624-64-6Relevant articles and documents
Hydrocarbon reactions on MoS2 revisited, II: Catalytic properties in alkene hydrogenation, cis-trans isomerization, and H2/D2 exchange
Polyakov, Mykola,Poisot, Martha,Bensch, Wolfgang,Muhler, Martin,Gruenert, Wolfgang
, p. 137 - 144 (2008)
MoS2 prepared by thermal decomposition of ammonium tetrathiomolybdate in inert gas at temperatures up to 773 K was activated by treatments involving thermoevacuation at 723 K and/or reduction at 573 K. The effect of different activations on the activity in ethylene hydrogenation, cis-trans isomerization of 2-butene, and H2/D2 isotope exchange (all measured at temperatures around 473 K) was compared, taking into account the extent of Mo exposition as measured by oxygen chemisorption. It was found that activation had a widely varying impact on the test reactions, indicating that these proceed on sites with different numbers of vacancies. Hydrogenation activity was boosted by two orders of magnitude when reduction of the catalyst at 573 K was followed by thermoevacuation at 723 K, whereas this change was moderate with H2/D2 exchange and negative with cis-trans isomerization. For the latter reaction, mere thermoevacuation was a suitable activation, and the impact of subsequent catalyst reduction was negative, whereas appreciable activity in the former reactions was obtained only when thermoevacuation was combined with a subsequent reduction. The data suggest that all three reactions proceeded on different sites, probably 3 vacancies per Mo for olefin hydrogenation, 2 vacancies per Mo for H2/D2 exchange, and 1 vacancy per Mo for cis-trans isomerization, with the latter two reactions involving adjacent {single bond}SH groups. Sites with greater Mo exposure than stated may be suitable for H2/D2 exchange but not for cis-trans isomerization. With increasing severity of the activation treatments, sites with a small number of vacancies appeared to combine and migrate toward the rims or to escape into the bulk. Therefore, very high hydrogenation activity may be seen on surfaces with an oxygen chemisorption capacity far from the maximum value occurring after less drastic treatments. Our findings imply that a combination of chemisorption studies with test reactions may be a valuable tool for surface characterization of sulfide catalysts.
The Photocatalytic Isomerization of 2-Butenes on ZrO2 Catalyst with Low Coordinated Surface Sites
Moon, Sang-Chul,Hieida, Takeshi,Yamashita, Hiromi,Anpo, Masakazu
, p. 447 - 448 (1995)
The photocatalyzed isomerization of cis-2-butene has been investigated on active ZrO2 catalysts which exhibited a typical photoluminescence associated with low coordinated surface sites.A geometrical isomerization reaction occurred predominantly and with high efficiency under UV-irradiation of the ZrO2 catalyst in the presence of cis-2-butene.A good parallel between the photoluminescence intensity and the rate of photocatalytic activity clearly indicated that the low coordinated surface sites play a significant role in the photocatalytic isomerization of cis-2-butene on the active ZrO2 catalysts.
Sulfide catalysis without coordinatively unsaturated sites: Hydrogenation, cis-trans isomerization, and H2/D2 scrambling over MoS2 and WS2
Drescher, Thomas,Niefind, Felix,Bensch, Wolfgang,Gruenert, Wolfgang
, p. 18896 - 18899 (2012)
Simple test reactions as ethene hydrogenation, 2-butene cis-trans isomerization and H2/D2 scrambling were shown to be catalyzed by MoS2 and WS2 in surface states which did not chemisorb oxygen and were, according to XPS analysis, saturated by sulfide species. This is a clear experimental disproof of classical concepts that require coordinative unsaturation for catalytic reactions to occur on such surfaces. It supports new concepts developed on model catalysts and by theoretical calculations so far, which have been in need of confirmation from real catalysis.
A Novel Metathesis Catalyst Consisting of Non-transition Elements. The Metathesis of Alkenes over Tetramethyltin/Dehydroxylated Alumina
Ahn, Ho-Geun,Yamamoto, Kei,Nakamura, Ryuichi,Niiyama, Hiroo
, p. 503 - 506 (1992)
Sn(CH3)4/Al2O3 prepared by the deposition of Sn(CH3)4 to alumina which was previously dehydroxylated by heating at 773-1223 K was found to be an active catalyst for the metathesis of alkenes.The catalytic activity greatly depended on the pretreatment temperature of the alumina and the amount of Sn(CH3)4 deposited.
Photocatalyzed Isomerization of Butenes over Metal Sulfides. High Photocatalytic Activity and Its Origin
Kodama, Sukeya,Matsumoto, Atsushi,Kubokawa, Yutaka,Anpo, Masakazu
, p. 3765 - 3770 (1986)
Photocatalytic activity of CdS and ZnS for the cis-trans isomerization of 2-butene is much higher than that of TiO2 and ZnO, though the double bond shift isomerization to 1-butene hardly proceeds in contrast with the case of the oxides.The addition of O2 or NO molecules leads to the remarkable inhibition of photocatalyzed isomerization.From these results together with the ESR measurements before and after UV irradiation of the sulfide catalyst either in the presence or in the absence of butene, the following conclusions emerge: sulfur radicals such as Sn, which are produced by the hole trapping by lattice S2- ions and/or sulfur clusters existing in the catalyst inherently, play a significant role in the weakening of the C=C double bond of 2-butene via the interaction with the molecules; the stability of such sulfur radicals results in the much higher photocatalytic activity of CdS and ZnS catalysts as compared with that of metal oxide catalysts.
Tuning crystal phase of molybdenum carbide catalyst to induce the different selective hydrogenation performance
Ding, Ziluo,Hou, Ruijun,Sun, Kening,Xu, Yamei,Yang, Qiuchen
, (2021/12/04)
α-MoC, β-Mo2C, and MoC-Mo2C were synthesized and investigated in the selective hydrogenation of 1,3-butadiene to understand the effect of crystal phases. The catalysts were characterized by XRD, N2-physisorption, SEM, TEM, XPS and chemisorptions. The adsorption properties and electronic properties over MoC(001) and Mo2C(001) were investigated by DFT calculations. The catalysts were evaluated at low and high temperatures in a fixed-bed reactor. β-Mo2C exhibits high activity and low butenes selectivity, due to the high concentration of hydrogen at each active site as well as the stronger adsorption and higher capacity of alkene; MoC-Mo2C shows better stability due to synergetic effect. At high temperature, the reaction rate is more dependent on the PH2 than PC4H6. Increasing PH2 could promote the activity and reduce oligomers formation. β-Mo2C exhibits the best performance at high temperatures concerning its high activity and the inhibition of oligomerization. This work is valuable for the non-precious metal catalyst development.
Selective dehydration of 1-butanol to butenes over silica supported heteropolyacid catalysts: Mechanistic aspect
Dutta, Saikat,Kella, Tatinaidu,Mal, Sib Sankar,Shee, Debaprasad,Vennathan, Anjana Anandan
, (2021/11/03)
Butenes are considered as important olefinic building block to produce fuels/fuel additives and commodity chemicals. In the present investigation, selective dehydration of 1-butanol to butenes was studied in a continuous-flow fixed-bed reactor using various silica-supported heteropolyacid (HPA) catalysts such as phosphotungstic acid (PTA), silicotungstic acid (STA), phosphomolybdic acid (PMA), and silicomolybdic acid (SMA) as the solid acid catalysts. The physicochemical properties of these HPA were determined by BET, powder XRD, FTIR, NH3-TPD, and Py-FTIR. The acid strength and Br?nsted/Lewis (B/L) acid ratio were increased with higher loading of HPA on silica. The nature of HPA (addenda and hetero atom) and loading of HPA are important factors for the dehydration of 1-butanol and selectivity towards butenes. PTA and STA showed superior catalytic activity than PMA and SMA. The reaction temperature and WHSV also strongly affected the butanol conversion and selectivity of butenes. The selectivity of di-n?butyl ether decreases with the rising temperature from 523 K to 623 K. The isomerization of 1-butene leading to the formation of other butene isomers depends on the HPA loading, temperature, and WHSV. The presence of molybdenum addendum atom in PMA and SMA promotes dehydrogenation and hydrogenation, leading to the formation of various light hydrocarbons. The 20PTA/SiO2 catalyst afforded 99.8% selectivity towards butenes at quantitative conversion of 1-butanol, whereas the 20STA/SiO2 catalyst gave nearly 97.0% conversion of 1-butanol and 99.9% butenes selectivity at 673 K, 37.4 h?1 of WHSV.
CATALYTIC HYDROCARBON DEHYDROGENATION
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Paragraph 0063; 0064; 0124; 0125, (2021/03/13)
A catalyst for dehydrogenation of hydrocarbons includes a support including zirconium oxide and Linde type L zeolite (L-zeolite). A concentration of the zirconium oxide in the catalyst is in a range of from 0.1 weight percent (wt. %) to 20 wt. %. The catalyst includes from 5 wt. % to 15 wt. % of an alkali metal or alkaline earth metal. The catalyst includes from 0.1 wt. % to 10 wt. % of tin. The catalyst includes from 0.1 wt. % to 8 wt. % of a platinum group metal. The alkali metal or alkaline earth metal, tin, and platinum group metal are disposed on the support.