Direct synthesis of acetic acid by simultaneous co-activation of methane and CO2 over Cu-exchanged ZSM-5 catalysts

Rabie, Abdelrahman M.; Betiha, Mohamed A.; Park, Sang-Eon

doi:10.1016/j.apcatb.2017.05.053

Cited by 91 publications

(48 citation statements)

References 38 publications

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“…They also examined other possible dopants, such as Al, Ga, Cd, In, and Ni, and found a positive correlation between the activation barrier of C−C coupling and the electronegativity of the dopant. In addition, carboxylation reactions of methane and other simple alkanes with CO 2 have also been reported …”

Section: Carboxylation Of C(sp3)−h Bonds With Co2mentioning

confidence: 99%

C−H Bond Carboxylation with Carbon Dioxide

et al. 2019

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Carbon dioxide is a nontoxic, renewable, and abundant C1 source, whereas C−H bond functionalization represents one of the most important approaches to the construction of carbon–carbon bonds and carbon–heteroatom bonds in an atom‐ and step‐economical manner. Combining the chemical transformation of CO2 with C−H bond functionalization is of great importance in the synthesis of carboxylic acids and their derivatives. The contents of this Review are organized according to the type of C−H bond involved in carboxylation. The primary types of C−H bonds are as follows: C(sp)−H bonds of terminal alkynes, C(sp2)−H bonds of (hetero)arenes, vinylic C(sp2)−H bonds, the ipso‐C(sp2)−H bonds of the diazo group, aldehyde C(sp2)−H bonds, α‐C(sp3)−H bonds of the carbonyl group, γ‐C(sp3)−H bonds of the carbonyl group, C(sp3)−H bonds adjacent to nitrogen atoms, C(sp3)−H bonds of o‐alkyl phenyl ketones, allylic C(sp3)−H bonds, C(sp3)−H bonds of methane, and C(sp3)−H bonds of halogenated aliphatic hydrocarbons. In addition, multicomponent reactions, tandem reactions, and key theoretical studies related to the carboxylation of C−H bonds are briefly summarized. Transition‐metal‐free, organocatalytic, electrochemical, and light‐driven methods are highlighted.

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Section: Carboxylation Of C(sp3)−h Bonds With Co2mentioning

confidence: 99%

C−H Bond Carboxylation with Carbon Dioxide

et al. 2019

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“…Figure 8 depicts two well‐defined peaks at 932.5 and 952 eV for both the samples; that is, HCu(0.2 M)NZ and HCu(0.5 M)NZ could be assigned to Cu2p 3/2 and Cu2p 1/2 , respectively. A satellite peak is observed for the HCu(0.5 M)NZ at binding energy of 941–946 eV indicating that the copper ions are in bivalent form or it indicates the formation of CuO 64,65 . The satellite peaks have originated by the electron transfer from ligand's orbital to 3D orbital of copper.…”

Section: Resultsmentioning

confidence: 99%

Effect of copper on textural and acidic properties of hierarchical nanocrystalline ZSM‐5

P¹,

Kumari²,

Aneesh³

2020

Asia-Pacific J Chem Eng

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In this work, hierarchically porous nanocrystalline ZSM-5 was synthesized hydrothermally. Different concentrations of copper were incorporated into the matrix by ion exchange method. The synthesized samples were characterized by means of X-ray diffraction (XRD), Fourier-transform infrared (FTIR), energydispersive X-ray spectroscopy, scanning electron microscopy, X-ray photoelectron spectroscopy (XPS), ultraviolet (UV), 27 Al magic angle spinning nuclear magnetic resonance spectroscopy, and nitrogen sorption analysis. The acid sites on the surface of Cu-ZSM-5 have been systematically investigated using temperature-programmed desorption of ammonia (NH 3-TPD) and pyridine sorption followed by FTIR. The diffraction pattern obtained from XRD studies confirmed the typical Mobil Five. NH 3-TPD reveals the enhancement of acidity achieved by copper. The FTIR spectra of pyridine desorbed samples show that the intensity of bands corresponding to Lewis acidity increases by modification. The ZSM-5 zeolite samples exhibit spherical-shaped MFI crystal structure. The UV spectrum indicates that copper has been doped in the form of cations or in the form of oxides. XPS analysis confirms that the copper exists as Cu(I) and Cu(II). The nitrogen sorption isotherms reveal that the modified samples are mesoporous in nature. The pore volume and diameter were found to be enhanced by the modification. The better textural properties and acidic properties of the Cu-ZSM-5 can make it suitable for catalyzing organic reactions. K E Y W O R D S acidic and textural properties, copper, hierarchical nanocrystalline ZSM-5, ion exchange

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“…In a very recent article Park et al. reported the synthesis of acetic acid by simultaneous co‐activation of CH 4 and CO 2 over Cu‐loaded Li/Na/K/Ca‐ZSM‐5 materials in a micro‐reactor at 425–525 °C with slow feeding of these gas mixtures. Here the Cu NPs facilitates the C−H activation, whereas the alkali and alkaline earth metal sites promote the activation of CO 2 molecules so that the C−C bond formation reaction occurs, leading to the selective formation of CH 3 CO 2 H. Chen et al.…”

Section: Catalytic Sites and Mechanistic Aspects Of Co2 Fixation Reacmentioning

confidence: 99%

“…Zn-doped ceriaw as found to be av ery efficient catalyst in activating the CÀHb ond of methanei nt he presence of CO 2 to form the CÀCc ouplingp roduct acetic acid. [206] Here the Zn sites stabilized the ÀCH 3 moiety through the formationo fa ZnÀCb ond, whereas ceria activated the CO 2 molecules and thus CÀCc oupling proceeded smoothly.I nav ery recent article Park et al reported the synthesis of acetic acid by simultaneous co-activation of CH 4 and CO 2 over Cu-loaded Li/Na/K/Ca-ZSM-5 materials [207] in am icro-reactor at 425-525 8Cw ith slow feeding of these gas mixtures. Here the Cu NPs facilitates the CÀHa ctivation, whereas the alkali anda lkaline earth metal sites promote the activation of CO 2 molecules so that the CÀC bond formation reactionoccurs, leading to the selectiveformation of CH 3 CO 2 H. Chen et al have also reportedt he synthesis of ethanol (C 2 H 5 OH)bypassing CO 2 into an aqueous dispersion of bimetallico xysulfides of Cu/Ni, Cu/Co,a nd Cu/Sn as heterogeneous catalyst under ambient conditions.…”

Section: Catalytic Sites and Mechanistic Aspects Of Co 2 Fixation Reamentioning

confidence: 99%

Supported Porous Nanomaterials as Efficient Heterogeneous Catalysts for CO₂ Fixation Reactions

Bhanja

Modak

Bhaumik

2018

Chemistry A European J

108

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CO is a major greenhouse gas responsible for global warming and can act as an abundant and inexpensive C1 source for enhancing the chain length/functionalization of a wide range of reactive organic molecules. It is moderately reactive, nontoxic and renewable. Thus, CO fixation reactions are important to meet the global challenges, that is, to mitigate the concentration of CO in the atmosphere through its fruitful utilization, which is of great interest from economic and environmental perspectives. Various metallic nanoparticles as well as metal oxides can be supported over high surface area porous materials and the resulting nanomaterial can act as heterogeneous and reusable solid catalyst for CO fixation reactions for the synthesis of a large number of fuels, natural products agrochemicals, and pharmaceutical compounds. Here we present an overview of the recent progress as well as promising future of metal/metal oxide nanoparticles supported over porous nanomaterials as heterogeneous catalysts for a wide spectrum of these CO fixation reactions.

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Direct synthesis of acetic acid by simultaneous co-activation of methane and CO2 over Cu-exchanged ZSM-5 catalysts

Cited by 91 publications

References 38 publications

C−H Bond Carboxylation with Carbon Dioxide

C−H Bond Carboxylation with Carbon Dioxide

Effect of copper on textural and acidic properties of hierarchical nanocrystalline ZSM‐5

Supported Porous Nanomaterials as Efficient Heterogeneous Catalysts for CO₂ Fixation Reactions

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Direct synthesis of acetic acid by simultaneous co-activation of methane and CO2 over Cu-exchanged ZSM-5 catalysts

Cited by 91 publications

References 38 publications

C−H Bond Carboxylation with Carbon Dioxide

C−H Bond Carboxylation with Carbon Dioxide

Effect of copper on textural and acidic properties of hierarchical nanocrystalline ZSM‐5

Supported Porous Nanomaterials as Efficient Heterogeneous Catalysts for CO2 Fixation Reactions

Contact Info

Product

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Supported Porous Nanomaterials as Efficient Heterogeneous Catalysts for CO₂ Fixation Reactions