Ethylene hydroformylation and carbon monoxide hydrogenation over modified and unmodified silica supported rhodium catalysts

Hanaoka, Toshiaki; Arakawa, Hironori; Matsuzaki, Takehiko; Sugi, Yoshihiro; Kan'no, Ken‐ichi; Abe, Yoshimoto

doi:10.1016/s0920-5861(00)00261-3

Cited by 79 publications

(60 citation statements)

References 16 publications

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“…We consider these observations to be strong evidence that propionaldehyde formation occurs more favorably on undercoordinated Rh sites over the hd p i ¼ 7.1 nm to 2.5 nm size range. This observation is consistent with and corroborated by previous technical catalyst studies of C 2 H 4 hydroformylation on supported Rh catalysts, which show a similar relationship between dispersion and propionaldehyde TOF (18,19).…”

Section: Discussionsupporting

confidence: 92%

“…Insightful studies by Chuang and coworkers (14)(15)(16)(17) and others (18,19) have investigated C 2 H 4 hydroformylation on oxide supported Rh particles to gain information on the reaction mechanism and reactivity of various adsorbed CO surface species. Motivated by the desire to understand oxygenate reaction pathways in CO hydrogenation catalysis, investigators have utilized C 2 H 4 hydroformylation as a probe reaction to understand CO insertion into adsorbed surface ethyl species (R-C 2 H 5 ), without the complications of the CO dissociation step.…”

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confidence: 99%

“…Studies of C 2 H 4 hydroformylation on cluster derived (19) and traditional (18) Rh powder catalysts have shown that propionaldehyde formation (TOF) is increased as Rh dispersion is increased. Competing ethylene hydrogenation TOF was observed to be structure insensitive over this particle dispersion range in one case (19), but structure sensitive in another study, exhibiting a maximum activity near 4 nm (18). Studies of Rh alloy surfaces (e.g., RhZn (21), RhIr (22), and RhS (23)) have suggested isolated Rh sites on alloy surfaces are favorable for CO insertion under CO hydrogenation or hydroformylation conditions.…”

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confidence: 99%

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Planar oxide supported rhodium nanoparticles as model catalysts

McClure

Lundwall²,

Goodman³

2010

Proc. Natl. Acad. Sci. U.S.A.

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C 2 H 4 ∕CO∕H 2 reaction is investigated on Rh∕SiO 2 model catalyst surfaces. Kinetic reactivity and infrared spectroscopic measurements are investigated as a function of Rh particle size under near atmospheric reaction conditions. Results show that propionaldehyde turnover frequency (TOF) (CO insertion pathway) exhibits a maximum activity near hd p i ¼ 2.5 nm. Polarization modulation infrared reflection absorption spectroscopy under CO and reaction (C 2 H 4 ∕CO∕H 2 ) conditions indicate the presence of Rh carbonyl species (RhðCOÞ 2 , Rh(CO)H) on small Rh particles, whereas larger particles appear resistant to dispersion and carbonyl formation. Combined these observations suggest the observed particle size dependence for propionaldehyde production via CO insertion is driven by two factors: (i) an increase in propionaldehyde formation on undercoordinated Rh sites and (ii) creation of carbonyl hydride species (Rh(CO)H)) on smaller Rh particles, whose presence correlates with the lower activity for propionaldehyde formation for hd p i < 2.5 nm.Ethylene hydroformylation | CO insertion | polarization modulation infrared reflection absorption spectroscopy | Rh/SiO2 A complicating effect of understanding the structure-activity relationships of heterogeneous catalytic reactions at ambient pressures (near 1 atm or above) is the known ability of reactant gas environments to alter the morphology, particle dispersion, and even the types of adsorbates present on certain supported nanoparticle (NP) systems (1-4). For example, elevated pressure CO ambients have been shown to oxidatively disrupt and disperse Rh nanoparticles, creating highly dispersed gem-dicarbonyl species RhðCOÞ 2 on oxide supports (1-3, 5-8). Under elevated pressure (CO∕H 2 ) and (CO 2 ∕H 2 ) hydrogenation reaction conditions, Rh(CO)H carbonyl hydride species can also be formed (3, 9-12). The creation and stability of such carbonyl species (RhðCOÞ 2 , Rh(CO)H) can depend on particle size, gas pressure, and surface temperature. The cumulative effect of such factors could potentially have an important effect on the overall catalytic properties of the supported Rh NP surface, especially for catalytic reactions involving surface bound CO. Developing an understanding of how such factors can affect the catalytic properties of supported Rh NPs is important from a fundamental surface chemistry perspective. Unraveling these details will require the ability to conduct spectroscopic and kinetic investigations of an informative probe reaction (i) under near atmospheric reaction conditions and (ii) on supported Rh nanoparticles surfaces with well defined initial particle size distributions.CO insertion into adsorbed alkyl groups (R-C x H y ) to form oxygenates (e.g., alcohols, aldehydes) is an important reaction step in many heterogeneous catalytic reactions. For example, C 2 H 4 hydroformylation (C 2 H 4 þ CO þ H 2 ) is a well known reaction for the synthesis of aldehydes via the CO insertion reaction (13). Insightful studies by Chuang and coworkers (14-17) and others (...

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Section: Discussionsupporting

confidence: 92%

mentioning

confidence: 99%

mentioning

confidence: 99%

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Planar oxide supported rhodium nanoparticles as model catalysts

McClure

Lundwall²,

Goodman³

2010

Proc. Natl. Acad. Sci. U.S.A.

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“…For supported Rhmetal catalysts TOF's were reported of 3.85 · 10 3 lmol/ (mol Rh s) for gas phase ethylene hydroformylation at 180°C and 20 bar [12], and about 2.1 lmol/(mol Rh s) for propene hydroformylation at atmospheric pressure [13]. The latter study also reported that hydrogenation and hydroformylation proceeded with roughly equal rates at atmospheric pressure, which is in agreement with our results obtained on the decomposed catalyst (table 1).…”

Section: Discussionmentioning

confidence: 99%

Gas phase hydroformylation of ethylene using organometalic Rh-complexes as heterogeneous catalysts

et al. 2005

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The heterogeneously catalysed gas phase hydroformylation of ethylene to propionaldehyde was studied over solid RhCl(PPh 3 ) 3 and RhCl(CO)(PPh 3 ) 2 . At 3 bar and 185°C, an active phase formed from RhCl(PPh 3 ) 3 which was different from RhCl(CO)(PPh 3 ) 2 under the reaction conditions studied. The selectivity of RhCl(PPh 3 ) 3 to propanal was much better than that of supported Rhmetal. Thus, solid metal-complexes operated in gas phase reactions clearly hold promise as a new class of heterogeneous catalysts.

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“…It has been known that rhodium is the most active catalyst for hydroformylation. Although the catalyst development for the gas-phase [1,2] and liquid-phase [3][4][5][6] hydroformylation has been performed, the additive effect of various components on heterogeneous Rh catalysts has been investigated [7][8][9][10][11][12][13][14][15]. It has been reported that the additives such as Fe, Zn promote the formation of alcohols in ethylene hydroformylation [1,8].…”

Section: Introductionmentioning

confidence: 99%

Promoting Effect of Mo on Alcohol Formation in Hydroformylation of Propylene and Ethylene on Mo-Rh/SiO2

et al. 2005

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It is found that the addition of Mo to Rh/SiO 2 (Mo-Rh/SiO 2 ) promoted alcohol formation in hydroformylation of propylene and ethylene, at the same time it drastically enhanced the activity of hydroformylation and hydrogenation. It is suggested that H 2 adsorption sites, which are not inhibited by CO adsorption, are present on Mo-Rh/SiO 2 . The sites can cause high H 2 activation, and it can be related to the additive effect of Mo in hydroformylation reactions.

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Ethylene hydroformylation and carbon monoxide hydrogenation over modified and unmodified silica supported rhodium catalysts

Cited by 79 publications

References 16 publications

Planar oxide supported rhodium nanoparticles as model catalysts

Planar oxide supported rhodium nanoparticles as model catalysts

Gas phase hydroformylation of ethylene using organometalic Rh-complexes as heterogeneous catalysts

Promoting Effect of Mo on Alcohol Formation in Hydroformylation of Propylene and Ethylene on Mo-Rh/SiO2

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