A tensile strain, in particular, when not released through the occurrence of dislocations, enhances ionic conduction through the reduction of activation energy. Within this complex framework, high pressure X-ray diffraction investigations performed on the bulk material are of great help in estimating the bulk modulus of the material, and hence its compressibility, namely its tolerance toward the application of a compressive/tensile stress. In this review, an overview is given about the correlation between structure and transport properties in rare earth-doped ceria films, and the role of high pressure X-ray diffraction studies in the selection of the most proper compositions for the design of thin films.


2019 ◽  
Vol 6 (6) ◽  
pp. 1668-1672 ◽  
Author(s):  
Zhidong Huang ◽  
Lei Shang ◽  
Huiying Qi ◽  
Zhe Zhao ◽  
Baofeng Tu ◽  
...  

Author(s):  
Joseph W. Gregory ◽  
S. David Jackson

AbstractThe cascade reactions of phenylacetylene to ethylcyclohexane and 1-phenyl-1-propyne to propylcyclohexane were studied individually, under deuterium and competitively at 343 K and 3 barg pressure over a Rh/silica catalyst. Both systems gave similar activation energies for alkyne hydrogenation (56 ± 4 kJ mol−1 for phenylacetylene and 50 ± 4 kJ mol−1 for 1-phenyl-1-propyne). Over fresh catalyst the order of reactivity was styrene > phenylacetylene ≫ ethylbenzene. Whereas with the cascade hydrogenation starting with phenylacetylene, styrene hydrogenated much slower phenylacetylene even once all the phenylacetylene was hydrogenated. The activity of ethylbenzene was also reduced in the cascade reaction and after styrene hydrogenation. These reductions in rate were likely due to carbon laydown from phenylacetylene and styrene. Similar behavior was observed with the 1-phenyl-1-propyne cascade. Deuterium experiments revealed similar positive KIEs for phenylacetylene (2.6) and 1-phenyl-1-propyne (2.1). Ethylbenzene hydrogenation/deuteration gave a KIE of 1.6 obtained after styrene hydrogenation in contrast to the inverse KIE of 0.4 found with ethylbenzene hydrogenation/deuteration over a fresh catalyst, indicating a change in rate determining step. Competitive hydrogenation between phenylacetylene and styrene reduced the rate of phenylacetylene hydrogenation but increased selectivity to ethylbenzene suggesting a change in the flux of sub-surface hydrogen. In the competitive reaction between 1-phenyl-1-propyne and propylbenzene, the rate of hydrogenation of 1-phenyl-1-propyne was increased and the rate of alkene isomerization was decreased, likely due to an increase in the hydrogen flux for hydrogenation and a decrease in the hydrogen species active in methylstyrene isomerization.


2021 ◽  
pp. 160444
Author(s):  
S.U. Costilla-Aguilar ◽  
M.I. Pech-Canul ◽  
M.J. Escudero ◽  
R.F. Cienfuegos-Pelaes ◽  
J.A. Aguilar-Martínez

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