Vapor-Phase Dehydrocoupling of Methanol to Methyl Formate over CuAl2O4

Sato, Satoshi; Iijima, Manabu; Nakayama, Toshiko; Sodesawa, Toshiaki; Nozaki, Fumio

doi:10.1006/jcat.1997.1719

Cited by 67 publications

(28 citation statements)

References 27 publications

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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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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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“…Dehydrogenation of alcohols can produce the corresponding aldehydes and ketones, as well as H 2 and esters. [268][269][270] The catalysts for this reaction involve Cu, 271 Fe, 272 and noble metals like Au, 273 Pd, 274 Ir, 270 Ag, 275 Os, and Ru. 276 Chen and coworkers investigated the dehydrogenation of ethanol to acetaldehyde on Fe-based amorphous alloy catalysts.…”

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confidence: 99%

Synthesis and catalysis of chemically reduced metal–metalloid amorphous alloys

et al. 2012

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Amorphous alloys structurally deviate from crystalline materials in that they possess unique short-range ordered and long-range disordered atomic arrangement. They are important catalytic materials due to their unique chemical and structural properties including broadly adjustable composition, structural homogeneity, and high concentration of coordinatively unsaturated sites. As chemically reduced metal-metalloid amorphous alloys exhibit excellent catalytic performance in applications such as efficient chemical production, energy conversion, and environmental remediation, there is an intense surge in interest in using them as catalytic materials. This critical review summarizes the progress in the study of the metal-metalloid amorphous alloy catalysts, mainly in recent decades, with special focus on their synthetic strategies and catalytic applications in petrochemical, fine chemical, energy, and environmental relevant reactions. The review is intended to be a valuable resource to researchers interested in these exciting catalytic materials. We concluded the review with some perspectives on the challenges and opportunities about the future developments of metal-metalloid amorphous alloy catalysts.

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“…Some research groups [4,[6][7][8] reported that Cu(0) plays a significant role among active sites in the formation of MF. Sato et al [5] concluded that all the three copper species, Cu(0), Cu(I), Cu(II) are active, depending on the pretreatments and reaction temperatures. TPR results demonstrate that copper was fully reduced in the present catalyst.…”

Section: Methodsmentioning

confidence: 99%

Dehydrocoupling of methanol to methyl formate overa a Cu/Cr2O3 catalyst

Wang

Ruan

Han

1999

React Kinet Catal Lett

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A Cu/Cr203 catalyst was prepared by co-precipitation method, studied in methanol dehydrocoupling to methyl formate in different gas streams and characterized by BET, XRD, TPR, TPD of NH3 and CO2, etc. The results demonstrate that the catalyst can catalyze the dehydroeoupling of methanol to methyl formate in high efficiency, e.g. 99% selectivity to methyl formate at 48% conversion of methanol. The results further indicate that metallic copper might be the active species for the formation of methyl formate.

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Vapor-Phase Dehydrocoupling of Methanol to Methyl Formate over CuAl2O4

Cited by 67 publications

References 27 publications

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

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

Synthesis and catalysis of chemically reduced metal–metalloid amorphous alloys

Dehydrocoupling of methanol to methyl formate overa a Cu/Cr2O3 catalyst

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