Catalysis by heteropoly compounds Part 39 The structure and redox behaviour of vanadium species in molybdovanadophosphoric acid catalysts during partial oxidation of isobutane

Inumaru, Kei; Ono, Akira; Kubo, Hiroshi; Misono, Makoto

doi:10.1039/a708629f

Cited by 61 publications

(33 citation statements)

References 22 publications

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“…[26] Table 2. [ 27] This confirmed that the majority of Pc enters was located in Keggin ions supported on SBA-15. [28] The peak in the spectrum of H 3 PO 4 -SBA-15 at 0.8 ppm could be assigned to molecular H 3 PO 4 .I nt he spectrumo fa ctivated H 3 PO 4 -SBA-15, four pronounced peaks can be seen at chemical shifts of 0.8, À10.8, À22.8, and À35.9 ppm.…”

supporting

confidence: 82%

Role of Vanadium and Phosphorus in Substituted Keggin‐Type Heteropolyoxo Molybdates Supported on Silica SBA‐15 in Selective Propene Oxidation

2015

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Vanadium‐containing Keggin‐type heteropolyoxo molybdate ([PV2Mo10O40]5−) was supported on silica SBA‐15 (denoted as PV2Mo10‐SBA‐15). The structural evolution and catalytic activity of PV2Mo10‐SBA‐15 and a suitable reference V2Mo10Ox‐SBA‐15 were investigated under selective propene oxidation conditions by using in situ X‐ray absorption spectroscopy. 31P MAS NMR measurements of supported PV2Mo10‐SBA‐15 and reference H3PO4‐SBA‐15 were performed after the catalytic reaction. PV2Mo10‐SBA‐15 formed a mixture of mainly tetrahedral [MoOx] and [VOx] units during thermal treatment under propene oxidation conditions. Changes in the average local structure around V centers coincided with the changes in the average local structure around Mo centers and the onset of catalytic activity. In addition, mainly tetrahedral [MoOx] and [VOx] units seemed to be in close proximity and interacted under catalytic conditions. Conversely, in the reference material V2Mo10Ox‐SBA‐15 synthesized with individual V and Mo source precursors, Mo and V centers appeared to be more separated from each other. The structural environment of P in PV2Mo10‐SBA‐15 under catalytic conditions corresponded to a mixture of various species. P was connected to both the support material SBA‐15 via POSi bonds and [MoOx] or [VOx] units. Apparently, the proximity of V and Mo in Keggin precursors was a prerequisite for obtaining (Mo,V) oxide species on the support material.

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confidence: 82%

Role of Vanadium and Phosphorus in Substituted Keggin‐Type Heteropolyoxo Molybdates Supported on Silica SBA‐15 in Selective Propene Oxidation

2015

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“…Examples of the applicability of POMs for alkane oxidation include isobutane to methacrolein and methacrylic acid using H 3 PMo 12 O 40 and vanadium-substituted derivatives, [92][93][94] oxidative dehydrogenation of alkanes using iron-substituted heteropolytungstates and heteropolymolybdates, 92,93 propane oxidation to acrylic acid, 95 and methane oxidation to formic acid using Pd-Cs salts of PVMo 11 O 40 . [94][95][96] There is also evidence suggesting that improved activity and selectivity for various metal-catalyzed oxidation processes can be achieved by coupling redox-active metal centers with redox-active POMs.…”

Section: Selective Oxidation Of Hydrocarbons To Oxygenated Productmentioning

confidence: 99%

Catalysis Research of Relevance to Carbon Management: Progress, Challenges, and Opportunities

et al. 2001

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“…The lactone has not been reported by other research groups. Methacrylic acid was an expected product and is commonly reported from catalytic oxidations conducted using higher pressures and non-molecular flow conditions [2,3,5,9,[26][27][28][29][30][31][32][33][34][35][36][37][38][39][40], but was not observed. The lactone is an isomer of methacrylic acid and its appearance, and the concomitant absence of methacrylic acid, suggests that it is an intermediate for methacrylic acid.…”

Section: Introductionmentioning

confidence: 86%

Mechanistic Investigation into the Rearrangement of Lactone into Methacrylic Acid over Phosphomolybdic Acid Catalyst

et al. 2010

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The rearrangement of 3-methyl-2-oxetanone (lactone) into methacrylic acid has been explored using DFT methods. Calculations were performed for (i) intramolecular, (ii) lactone-lactone and (iii) water and phosphomolybdic acid catalyzed conversions. The water and acid surface catalyzed route exhibited the lowest activation barrier (156 kJ mol -1 ) of the three reaction pathways and overall is slightly endothermic (DH f = 37 kJ mol -1 ).

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Catalysis by heteropoly compounds Part 39 The structure and redox behaviour of vanadium species in molybdovanadophosphoric acid catalysts during partial oxidation of isobutane

Cited by 61 publications

References 22 publications

Role of Vanadium and Phosphorus in Substituted Keggin‐Type Heteropolyoxo Molybdates Supported on Silica SBA‐15 in Selective Propene Oxidation

Role of Vanadium and Phosphorus in Substituted Keggin‐Type Heteropolyoxo Molybdates Supported on Silica SBA‐15 in Selective Propene Oxidation

Catalysis Research of Relevance to Carbon Management: Progress, Challenges, and Opportunities

Mechanistic Investigation into the Rearrangement of Lactone into Methacrylic Acid over Phosphomolybdic Acid Catalyst

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