Nanocrystalline gold catalysts: A reflection on catalyst discovery and the nature of active sites

Hutchings, Graham J.

doi:10.1007/bf03214947

Cited by 32 publications

(39 citation statements)

References 30 publications

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“…This conclusion is consistent with the discussion in the previous part and published experimental studies, in which BaCl2 gives the highest activity [9,10]. It is interesting that noble metals, such as Au and Ru, do not show advantages for this reaction, despite their prominent performance for acetylene hydrochlorination reaction (activity sequence of AuCl3 > RuCl3 > BaCl2 has been reported, Figure S3) [19][20][21][22]. Section 2.7 provides the explanation of reversed activity sequences for the two reactions.…”

Section: Energy Profilessupporting

confidence: 91%

Catalytic Mechanism Comparison Between 1,2-Dichloroethane-Acetylene Exchange Reaction and Acetylene Hydrochlorination Reaction for Vinyl Chloride Production: DFT Calculations and Experiments

Man

Luo

2020

Catalysts

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The catalytic mechanism and activation energies of metal chlorides RuCl 3 , AuCl 3 , and BaCl 2 for 1,2-dichloroethane (DCE)-acetylene exchange reaction were studied with a combination of density functional theory (DFT) calculations and experiments. Two reported reaction pathways were discussed and acetylene-DCE complex pathway was supported through adsorption energy analysis. The formation of the second vinyl chloride monomer (VCM) was proven to be the rate-determining step, according to energy profile analysis. Activity sequence of BaCl 2 > RuCl 3 > AuCl 3 was predicted and experimentally verified. Furthermore, reversed activity sequences of this reaction and commercialized acetylene hydrochlorination reaction were explained: the adsorption abilities of reactants are important for the former reaction, but chlorine transfer is important for the latter.When comparing with traditional acetylene hydrochlorination process, the newly reported Jiang-Zhong VCM process has outstanding advantages: (1) higher yield of main product due to reuse of byproduct DCE; (2) lower heat effect due to good balance of endothermic (DCE decomposition) and exothermic (acetylene hydrochlorination) reactions; (3) avoidance of corrosive HCl; and, (4) halved acetylene consumption and corresponding waste generated from coal-based acetylene production. The new route can be regarded as a combination of the coal and petroleum chemical industry and it opens up new possibilities for greener VCM production. However, the published results on this new route are notably limited and an instructive understanding is of great importance.Density functional theory (DFT) is becoming a very useful tool for computational material science and chemistry [8]. However, to the best of our knowledge, no DFT study has been reported for the new Jiang-Zhong VCM process, and the experimental exploration is also in the early stage. It is highly useful for guiding the rational development of novel DCE-acetylene exchange catalysts with the assistance of computational chemistry.In this work, the catalytic reaction mechanisms of RuCl 3 , AuCl 3 , and BaCl 2 for DCE-acetylene exchange reaction were studied in detail by DFT calculation. The experiments were further carried out and a high consistency between DFT calculations and experimental results was achieved. When comparing with the traditional acetylene hydrochlorination reaction, the reversed activity sequence was anticipated, which was explained by the differences in mechanisms. The work provided guidance for the deep understanding and screening methodology of catalysts for DCE-acetylene exchange reaction, which can accelerate the development of this green and highly efficient route for VCM production.

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Section: Energy Profilessupporting

confidence: 91%

Catalytic Mechanism Comparison Between 1,2-Dichloroethane-Acetylene Exchange Reaction and Acetylene Hydrochlorination Reaction for Vinyl Chloride Production: DFT Calculations and Experiments

Man

Luo

2020

Catalysts

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“…Since their introduction by Haruta,1 oxide‐supported gold catalysts with gold nanoparticles (NPs) of a few nanometers in diameter have attracted enormous interest because of their high activity for various oxidation and reduction reactions,2 most prominently the CO oxidation reaction 2–6. Mechanistic details and hence the physical origin of their high activity, however, are still controversial.…”

Section: Irreversible and Reversible (Osc) Loss Of Oxygen In The Redumentioning

confidence: 99%

Active Oxygen on a Au/TiO₂ Catalyst: Formation, Stability, and CO Oxidation Activity

2011

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Ideal location: The active oxygen for CO oxidation on Au/TiO2 catalysts is a highly stable oxygen species, whose formation is facile and hardly activated. This species is proposed to be surface lattice oxygen at the perimeter of the Au–TiO2 interface, activated by the presence of the Au nanoparticle. At higher temperatures, thermally activated Olatt migration also gives access to adjacent Olatt species.

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“…[20][21][22][23][24] To reach nearly 99% yield of FDCA, the reaction time for Au NPs on nanoparticulate CeO 2 was half of that for the Au on non-nanometric CeO 2 . 15 Reductive pretreatment of the Au/CeO 2 was shown to efficiently increase the catalytic activity because it increased the amount of Ce 3+ and oxygen vacancies.…”

Section: Introductionmentioning

confidence: 99%

Superior catalytic performance of Ce_1−xBi_xO_2−δsolid solution and Au/Ce_1−xBi_xO_2−δfor 5-hydroxymethylfurfural conversion in alkaline aqueous solution

Miao

Zhang

Pan

et al. 2015

Catal. Sci. Technol.

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Nanocrystalline gold catalysts: A reflection on catalyst discovery and the nature of active sites

Cited by 32 publications

References 30 publications

Catalytic Mechanism Comparison Between 1,2-Dichloroethane-Acetylene Exchange Reaction and Acetylene Hydrochlorination Reaction for Vinyl Chloride Production: DFT Calculations and Experiments

Catalytic Mechanism Comparison Between 1,2-Dichloroethane-Acetylene Exchange Reaction and Acetylene Hydrochlorination Reaction for Vinyl Chloride Production: DFT Calculations and Experiments

Active Oxygen on a Au/TiO₂ Catalyst: Formation, Stability, and CO Oxidation Activity

Superior catalytic performance of Ce_1−xBi_xO_2−δsolid solution and Au/Ce_1−xBi_xO_2−δfor 5-hydroxymethylfurfural conversion in alkaline aqueous solution

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Nanocrystalline gold catalysts: A reflection on catalyst discovery and the nature of active sites

Cited by 32 publications

References 30 publications

Catalytic Mechanism Comparison Between 1,2-Dichloroethane-Acetylene Exchange Reaction and Acetylene Hydrochlorination Reaction for Vinyl Chloride Production: DFT Calculations and Experiments

Catalytic Mechanism Comparison Between 1,2-Dichloroethane-Acetylene Exchange Reaction and Acetylene Hydrochlorination Reaction for Vinyl Chloride Production: DFT Calculations and Experiments

Active Oxygen on a Au/TiO2 Catalyst: Formation, Stability, and CO Oxidation Activity

Superior catalytic performance of Ce1−xBixO2−δsolid solution and Au/Ce1−xBixO2−δfor 5-hydroxymethylfurfural conversion in alkaline aqueous solution

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Active Oxygen on a Au/TiO₂ Catalyst: Formation, Stability, and CO Oxidation Activity

Superior catalytic performance of Ce_1−xBi_xO_2−δsolid solution and Au/Ce_1−xBi_xO_2−δfor 5-hydroxymethylfurfural conversion in alkaline aqueous solution