Acid–base concerted mechanism in the dehydration of 1,4-butanediol over bixbyite rare earth oxide catalysts

Sato, Fumiya; Sato, Satoshi; Yamada, Yoshio; Nakamura, Masashi; Shiga, Akinobu

doi:10.1016/j.cattod.2013.08.005

Cited by 24 publications

(6 citation statements)

References 30 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…According to the ab initio calculations (B3LYP‐6‐31G*) an intermediary propen‐1,2‐diol is thermodynamically favored by about 30 kJ mol −1 owing to its intramolecular hydrogen bond compared with the isomeric propen‐1,3‐diol. Thus, a detailed mechanistic interpretation has to consider a concerted E2 elimination, which is typical for the dehydration of primary alcohols, as well as glycidol as an alternative dehydration product, which can be hydrogenated to 1,2‐PDO, too …”

Section: Resultssupporting

confidence: 85%

The Role of Metallic Copper in the Selective Hydrodeoxygenation of Glycerol to 1,2‐Propanediol over Cu/ZrO₂

et al. 2018

View full text Add to dashboard Cite

A series of Cu/ZrO2 catalysts with nominal CuO loadings of 5, 10, 18 and 31 wt.% was synthesized by co‐precipitation, characterized and applied in the hydrodeoxygenation of glycerol under mild reaction conditions (200 °C, 25 bar H2). These catalysts were highly selective for the cleavage of C−O bonds while preserving C−C bonds leading to 95 % selectivity to 1,2‐propanediol. The conversion of glycerol was observed to be linearly correlated with the specific copper surface area derived from N2O frontal chromatography. The reaction was found to occur through the dehydration of glycerol to acetol followed by its hydrogenation to 1,2‐propanediol. Metallic copper was identified as the active site for both reactions suggesting the acid ZrO2 sites to be blocked by water. Reusability studies showed that the catalyst was relatively stable and the conversion decreased by only 18 % after three cycles.

show abstract

Section: Resultssupporting

confidence: 85%

The Role of Metallic Copper in the Selective Hydrodeoxygenation of Glycerol to 1,2‐Propanediol over Cu/ZrO₂

et al. 2018

View full text Add to dashboard Cite

show abstract

Section: Speculative Reaction Mechanism Over Cao/zro 2 Catalystmentioning

confidence: 97%

“…We have calculated the stable adsorption structure of 1,4-BDO on Er 2 O 3 catalyst in the dehydration of 1,4-BDO using theoretical calculations [33]. We have demonstrated a probable acid-base concerted mechanism over Er 2 O 3 in the formation of 3-buten-1-ol from 1,4-BDO [31,33]. The most reasonable adsorption structure is a tridentate coordination that the position-2 hydrogen atom of 1,4-BDO is placed on the top of an oxygen anion of Er 2 O 3 , and that two hydroxyl groups of 1,4-BDO fill two oxygen vacancies of the Er 2 O 3 surface.…”

Section: Speculative Reaction Mechanism Over Cao/zro 2 Catalystmentioning

confidence: 99%

Selective dehydration of 2,3-butanediol to 3-buten-2-ol over ZrO2 modified with CaO

Duan

Yamada

Sato

2014

Applied Catalysis A: General

Self Cite

View full text Add to dashboard Cite

Vapor-phase catalytic dehydration of 2,3-butanediol (2,3-BDO) was investigated over several metal oxides loaded on well-crystallized monoclinic ZrO 2. In the dehydration of 2,3-BDO, unsaturated alcohol, i.e. 3-buten-2-ol (3B2OL), was preferentially produced together with major by-products such as butanone and 3-hydroxy-2-butanone over ZrO 2-based catalysts. The selectivity to 3B2OL over monoclinic ZrO 2 was greatly enhanced by the alkaline-earth oxides such as CaO, SrO, and BaO. At a CaO loading of 3 wt.% on the monoclinic ZrO 2 , a Ca-O-Zr hetero-linkage was formed to generate new basic sites, and the selectivity to 3B2OL exceeded 76% at 350 o C. Poisoning experiments using CO 2 and NH 3 strongly suggest that the formation of 3B2OL from 2,3-BDO proceeds over base-acid concerted sites.

show abstract

“…Alumina has been extensively studied for this reaction . Other oxides such as ZrO 2 and rare earth oxides have been examined as well. Chokkaram and Davis found that the activity of ZrO 2 resembles thoria for both dehydration and 1‐alkene selectivity for 2‐octanol.…”

Section: Introductionmentioning

confidence: 99%

Dehydration of 2‐Octanol over Ca‐doped CeO₂ Catalysts

et al. 2017

View full text Add to dashboard Cite

Vapor‐phase catalytic dehydration of 2‐octanol was investigated over Ca‐doped CeO2 at 375 °C and atmospheric pressure. Ca doping up to 0.15 wt % was found to increase the dehydration activity for 2‐octanol, whereas further increases in Ca content (0.50 and 1.25 wt %) detrimentally affected the conversion. Catalyst surface area and pore volume increased with increasing Ca content in Ca‐doped CeO2. Hydrogen temperature‐programmed reduction (TPR) profiles indicate that the partially reduced state of surface ceria (i.e., Ce3+), which increases with increasing Ca loading up to 0.15 wt %, might play an important role in promoting dehydration.

show abstract

Acid–base concerted mechanism in the dehydration of 1,4-butanediol over bixbyite rare earth oxide catalysts

Cited by 24 publications

References 30 publications

The Role of Metallic Copper in the Selective Hydrodeoxygenation of Glycerol to 1,2‐Propanediol over Cu/ZrO₂

The Role of Metallic Copper in the Selective Hydrodeoxygenation of Glycerol to 1,2‐Propanediol over Cu/ZrO₂

Selective dehydration of 2,3-butanediol to 3-buten-2-ol over ZrO2 modified with CaO

Dehydration of 2‐Octanol over Ca‐doped CeO₂ Catalysts

Contact Info

Product

Resources

About

Acid–base concerted mechanism in the dehydration of 1,4-butanediol over bixbyite rare earth oxide catalysts

Cited by 24 publications

References 30 publications

The Role of Metallic Copper in the Selective Hydrodeoxygenation of Glycerol to 1,2‐Propanediol over Cu/ZrO2

The Role of Metallic Copper in the Selective Hydrodeoxygenation of Glycerol to 1,2‐Propanediol over Cu/ZrO2

Selective dehydration of 2,3-butanediol to 3-buten-2-ol over ZrO2 modified with CaO

Dehydration of 2‐Octanol over Ca‐doped CeO2 Catalysts

Contact Info

Product

Resources

About

The Role of Metallic Copper in the Selective Hydrodeoxygenation of Glycerol to 1,2‐Propanediol over Cu/ZrO₂

The Role of Metallic Copper in the Selective Hydrodeoxygenation of Glycerol to 1,2‐Propanediol over Cu/ZrO₂

Dehydration of 2‐Octanol over Ca‐doped CeO₂ Catalysts