Efficient Room-Temperature Aqueous-Phase Hydrogenation of Phenol to Cyclohexanone Catalyzed by Pd Nanoparticles Supported on Mesoporous MMT-1 Silica with Unevenly Distributed Functionalities

Lin, Chi-Jui; Huang, Shao-Hsien; Lai, Nien-Chu; Yang, Chia-Min

doi:10.1021/acscatal.5b00380

Cited by 56 publications

(29 citation statements)

References 47 publications

(175 reference statements)

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“…1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 aqueous system is 5420 mmol phenol converted/mmol Pd at 6 h, which is three times higher than the dilute system (1 600 mmol phenol converted/ mmol Pd). The estimated turnover frequency is 500-1000 mmol phenol converted/(mmol Pd · h), which is as good as any literature values reported, [36,37,38] which are in the range of 50-1000 mmol phenol converted/ (mmol Pd · h).…”

Section: Phenol Hydrogenationsupporting

confidence: 85%

Palladium‐Containing and Metal‐Free Supported Dendrons As Catalysts in Multistep Conversion of Oxygenates to Fuels

Lou

Shantz

2019

ChemCatChem

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This article reports a three‐step process: 1) the hydrogenation of phenol, 2) aldol condensation between the cyclohexanone produced in reaction 1 and an aldehyde, and 3) hydrogenation of the aldol reaction product. This is achieved using palladium containing supported dendrons for reactions 1 and 3 and non‐metal containing supported dendrons for reaction 2. Palladium/dendron‐OMS catalyzes the phenol hydrogenation with a cyclohexanol yield of 85 %, the parent dendrons (no Pd) catalyze the Aldol reaction with over 80 % yield in some cases, and the Pd‐dendron samples can be used to hydrogenate the aldol coupling product at high yields, not dissimilar from what one observes from aqueous phase reforming (APR). The operating conditions of low temperature and low‐pressure hydrogen in aqueous media are consistent with green chemistry goals.

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Section: Phenol Hydrogenationsupporting

confidence: 85%

Palladium‐Containing and Metal‐Free Supported Dendrons As Catalysts in Multistep Conversion of Oxygenates to Fuels

Lou

Shantz

2019

ChemCatChem

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“…Phenol hydrogenation is an important industrial process for the production of cyclohexanone and cyclohexanol. Cyclohexanone is a key intermediate in the synthesis of nylon and polyamide resins [6], while cyclohexanol is used widely in fine chemistry and perfume industry [7]. Other products such as benzene and cyclohexane [8][9][10][11] are also mentioned in the literature and have been related to the type of catalyst and solvent [9].…”

Section: Introductionmentioning

confidence: 99%

Low temperature hydrogenation and hydrodeoxygenation of oxygen-substituted aromatics over Rh/silica: part 1: phenol, anisole and 4-methoxyphenol

Alshehri

Feral

Kirkwood

et al. 2019

Reac Kinet Mech Cat

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The hydrogenation and competitive hydrogenation of anisole, phenol and 4-methoxyphenol was studied in the liquid phase over a Rh/silica catalyst at 323 K and 3 barg hydrogen pressure. The rate of conversion of the reactants to products gave an order of anisole ≫ phenol > 4-methoxyphenol with hydrogenation and hydrodeoxygenation products being produced. Anisole, the most reactive substrate, was rapidly converted to methoxycyclohexane, cyclohexane, cyclohexanone and cyclohexanol, while phenol was hydrogenated to cyclohexanone, cyclohexanol and cyclohexane. In both cases cyclohexanol was produced as a secondary product from cyclohexanone hydrogenation. The yield of cyclohexane, the hydrodeoxygenation (HDO) product was > 20% from both reactants and was formed as a primary product from the aromatic species. Hydrogenation of 4-methoxyphenol was selective to 4-methoxycyclohexanone with no alcohol formation, while the hydrogenolysis products revealed that the catalyst was more active for demethoxylation than dehydroxylation. A comparative strength of adsorption was determined from competitive hydrogenation and gave an order of anisole > phenol > 4-methoxyphenol. Competitive, pair hydrogenation inhibited HDO and stopped cyclohexane from being produced from phenol and 4-methoxyphenol, although it was still produced from anisole. An increased rate of hydrogenation for 4-methoxyphenol was observed for competitive reactions with phenol and anisole but not when all three reactants were present. In contrast to the pair reactions, when all three reactants were present HDO occurred with all aromatics producing cyclohexane. Replacing hydrogen with deuterium revealed an inverse kinetic isotope effect for ring hydrogenation of 4-methoxyphenol but not phenol or anisole, which both had a positive KIE.

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“…Catalytic ring hydrogenation of phenol is one of the methods to produce cyclohexanone in the chemical industry. Over various metal catalysts such as rhodium (Rh) and palladium (Pd), ring hydrogenation of phenol has been carried out with the addition of hydrogen (H 2 ) gas at an elevated temperature . However, from the viewpoint of green chemistry, a method for the production of cyclohexanone at ambient temperature without the use of H 2 gas is highly desired.…”

Section: Introductionmentioning

confidence: 99%

Photocatalytic Selective Ring Hydrogenation of Phenol to Cyclohexanone over a Palladium‐Loaded Titanium(IV) Oxide under Hydrogen‐Free Conditions

et al. 2019

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Photocatalytic ring hydrogenation of phenol proceeded in an aqueous suspension of palladium-loaded TiO 2 at room temperature in the presence of oxalic acid as a hole scavenger, and cyclohexanone was produced in a high yield (90 %) without the use of hydrogen gas. Cyclohexanone was formed via keto-enol tautomerism of cyclohexenol. The effects of hole scavengers and solvents on the hydrogenation of phenol can be explained by the adsorption behaviour of phenol and hole scavengers in the solvents. Over a Pd-TiO 2 photocatalyst, the apparent activation energy (Ea) in the ring hydrogenation of phenol and the Ea value in the hydrogenation of cyclohexanone were estimated to be 25 kJ mol À 1 and 36 kJ mol À 1 , respectively, as calculated by using the Arrhenius equation. We concluded that the difference in the Ea values is attributable to the selective production of cyclohexanone and the decreased production of cyclohexanol in the ring hydrogenation of phenol over a Pd-TiO 2 photocatalyst.

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Efficient Room-Temperature Aqueous-Phase Hydrogenation of Phenol to Cyclohexanone Catalyzed by Pd Nanoparticles Supported on Mesoporous MMT-1 Silica with Unevenly Distributed Functionalities

Cited by 56 publications

References 47 publications

Palladium‐Containing and Metal‐Free Supported Dendrons As Catalysts in Multistep Conversion of Oxygenates to Fuels

Palladium‐Containing and Metal‐Free Supported Dendrons As Catalysts in Multistep Conversion of Oxygenates to Fuels

Low temperature hydrogenation and hydrodeoxygenation of oxygen-substituted aromatics over Rh/silica: part 1: phenol, anisole and 4-methoxyphenol

Photocatalytic Selective Ring Hydrogenation of Phenol to Cyclohexanone over a Palladium‐Loaded Titanium(IV) Oxide under Hydrogen‐Free Conditions

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