Reaction Paths in the Hydrogenolysis of Acetic Acid to Ethanol over Pd(111), Re(0001), and PdRe Alloys

Pallassana, Venkataraman; Neurock, Matthew

doi:10.1006/jcat.2002.3585

Cited by 125 publications

(131 citation statements)

References 40 publications

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“…These intermediates were not seen in the liquid samples, possibly because they remain adsorbed on the catalyst and/ or they are highly reactive. As discussed previously, the C 18 compound could be formed on metal sites via C-O hydrogenolysis on Pt sites [18] or on oxygen vacancies as suggested by Ponec et al [16]. Condensation products were seen in both cases (Figs.…”

Section: Liquid Phase Conversionmentioning

confidence: 77%

“…Oxygen removal occurs on the reducible oxide via an oxygen vacancy mechanism, while the metal provides dissociated hydrogen to reduce the oxides [16]. Reduction of carboxylic acids to corresponding alcohols and aldehydes has been both theoretically and experimentally examined over Cu, Pd, and Re catalysts [17][18][19][20]. Theoretical studies [20] have shown that the metal catalyzed hydrogenation of acetic acid requires a balance between C-O-bond-breaking, which results in aldehyde/ alcohol products, and b C-H-bond-rupturing, which leads to decarboxylation/decarbonylation products.…”

Section: Introductionmentioning

confidence: 99%

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Catalytic Deoxygenation of Methyl-Octanoate and Methyl-Stearate on Pt/Al2O3

et al. 2009

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The deoxygenation of methyl octanoate and methyl stearate over alumina-supported Pt was studied in both the vapor phase in a flow reactor and in the liquid phase in a semibatch reactor. The conversion of both methyl esters resulted in hydrocarbons with one carbon less than the fatty acid of the corresponding ester as the dominant products. In the vapor phase, acid and other oxygenates were observed in low concentrations, but they were not detected when the reaction was conducted in the liquid phase. Under He, condensation products (from esterification and ketonization) were observed. By contrast, under H 2 , mostly paraffins were obtained. These results show promise to directly produce standard diesel components from biodiesel.

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Section: Liquid Phase Conversionmentioning

confidence: 77%

Section: Introductionmentioning

confidence: 99%

Catalytic Deoxygenation of Methyl-Octanoate and Methyl-Stearate on Pt/Al2O3

et al. 2009

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“…These catalysts all contain highly active PdARe sites that are selective to FAL; however, the DCS catalyst is distinguished by weak adsorption of CO on Re and Pd twofold bridging sites and the nearly complete elimination of threefold bridging CO on Pd. One can speculate that a Pd 0.33 Re 0.67 surface alloy as modeled by Neurock and coworkers [70] might be optimum (or nearly so) for furfural hydrogenation [36]. Interaction of the carbonyl oxygen with oxophilic Re atoms may enhance furfural adsorption.…”

Section: Discussionmentioning

confidence: 98%

Catalysts for selective hydrogenation of furfural derived from the double complex salt [Pd(NH3)4](ReO4)2 on γ-Al2O3

Thompson

Lamb

2017

Journal of Catalysis

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a b s t r a c tThe double complex salt [Pd(NH 3 ) 4 ](ReO 4 ) 2 was employed as precursor of supported bimetallic catalysts for selective hydrogenation of furfural. Direct reduction of [Pd(NH 3 ) 4 ](ReO 4 ) 2 on c-Al 2 O 3 in flowing H 2 at 400°C yields bimetallic nanoparticles 1-2 nm in size that exhibit significant interaction between the metals, as evidenced by temperature-programmed hydride decomposition (complete suppression of b-PdH x formation), extended X-ray absorption fine structure spectroscopy at the Pd K and Re L III edges (PdARe distance = 2.72 Å), and scanning transmission electron microscopy with energy dispersive X-ray analysis. In contrast, calcination of [Pd(NH 3 ) 4 ](ReO 4 ) 2 on c-Al 2 O 3 at 350°C in air and subsequent reduction in H 2 at 400°C results in metal segregation and formation of large (>50 nm) supported Pd particles; Re species cover the Pd particles and c-Al 2 O 3 support. A PdRe 1:2 catalyst prepared by sequential impregnation and calcination using HReO 4 and [Pd(NH 3 ) 4 ](NO 3 ) 2 has a similar morphology.The catalyst derived by direct reduction of [Pd(NH 3 ) 4 ](ReO 4 ) 2 on c-Al 2 O 3 exhibits remarkably high activity for selective hydrogenation of furfural to furfuryl alcohol (FAL) at 150°C and 1 atm. Suppression of H 2 chemisorption via elimination of Pd threefold sites, as evidenced by CO diffuse-reflectance infrared Fourier transform spectroscopy, correlates with increased FAL selectivity.

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“…[34,51]. The Neurock research group has reported DFT-based binding energies for a number of key species participating in C 2 chemistry on Pd and Re [52]. In another DFT study of various pathways for ethanol decomposition on Pt (111), Dumesic and colleagues have reported energetics for the C-C and C-O bond cleavage in surface species [53].…”

Section: Computational Studiesmentioning

confidence: 99%

Microkinetic modeling and analysis of ethanol partial oxidation and reforming reaction pathways on platinum at short contact times

Koehle

Mhadeshwar

2012

Chemical Engineering Science

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2013iii ACKNOWLDGEMENTSThere are many people without whom this thesis would not have been possible. I must thank Ashish Mhadeshwar for the incredible amount of knowledge he imparted and the guidance he provided in order for this research to be conducted, shared at conferences and published. Many thanks to Doug Cooper, Bill Mustain and Ranjan Srivastava for standing in as advisors and providing support that was above and beyond expectations. I want to thank everyone that has become part of my UConn family, without whom this project would have been possible but much less fun:

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Reaction Paths in the Hydrogenolysis of Acetic Acid to Ethanol over Pd(111), Re(0001), and PdRe Alloys

Cited by 125 publications

References 40 publications

Catalytic Deoxygenation of Methyl-Octanoate and Methyl-Stearate on Pt/Al2O3

Catalytic Deoxygenation of Methyl-Octanoate and Methyl-Stearate on Pt/Al2O3

Catalysts for selective hydrogenation of furfural derived from the double complex salt [Pd(NH3)4](ReO4)2 on γ-Al2O3

Microkinetic modeling and analysis of ethanol partial oxidation and reforming reaction pathways on platinum at short contact times

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