Influence of peroxometallic intermediaries present on polyoxometalates nanoparticles surface on the adipic acid synthesis

Alcañiz-Monge, Juan; Trautwein, Guido; Garcı́a-Garcı́a, Avelina

doi:10.1016/j.molcata.2014.07.023

Cited by 34 publications

(15 citation statements)

References 40 publications

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“…1) showed the characteristic vibration bands of the Keggin structure in the spectral range of 1200-400 cm −1 [36]. The vibration band corresponding to phosphorus-oxygen, v as P-O a , was observed at 1062 cm −1 and those assigned to metal-oxygen, AA yield (% ) = 100 × w (AA) exp ∕w (AA) the of different IR vibration bands, confirming thus that the introduction of a metal atom in cationic position does not disturb the Keggin anion symmetry as already reported in other studies [4,26]. The UV-visible spectra of different solids (Fig.…”

Section: Characterization Resultssupporting

confidence: 81%

“…With an equimolar mixture (50/50%), AA formation was not observed, contrarily to the industrial process. The negative effect of alcohol presence in the reaction mixture has already been mentioned [4,8,20,26,28,39]. It was attributed to the formation of hydrogen bonds between the C=O group of the ketone and the hydrogen of the C-OH group of cyclohexanol, which makes the -one oxidation of the mixture difficult.…”

Section: Adipic Acid Synthesis From Cyclohexanone/ Cyclohexanol Oxidamentioning

confidence: 99%

“…HMPMo 12 O 40 heteropoly salts were prepared using a cationic exchange method [4,26,39] The M presence confirmation was realized using the complexation tests shown in Table 1.…”

Section: Materials Synthesismentioning

confidence: 99%

“…In organic synthesis, H 2 O 2 is widely used in alkene epoxidation reactions [12,13,18] and Baeyer-Villiger oxidation reactions of cyclic ketones and aldehydes [37,38,40,41]. In the case of AA synthesis, H 2 O 2 was used in the presence of different catalysts such as µ 3 -oxo-bridged Co/ Mn cluster complexes CoMn 2 (O) [9], [Mn III T(p-Cl)PP] Cl [23], N-hydroxyphthalimide combined with Mn(acac) 2 or Co(OAc) 2 [19] [1]. In these processes, H 2 O 2 was added to the reaction mixture at the same time as the substrate (cyclohexene, cyclohexanone or cyclohexanol) and catalyst.…”

Section: Introductionmentioning

confidence: 99%

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Transition metal-substituted Keggin-type polyoxometalates as catalysts for adipic acid production

et al. 2019

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The adipic acid (AA) production was carried out in two stages: oxidation of cyclohexanone (-one) by Keggin-type polyoxometalate (POM), followed by oxidation of this latter by hydrogen peroxide. The process lasts 20 h and the temperature is maintained at 90 °C. AA is then recovered by cold crystallization (4 °C). The POMs have as formula HMPMo 12 O 40 (M:Co, Ni, Mn, Cu or Zn). The materials were characterized by FT-IR and UV-Vis spectroscopies and by thermogravimetric analysis. The purity of adipic acid was confirmed by FT-IR and 13 C and 1 H NMR analysis. The effects of POM composition, catalyst/-one molar ratio and the cyclohexanol addition to-one on adipic acid yield were examined. The whole catalysts were found to be effective toward cyclohexanone oxidation and the highest yield (53%) was obtained with HZnPMo 12 O 40 system for a catalyst/-one molar ratio of 1.89 × 10 −3. The alcohol addition to-one has a negative effect on adipic acid formation.

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Section: Characterization Resultssupporting

confidence: 81%

Section: Adipic Acid Synthesis From Cyclohexanone/ Cyclohexanol Oxidamentioning

confidence: 99%

“…HMPMo 12 O 40 heteropoly salts were prepared using a cationic exchange method [4,26,39] The M presence confirmation was realized using the complexation tests shown in Table 1.…”

Section: Materials Synthesismentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Transition metal-substituted Keggin-type polyoxometalates as catalysts for adipic acid production

et al. 2019

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“…In addition, POMs could not only serve as co-catalysts but could stabilize the active metal sites and regulate the electronic structure of catalysts to give rise to the enhancement of catalytic activities [32][33][34][35]. Over the years, our group has dedicated substantial efforts on the development of organically functionalized Anderson-type POMs [30,[36][37][38][39][40][41][42][43]. Thus, we predicted that the Anderson-type POMs with manganese as the active metal site might catalyze the green oxidation of cyclohexanone, cyclohexanol, and KA oil to AA with high reactivity.…”

Section: Introductionmentioning

confidence: 99%

Single-Atom Mn Active Site in a Triol-Stabilized β-Anderson Manganohexamolybdate for Enhanced Catalytic Activity towards Adipic Acid Production

et al. 2018

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Adipic acid is an important raw chemical for the commercial production of polyamides and polyesters. The traditional industrial adipic acid production utilizes nitric acid to oxidize KA oil (mixtures of cyclohexanone and cyclohexanol), leading to the emission of N 2 O and thus causing ozone depletion, global warming, and acid rain. Herein, we reported an organically functionalized β-isomer of Anderson polyoxometalates (POMs) nanocluster with single-atom Mn, β-{[H 3 NC(CH 2 O) 3 ] 2 MnMo 6 O 18 } − (1), as a highly active catalyst to selectively catalyze the oxidation of cyclohexanone, cyclohexanol, or KA oil with atom economy use of 30% H 2 O 2 for the eco-friendly synthesis of adipic acid. The catalyst has been characterized by single crystal and powder XRD, XPS, ESI-MS, FT-IR, and NMR. A cyclohexanone (cyclohexanol) conversion of >99.9% with an adipic acid selectivity of~97.1% (~85.3%) could be achieved over catalyst 1 with high turnover frequency of 2427.5 h −1 (2132.5 h −1). It has been demonstrated that the existence of Mn 3+ atom active site in catalyst 1 and the special butterfly-shaped topology of POMs both play vital roles in the enhancement of catalytic activity.

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A Simple Approach To Develop Tailored Mesoporosity in Nanostructured Heteropolysalts

Alcañiz-Monge

Trautwein

Bakkali

et al. 2017

Chemistry A European J

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Abstract:In this work, we describe a very simple approach to develop tailored mesoporosity in any nanostructured heteropolysalt with control over both the mesoporous volume and the pore size. This approach consisting in a treatment of the solid microporous precursor with a basic agent has been tested on the ammonium salt of the Keggin-type [PMo12O40] 3− heteropolyanion, and constitutes a novel procedure for the preparation of mesoporous solids with no precedents in the literature. The results obtained in this study allows for extracting two main conclusions: (i) The micro-and mesoporosity structures in the heteropolysalt nanoparticles are independent from each other; and (ii) The development of mesoporosity in the solid material must be related with a process of alkaline degradation within the core of the nanocrystals aggregating into the particles. These results afford additional valuable information to the model of porosity that is established for heteropolysalts at present.

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Influence of peroxometallic intermediaries present on polyoxometalates nanoparticles surface on the adipic acid synthesis

Cited by 34 publications

References 40 publications

Transition metal-substituted Keggin-type polyoxometalates as catalysts for adipic acid production

Transition metal-substituted Keggin-type polyoxometalates as catalysts for adipic acid production

Single-Atom Mn Active Site in a Triol-Stabilized β-Anderson Manganohexamolybdate for Enhanced Catalytic Activity towards Adipic Acid Production

A Simple Approach To Develop Tailored Mesoporosity in Nanostructured Heteropolysalts

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