State of copper-containing catalyst for methanol synthesis in the reaction medium

Yurieva, T. M.; Plyasova, L. M.; Kriger, T. A.; Зайковский, В. И.; Макарова, О. В.; Minyukova, T. P.

doi:10.1007/bf02069096

Cited by 24 publications

(12 citation statements)

References 6 publications

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“…It remains to be explained how the ZnO structure is stabilized when Cu is removed from solid solution by the reduction process. In catalytic systems consisting of Cu/ZnO, CuCr 2 O 4 and CuAl 2 O 4 spinels, it has been suggested that the sites vacated by Cu are occupied by protons forming OH groups, stabilizing the oxide structure (Yurieva et al, 1995;Plyasova, Solovyeva et al, 2000). None of the experimental techniques applied in the present study can differentiate a vacant site in ZnO from a site occupied by a proton, but we note that Plyasova, Solovyeva et al (2000) confirmed by neutron diffraction such a mechanism of Cu vacated sites, stabilized by protons in reduced CuAl 2 O 4 and in reduced CuCr 2 O 4 spinels (Plyasova et al, 1996).…”

Section: Volume Fractionmentioning

confidence: 99%

“…There appears to be wide agreement that the oxide catalyst formed by calcining coprecipitated (Cu,Zn)hydroxycarbonates contains ZnO with Cu in solid solution, and that Cu migrates to the ZnO surface during the reduction process, forming dispersed structures with particularly high catalytic activity (Ketchik et al, 1982;Yurieva et al, 1993Yurieva et al, , 1995Stirling et al, 1993;Plyasova, 1996;Poels & Brands, 2000). Stirling et al (1993) found that a maximum of about 1 mol% CuO can dissolve in ZnO, but they calcined the studied catalysts at very high temperatures, 1053-1173 K, whereas Ketchik et al (1982) showed that ZnO in catalysts calcined at 623 K may contain up to 10 mol% CuO in solid solution.…”

Section: Introductionmentioning

confidence: 98%

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Activation of a Cu/ZnO catalyst for methanol synthesis

Andreasen¹,

Rasmussen

Helveg

et al. 2006

J Appl Cryst

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SynopsisIn situ resonant X-ray diffraction, in situ resonant small angle X-ray scattering and in situ electron energy loss spectroscopy have been applied to the study of nano-scale and crystalline structure during activation of a Cu/ZnO catalyst for methanol synthesis. AbstractThe structural changes during activation by temperature programmed reduction of a Cu/ZnO catalyst for methanol synthesis has been studied by several in situ techniques.

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Section: Volume Fractionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 98%

Activation of a Cu/ZnO catalyst for methanol synthesis

Andreasen¹,

Rasmussen

Helveg

et al. 2006

J Appl Cryst

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“…Then, the boundary value of precursor pressure for the formation of copper phase is determined by the equality of these two fluxes = at a maximum pressure of copper dimer vapors. The equation describing the variations of copper vapor pressure can be written as (13) i.e., the pressure of copper vapors in a reactor is determined by the rates of precursor decomposition, nucleation of copper vapors, and vapor condensation on the surface of growing particles.…”

Section: 4-pentanedione Acetonementioning

confidence: 99%

“…The production of copper and copper oxides in an ultradispersed form is also of importance due to their wide use in versatile chemical processes as catalysts with a large surface area, for example, in the water-gas shift reaction [8], dehydrogenation reaction of butanol [9] and oxidation of carbon monoxide [10,11]. Copper-based catalysts are used in commercial synthesis of methanol [8,[12][13][14], which is considered as an ecologically pure fuel for power industry. For example, twenty-two various fields based on the use of the catalytic properties of copper oxides are listed in Samsonov's reference book on oxide application [15].…”

Section: Introductionmentioning

confidence: 99%

Synthesis of nanoparticles using vapor-phase decomposition of copper(II) acetylacetonate

Nasibulin¹,

Shurygina

Kauppinen³

2005

Colloid J

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Experimental data on the synthesis of crystalline Cu, Cu 2 O, and CuO nanoparticles obtained earlier by the vapor-phase decomposition of copper(II) acetylacetonate (Cu(acac) 2 ) were systematized and generalized. Studies were performed using a laminar flow reactor at atmospheric pressure within the ranges of precursor partial vapor pressure P prec = 0.06-44 Pa and reactor temperature from 432 to 1216 ° C. The decomposition of Cu(acac) 2 was studied in an inert nitrogen atmosphere and in the presence of various reagents (water vapors, H 2 , O 2 , and CO). The composition of synthesized particles varied from pure copper to its oxides (Cu 2 O and CuO) depending on experimental conditions and used reagents. A semi-empirical kinetic model was proposed for describing the product dynamics. The hypothesis on the predominant role of copper dimers in a particle's growth was stated. It was established that the composition of products is determined by the surface reactions on growing particles and is dependent on the ratio between the concentrations of the gaseous reagents. Calculated phase diagrams of the products of Cu(acac) 2 decomposition in the presence of various reagents were in good agreement with experimental data. The proposed method of construction of the phase diagram of decomposition products can be employed for other systems. It was established that, upon the Cu(acac) 2 decomposition in the presence of CO, carbon nano-onions were formed in addition to copper nanoparticles.

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“…The data of refs [10,11] also give ground to suppose that the reduction of copper cations from the a.m.-ZnO solid solution is reversible: the epitaxial Cu 0 particles are easily re-oxidizable and can return back to the a.m.-ZnO structure under the action of low partial pressures of oxygen. Meanwhile, the air treatment transforms the epitaxial Cu 0 particles to the CuO phase.…”

Section: Introductionmentioning

confidence: 99%

Evolution of the Cu/ZnO methanol synthesis catalyst during its reduction and re-oxidation

Pelipenko

Kochubey

Khassin

et al. 2005

React Kinet Catal Lett

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Cu K EXAFS studies of the structure of Cu-Zn oxide catalyst were performed for the as prepared samples, those after its activation by hydrogen and after its subsequent re-oxidation. It was found that during the primary formation of the CuZnO solid solution, the copper ions are dissolved in the extended stacking faults of the ZnO lattice as ultra-small oxide clusters. Activation by hydrogen at 473 K leads to the reduction of most copper cations to Cu 0 with the formation of nanoparticles with the characteristic size of ca. 1.6 nm. The copper metal particles were re-oxidized to Cu 2+ at 523 K in a helium flow containing 0.05 vol. % oxygen. The re-oxidized cations do not form a CuO phase. Instead, they return to the extended stacking faults of ZnO. However, this time they form stripe-like clusters of square-planar coordinated copper cations.

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State of copper-containing catalyst for methanol synthesis in the reaction medium

Cited by 24 publications

References 6 publications

Activation of a Cu/ZnO catalyst for methanol synthesis

Activation of a Cu/ZnO catalyst for methanol synthesis

Synthesis of nanoparticles using vapor-phase decomposition of copper(II) acetylacetonate

Evolution of the Cu/ZnO methanol synthesis catalyst during its reduction and re-oxidation

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