Mechanistic Insights into the Conversion of Cyclohexene to Adipic Acid by H<sub>2</sub>O<sub>2</sub> in the Presence of a TAPO‐5 Catalyst

Lee, Sang-Ok; Raja, Robert; Harris, Kenneth D. M.; Thomas, John Meurig; Johnson, Brian F. G.; Sankar, Gopinathan

doi:10.1002/ange.200250351

Cited by 29 publications

(12 citation statements)

References 17 publications

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“…We have previously shown that individually these two metal dopants (as monometallic entities) are capable of catalysing a range of oxidation reactions. 22,23 However, we have recently demonstrated 9,16 that their simultaneous incorporation has the potential to induce catalytic synergy. Comprehensive UV/Vis studies demonstrated that the local environment around the titanium becomes more tetrahedral when cobalt is present in the same framework.…”

Section: Introductionmentioning

confidence: 99%

Spectroscopic and Computational Insights on Catalytic Synergy in Bimetallic Aluminophosphate Catalysts

et al. 2015

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A combined electronic structure computational and X-ray absorption spectroscopy study was used to investigate the nature of the active sites responsible for catalytic synergy in Co-Ti bimetallic nanoporous frameworks. Probing the nature of the molecular species at the atomic level has led to the identification of a unique Co-O-Ti bond, which serves as the loci for the superior performance of the bimetallic catalyst, when compared with its analogous monometallic counterpart. The structural and spectroscopic features associated with this active site have been characterized and contrasted, with a view to affording structureproperty relationships, in the wider context of designing sustainable catalytic oxidations with porous solids.

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Section: Introductionmentioning

confidence: 99%

Spectroscopic and Computational Insights on Catalytic Synergy in Bimetallic Aluminophosphate Catalysts

et al. 2015

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“…Indeed, the hydroperoxidation of CHD is one of the steps in the multi‐step one‐pot oxidation of cyclohexene to AA 8. 9 Heterogeneous catalysts have also been investigated in the direct oxidative cleavage of cyclohexene; Ti‐MMM‐2, Ce‐SBA‐15, TAPO‐5, and Ti‐AlSBA‐15 proved to be active with either HP10, 11 or tert ‐butylhydroperoxide 12…”

Section: Introductionmentioning

confidence: 99%

Oxidation of 1,2‐Cyclohexanediol to Adipic Acid with Oxygen: A Study Into Selectivity‐Affecting Parameters

Rozhko¹,

Raabová²,

Macchia³

et al. 2013

ChemCatChem

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The aerobic oxidation of trans‐1,2‐cyclohexanediol in the synthesis of adipic acid was studied. Two classes of catalysts are compared, 1) alumina‐supported Ru(OH)3, and 2) Keggin type P/Mo/V polyoxometalates. These two classes are representative examples because they are active in alcohol oxidation under quite different reaction conditions. In the former case, basic conditions are needed in order to activate the substrate, whereas with polyoxometalates, acidic conditions are used. Their catalytic behavior showed remarkable differences; in basic conditions, the reaction network was very complex, and several side reactions led to a number of by‐products, with a low selectivity to adipic acid in the end. The supported Ru(OH)3 catalyst was very efficient in 1,2‐cyclohexanediol oxidative dehydrogenation to 1,2‐cyclohexanedione, but several undesired reactions occurred starting from this key intermediate under basic conditions: rearrangement into 6‐hydroxycaprolactone and 1‐hydroxycyclopentanecarboxylic acid, and formation of the product of aldol condensation. The former compound was also an intermediate for adipic acid formation, but this reaction gave only a minor contribution to the reactant conversion. Polyoxometalates were extremely selective in 1,2‐cyclohexanediol conversion into adipic acid, but under acidic conditions the product reacted with the unconverted reactant to yield the corresponding ester.

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“…Cyclohexene, with the "right" catalyst is converted into adipic acid using H 2 O 2 as oxidant. [104,105] 7.2.2. Adipic Acid from Sustainable Sources by Using a Single-Site Supported Ru 10 Pt 2 Nanoparticle Catalyst…”

Section: Solvent-free Selective Hydrogenation Reactions As Candidatesmentioning

confidence: 98%

Single‐Site Heterogeneous Catalysts

2005

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Intellectually, the advantages that flow from the availability of single-site heterogeneous catalysts (SSHC) are many. They facilitate the determination of the kinetics and mechanism of catalytic turnover-both experimentally and computationally-and make accessible the energetics of various intermediates (including short-lived transition states). These facts in turn offer a rational strategic principle for the design of new catalysts and the improvement of existing ones. It is generally possible to prepare soluble molecular fragments that circumscribe the single-site, thus enabling a direct comparison to be made, experimentally, between the catalytic performance of the same active site when functioning as a heterogeneous (continuous solid) as well as a homogeneous (dispersed molecular) catalyst. This approach also makes it possible to modify the immediate atomic environment as well as the central atomic structure of the active site. From the practical standpoint, SSHC exhibit very high selectivities leading to the production of sharply defined molecular products, just as do their homogeneous analogues. Given that mesoporous silicas with very large internal surface areas are ideal supports for SSHC, and that more than a quarter of the elements of the Periodic Table may be grafted as active sites onto such silicas, there is abundant scope for creating new catalytic opportunities.

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Mechanistic Insights into the Conversion of Cyclohexene to Adipic Acid by H₂O₂ in the Presence of a TAPO‐5 Catalyst

Cited by 29 publications

References 17 publications

Spectroscopic and Computational Insights on Catalytic Synergy in Bimetallic Aluminophosphate Catalysts

Spectroscopic and Computational Insights on Catalytic Synergy in Bimetallic Aluminophosphate Catalysts

Oxidation of 1,2‐Cyclohexanediol to Adipic Acid with Oxygen: A Study Into Selectivity‐Affecting Parameters

Single‐Site Heterogeneous Catalysts

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Mechanistic Insights into the Conversion of Cyclohexene to Adipic Acid by H2O2 in the Presence of a TAPO‐5 Catalyst

Cited by 29 publications

References 17 publications

Spectroscopic and Computational Insights on Catalytic Synergy in Bimetallic Aluminophosphate Catalysts

Spectroscopic and Computational Insights on Catalytic Synergy in Bimetallic Aluminophosphate Catalysts

Oxidation of 1,2‐Cyclohexanediol to Adipic Acid with Oxygen: A Study Into Selectivity‐Affecting Parameters

Single‐Site Heterogeneous Catalysts

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Mechanistic Insights into the Conversion of Cyclohexene to Adipic Acid by H₂O₂ in the Presence of a TAPO‐5 Catalyst