Selective formation of 1-propanol via ethylene hydroformylation over the catalyst originated from RhVO4

Yamagishi, Takashi; Ito, Shin Ichi; Tomishige, Keiichi; Kunimori, Kimio

doi:10.1016/j.catcom.2005.03.008

“…Selectivity towards HF was similar, in the range of 55-65 mol %, and comparable to those reported in the literature for different solid ethylene hydroformylation catalysts. [47,48] A comparatively higher HF rate (3.7 h À 1 ) and selectivity (68 %) were determined for the reference Rh n /SiO 2 , which fall also in the range of previously observed performances for oxide-supported Rh catalysts. In stark contrast, Rh 1 / SnO 2 showed a hydroformylation TOF of 225 h À 1 , i.e.…”

Section: Resultssupporting

confidence: 79%

Rhodium Single‐Atom Catalyst Design through Oxide Support Modulation for Selective Gas‐Phase Ethylene Hydroformylation

Farpón

¹

,

Henao

²

,

Pleßow

³

et al. 2022

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A frontier challenge in single‐atom (SA) catalysis is the design of fully inorganic sites capable of emulating the high reaction selectivity traditionally exclusive of organometallic counterparts in homogeneous catalysis. Modulating the direct coordination environment in SA sites, via the exploitation of the oxide support's surface chemistry, stands as a powerful albeit underexplored strategy. We report that isolated Rh atoms stabilized on oxygen‐defective SnO2 uniquely unite excellent TOF with essentially full selectivity in the gas‐phase hydroformylation of ethylene, inhibiting the thermodynamically favored olefin hydrogenation. Density Functional Theory calculations and surface characterization suggest that substantial depletion of the catalyst surface in lattice oxygen, energetically facile on SnO2, is key to unlock a high coordination pliability at the mononuclear Rh centers, leading to an exceptional performance which is on par with that of molecular catalysts in liquid media.

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“…Chemie catalysts. [47,48] A comparatively higher HF rate (3.7 h À 1 ) and selectivity (68 %) were determined for the reference Rh n /SiO 2 , which fall also in the range of previously observed performances for oxide-supported Rh catalysts. In stark contrast, Rh 1 / SnO 2 showed a hydroformylation TOF of 225 h À 1 , i.e.…”

Section: Methodssupporting

confidence: 79%

Rhodium Single‐Atom Catalyst Design through Oxide Support Modulation for Selective Gas‐Phase Ethylene Hydroformylation

Farpón

¹

,

Henao

²

,

Pleßow

³

et al. 2022

View full text Add to dashboard Cite

A frontier challenge in single‐atom (SA) catalysis is the design of fully inorganic sites capable of emulating the high reaction selectivity traditionally exclusive of organometallic counterparts in homogeneous catalysis. Modulating the direct coordination environment in SA sites, via the exploitation of the oxide support's surface chemistry, stands as a powerful albeit underexplored strategy. We report that isolated Rh atoms stabilized on oxygen‐defective SnO2 uniquely unite excellent TOF with essentially full selectivity in the gas‐phase hydroformylation of ethylene, inhibiting the thermodynamically favored olefin hydrogenation. Density Functional Theory calculations and surface characterization suggest that substantial depletion of the catalyst surface in lattice oxygen, energetically facile on SnO2, is key to unlock a high coordination pliability at the mononuclear Rh centers, leading to an exceptional performance which is on par with that of molecular catalysts in liquid media.

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“…Based on these results, the modification of Rh/SiO 2 catalysts was attempted. Accidentally, at that time, our group studied the catalyst systems with strong metal-support interaction and strong metal oxide interaction, for example, Rh-VO x and Rh-MoO x [30][31][32], and these catalysts were first applied to the hydrogenolysis reactions. It is found that the addition of Re, Mo, and W to Rh/SiO 2 enhanced the catalytic activity of the glycerol hydrogenolysis (Fig.…”

Section: Hydrogenolysis Of Glycerol and Tetrahydrofurfurylmentioning

confidence: 98%

Selective Hydrogenolysis of C–O Bonds Using the Interaction of the Catalyst Surface and OH Groups

Tomishige

¹

,

Nakagawa

²

,

Tamura

³

2014

Topics in Current Chemistry

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Hydrogenolysis of C-O bonds is becoming more and more important for the production of biomass-derived chemicals. Since substrates originated from biomass usually have high oxygen content and various kinds of C-O bonds, selective hydrogenolysis is required. Rhenium or molybdenum oxide modified rhodium and iridium metal catalysts (Rh-ReO(x), Rh-MoO(x), and Ir-ReO(x)) have been reported to be effective for selective hydrogenolysis. This review introduces the catalytic performance and reaction kinetics of Rh-ReO(x), Rh-MoO(x), and Ir-ReO(x) in the hydrogenolysis of various substrates, where selectivity is especially characteristic. Based the model structure of the catalysts and the reaction mechanism, the role of the oxide components is to make the interaction between the OH groups in the substrates and the catalyst surface, and the role of metal components is to dissociate hydrogen molecule heterolytically to give hydride and proton.

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Selective formation of 1-propanol via ethylene hydroformylation over the catalyst originated from RhVO4

Cited by 21 publications

References 25 publications

Rhodium Single‐Atom Catalyst Design through Oxide Support Modulation for Selective Gas‐Phase Ethylene Hydroformylation

Rhodium Single‐Atom Catalyst Design through Oxide Support Modulation for Selective Gas‐Phase Ethylene Hydroformylation

Rhodium Single‐Atom Catalyst Design through Oxide Support Modulation for Selective Gas‐Phase Ethylene Hydroformylation

Selective Hydrogenolysis of C–O Bonds Using the Interaction of the Catalyst Surface and OH Groups

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