Tuning the catalytic activity of the heteronuclear coordination polymers [CoxZn1−x(tdc)(bipy)] and [CoxZn1−x(Me2trz–pba)2] in the epoxidation of cyclooctene via isomorphous substitution

Worch, Christian; Kettner, Florian; Lässig, Daniel; Lincke, Jörg; Krautscheid, Harald; Gläser, Roger

doi:10.1016/j.catcom.2013.08.012

Cited by 11 publications

(4 citation statements)

References 22 publications

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“…For instance, the cyclooctene conversion over a sample with x = 0.25 amounts to 22% after 24 h. This proves that the catalytic activity depends on the degree of Co 2+ -substitution while the crystal structure of the catalyst remains unchanged. Details on the catalytic studies including Co 2+ substitution are reported in an upcoming work …”

Section: Resultsmentioning

confidence: 99%

Synthesis, Crystal Structure and Catalytic Behavior of Homo- and Heteronuclear Coordination Polymers [M(tdc)(bpy)] (M²⁺ = Fe²⁺, Co²⁺, Zn²⁺, Cd²⁺; tdc^2– = 2,5-thiophenedicarboxylate)

et al. 2013

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A series of isostructural 3D coordination polymers (3)∞[M(tdc)(bpy)] (M(2+) = Zn(2+), Cd(2+), Co(2+), Fe(2+); tdc(2-) = 2,5-thiophenedicarboxylate; bpy = 4,4'-bipyridine) was synthesized and characterized by X-ray diffraction, thermal analysis, and gas adsorption measurements. The materials show high thermal stability up to approximately 400 °C and a solvent induced phase transition. Single crystal X-ray structure determination was successfully performed for all compounds after the phase transition. In the zinc-based coordination polymer, various amounts of a second type of metal ions such as Co(2+) or Fe(2+) could be incorporated. Furthermore, the catalytic behavior of the homo- and heteronuclear 3D coordination polymers in an oxidation model reaction was investigated.

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Section: Resultsmentioning

confidence: 99%

Synthesis, Crystal Structure and Catalytic Behavior of Homo- and Heteronuclear Coordination Polymers [M(tdc)(bpy)] (M²⁺ = Fe²⁺, Co²⁺, Zn²⁺, Cd²⁺; tdc^2– = 2,5-thiophenedicarboxylate)

et al. 2013

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“…Later, a series of isostructural, heteronuclear MOFs possessing Co 2+ and Zn 2+ ions within [Co x Zn 1−x (tdc)(bipy)] was reported as a heterogeneous catalyst for the epoxidation of cyclooctene with TBHP at 75 • C [52]. Catalytic experiments have shown that the conversion of cyclooctene gradually increases in respect to Co-content in the MOF solid; thus, Zn-free MOF exhibited the highest conversion, while the Co-free MOF showed poor activity.…”

Section: Olefin Oxidationmentioning

confidence: 99%

Cobalt-Based Metal Organic Frameworks as Solids Catalysts for Oxidation Reactions

et al. 2021

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Metal organic frameworks (MOFs) are porous crystalline solids whose frameworks are constituted by metal ions/nodes with rigid organic linkers leading to the formation of materials having high surface area and pore volume. One of the unique features of MOFs is the presence of coordinatively unsaturated metal sites in their crystalline lattice that can act as Lewis acid sites promoting organic transformations, including aerobic oxidation reactions of various substrates such as hydrocarbons, alcohols, and sulfides. This review article summarizes the existing Co-based MOFs for oxidation reactions organized according to the nature of substrates like hydrocarbon, alcohol, olefin, and water. Both aerobic conditions and peroxide oxidants are discussed. Emphasis is placed on comparing the advantages of using MOFs as solid catalysts with respect to homogeneous salts in terms of product selectivity and long-term stability. The final section provides our view on future developments in this field.

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“…The influence of different functional groups within the triazolyl isophthalate linker on the gas sorption properties was already observed recently with a related series of MOFs based on the paddle wheel motif [ 48 ]. In addition, triazole-based MOFs were shown to be active catalysts in the selective oxidation of cyclooctene and cyclohexene with TBHP [ 36 , 50 , 51 ]. Accordingly, the selective oxidation of cyclohexene with TBHP in the liquid phase was chosen as a test reaction in the present work to investigate the influence of the triazole substituents on the catalytic activity of the MOFs.…”

Section: Introductionmentioning

confidence: 99%

A Series of Robust Copper-Based Triazolyl Isophthalate MOFs: Impact of Linker Functionalization on Gas Sorption and Catalytic Activity †

et al. 2017

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The synthesis and characterization of an isomorphous series of copper-containing microporous metal-organic frameworks (MOFs) based on triazolyl isophthalate linkers with the general formula ∞3[Cu4(μ3-OH)2(R1-R2-trz-ia)3(H2O)x] are presented. Through size adjustment of the alkyl substituents R1 and/or R2 at the linker, the impact of linker functionalization on structure-property relationships was studied. Due to the arrangement of the substituents towards the cavities, the porosity (pore fraction 28%–39%), as well as the pore size can be adjusted by the size of the substituents of the triazole ring. Thermal analysis and temperature-dependent PXRD studies reveal a thermal stability of the MOFs up to 230 °C due to increasing framework stability through fine-tuning of the linker substitution pattern. Adsorption of CO2 (298 K) shows a decreasing maximum loading with increasing steric demand of the substituents of the triazole ring. Furthermore, the selective oxidation of cyclohexene with tert-butyl hydroperoxide (TBHP) is studied over the MOFs at 323 K in liquid chloroform. The catalytic activity increases with the steric demand of the substituents. Additionally, these isomorphous MOFs exhibit considerable robustness under oxidizing conditions confirmed by CO2 adsorption studies, as well as by the catalytic selective oxidation experiments.

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Tuning the catalytic activity of the heteronuclear coordination polymers [CoxZn1−x(tdc)(bipy)] and [CoxZn1−x(Me2trz–pba)2] in the epoxidation of cyclooctene via isomorphous substitution

Cited by 11 publications

References 22 publications

Synthesis, Crystal Structure and Catalytic Behavior of Homo- and Heteronuclear Coordination Polymers [M(tdc)(bpy)] (M²⁺ = Fe²⁺, Co²⁺, Zn²⁺, Cd²⁺; tdc^2– = 2,5-thiophenedicarboxylate)

Synthesis, Crystal Structure and Catalytic Behavior of Homo- and Heteronuclear Coordination Polymers [M(tdc)(bpy)] (M²⁺ = Fe²⁺, Co²⁺, Zn²⁺, Cd²⁺; tdc^2– = 2,5-thiophenedicarboxylate)

Cobalt-Based Metal Organic Frameworks as Solids Catalysts for Oxidation Reactions

A Series of Robust Copper-Based Triazolyl Isophthalate MOFs: Impact of Linker Functionalization on Gas Sorption and Catalytic Activity †

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Tuning the catalytic activity of the heteronuclear coordination polymers [CoxZn1−x(tdc)(bipy)] and [CoxZn1−x(Me2trz–pba)2] in the epoxidation of cyclooctene via isomorphous substitution

Cited by 11 publications

References 22 publications

Synthesis, Crystal Structure and Catalytic Behavior of Homo- and Heteronuclear Coordination Polymers [M(tdc)(bpy)] (M2+ = Fe2+, Co2+, Zn2+, Cd2+; tdc2– = 2,5-thiophenedicarboxylate)

Synthesis, Crystal Structure and Catalytic Behavior of Homo- and Heteronuclear Coordination Polymers [M(tdc)(bpy)] (M2+ = Fe2+, Co2+, Zn2+, Cd2+; tdc2– = 2,5-thiophenedicarboxylate)

Cobalt-Based Metal Organic Frameworks as Solids Catalysts for Oxidation Reactions

A Series of Robust Copper-Based Triazolyl Isophthalate MOFs: Impact of Linker Functionalization on Gas Sorption and Catalytic Activity †

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Synthesis, Crystal Structure and Catalytic Behavior of Homo- and Heteronuclear Coordination Polymers [M(tdc)(bpy)] (M²⁺ = Fe²⁺, Co²⁺, Zn²⁺, Cd²⁺; tdc^2– = 2,5-thiophenedicarboxylate)

Synthesis, Crystal Structure and Catalytic Behavior of Homo- and Heteronuclear Coordination Polymers [M(tdc)(bpy)] (M²⁺ = Fe²⁺, Co²⁺, Zn²⁺, Cd²⁺; tdc^2– = 2,5-thiophenedicarboxylate)