Kinetic studies of carbonylation of methanol to dimethyl carbonate over Cu+X zeolite catalyst

Anderson, Steven A.; Root, Thatcher W.

doi:10.1016/s0021-9517(02)00159-8

Cited by 87 publications

(79 citation statements)

References 13 publications

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“…The discussed initial reaction rate kinetics experiments strongly suggest that the conversion of methanol and CO 2 to DMC over ceria catalysts follows a Langmuir-Hinshelwood mechanism where the CO 2 and methanol are binding to the catalyst in separate steps, consistent with previous kinetics studies modeling the reaction from the reaction profile [16]. Interestingly, this result contrasts with that shown for the production of DMC from methanol and carbon monoxide over copper zeolite catalysts, which were found to have a non-negative rate order with respect to methanol and are believed to follow an ER mechanism [29]. This suggests that the production of DMC from CO 2 instead of CO may take a very different pathway for the production of DMC despite the apparent similarity of the overall reaction.…”

Section: Mechanistic Insightssupporting

confidence: 86%

Kinetic and mechanistic investigations of the direct synthesis of dimethyl carbonate from carbon dioxide over ceria nanorod catalysts

Marin

Bhalkikar

et al. 2016

Journal of Catalysis

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Section: Mechanistic Insightssupporting

confidence: 86%

Kinetic and mechanistic investigations of the direct synthesis of dimethyl carbonate from carbon dioxide over ceria nanorod catalysts

Marin

Bhalkikar

et al. 2016

Journal of Catalysis

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“…The addition of CH 3 OH to the latter species would produce DMC and H 2 O [reaction (4)]. This pathway is similar to that proposed by King [4,5] and by Anderson and Root [6,7]. Alternatively, CH 3 OH may be first added to Z − [Cu + (OH)(OCH 3 )] to produce Z − [Cu + (OCH 3 ) 2 ] plus water via reaction (5), after which CO reacts with the dimethoxide to form DMC [reaction (6)].…”

Section: Catalyst Activity and Selectivitysupporting

confidence: 57%

“…Cu-exchanged zeolites have been shown to be active catalysts for the oxidative carbonylation of methanol to dimethyl carbonate, with the principal byproducts being dimethoxymethane (DMM) and methyl formate (MF) [4][5][6][7][8][9]. Previous studies have shown that the structure and chemical composition of the zeolite influence the activity and selectivity of Cu-exchanged zeolites.…”

Section: Introductionmentioning

confidence: 99%

Effects of zeolite structure and composition on the synthesis of dimethyl carbonate by oxidative carbonylation of methanol on Cu-exchanged Y, ZSM-5, and Mordenite

Zhang

Briggs

Smit

et al. 2007

Journal of Catalysis

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“…[1][2][3][4] It is believed that low-temperature approaches will be most effective for generating tailored structures because of the metastable nature of many of the desired structures. 1 Supported Cu-containing catalysts have been studied for a number of industrially relevant reactions, [5][6][7][8] but little effort has been devoted to the generation of tailored sites. The introduction of isolated species onto mesoporous silica using molecular precursors of the form M[OSi(O t Bu) 3 ] n (M ) Ti 3a and Fe 3b ) under nonaqueous conditions has recently been reported.…”

mentioning

confidence: 99%

Atomic Level Control over Surface Species via a Molecular Precursor Approach: Isolated Cu(I) Sites and Cu Nanoparticles Supported on Mesoporous Silica

Fujdala

Drake²,

Bell³

et al. 2004

J. Am. Chem. Soc.

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There is a growing interest in the preparation of catalysts with well-defined and isolated sites, as such systems are ideally suited for structure-function investigations. 1 Recent studies indicate that atomically dispersed metals on high surface area silica materials are effective catalysts. [2][3][4] Thus, an important goal in catalysis research is the development of synthetic methods that provide atomic-level control over the nature of catalytic sites, with formation of isolated single sites or homogeneously distributed and more complicated structures (bimetallic sites, clusters, nanoparticles, etc.) providing new and improved catalysts. [1][2][3][4] It is believed that low-temperature approaches will be most effective for generating tailored structures because of the metastable nature of many of the desired structures. 1 Supported Cu-containing catalysts have been studied for a number of industrially relevant reactions, 5-8 but little effort has been devoted to the generation of tailored sites. The introduction of isolated species onto mesoporous silica using molecular precursors of the form M[OSi(O t Bu) 3 ] n (M ) Ti 3a and Fe 3b ) under nonaqueous conditions has recently been reported. The work presented herein provides direct evidence for atomic-level control over the nature of sites that result from grafting 9 Cu-containing molecular precursors onto the mesoporous silica SBA-15. 10 Reaction of the molecular precursors [CuOSi(O t Bu) 3 ] 4 11 (1) or [CuO t Bu] 4 12 (2) (as solutions in C 6 H 6 ) with the surface hydroxyl groups of SBA-15 under inert conditions provided grafted materials, isolated as light yellow powders after extensive washing with C 6 H 6 and drying in vacuo at 323 K. Quantities of the molecular precursors were used such that the final grafted materials contained ca. 3.5% (CuOSi/SBA(3.5) and CuO t Bu/SBA(3.5) from 1 and 2, respectively) and ca. 5.0% (CuOSi/SBA(5.0) and CuO t Bu/SBA(5.0) from 1 and 2, respectively) Cu by weight. 13 It is known that M[OSi-(O t Bu) 3 ] n species cleanly evolve 3nCH 2 C(CH 3 ) 2 and 3 / 2 nH 2 O upon mild thermolysis (373 to 473 K) to give MSi n O y materials. 1a,14 Previous studies of 1 indicate that it also exhibits loss of CH 2 C-(CH 3 ) 2 and H 2 O upon heating, although some reduction of Cu (to Cu metal) is evident under an inert atmosphere. 11 It was anticipated that grafting 1 onto SBA-15 would provide species that could eliminate CH 2 C(CH 3 ) 2 and H 2 O upon thermolysis to form Si-O surface linkages while maintaining some of the original Cu-OSi linkages to provide stabilized Cu(I) species (in the form of isolated tetramers or as single sites). Use of 2 in similar grafting reactions may also provide isolated sites; however, no additional Si-O surface linkages (and hence extra site stabilization) are provided by this precursor. Scheme 1 illustrates a possible grafting pathway and potential structure types for the resulting surface species.The molecular precursors are presumably well-separated on the surface, as the "OH" site-to-precursor ratios ...

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Kinetic studies of carbonylation of methanol to dimethyl carbonate over Cu+X zeolite catalyst

Cited by 87 publications

References 13 publications

Kinetic and mechanistic investigations of the direct synthesis of dimethyl carbonate from carbon dioxide over ceria nanorod catalysts

Kinetic and mechanistic investigations of the direct synthesis of dimethyl carbonate from carbon dioxide over ceria nanorod catalysts

Effects of zeolite structure and composition on the synthesis of dimethyl carbonate by oxidative carbonylation of methanol on Cu-exchanged Y, ZSM-5, and Mordenite

Atomic Level Control over Surface Species via a Molecular Precursor Approach: Isolated Cu(I) Sites and Cu Nanoparticles Supported on Mesoporous Silica

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