Oxidation states of copper during reduction of cupric oxide in methanol catalysts

Himelfarb, P.B.; Wawner, F. E.; Bieser, A.; VINES, S. N.

doi:10.1016/0021-9517(83)90072-6

Cited by 37 publications

(3 citation statements)

References 8 publications

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“…Copper oxide is of particular interest due to its use in heterogeneous catalysts for the oxidation of hydrocarbons [10], methanol [11], carbon monoxide [12] and nitric oxide [13]. CuO also has found applications within gas sensing [14][15][16] and lithium ion batteries [17,18].…”

Section: Introductionmentioning

confidence: 99%

The use of copper(II) oxide nanorod bundles for the non-enzymatic voltammetric sensing of carbohydrates and hydrogen peroxide

Batchelor‐McAuley

Wildgoose

et al. 2008

Sensors and Actuators B: Chemical

187

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Section: Introductionmentioning

confidence: 99%

The use of copper(II) oxide nanorod bundles for the non-enzymatic voltammetric sensing of carbohydrates and hydrogen peroxide

Batchelor‐McAuley

Wildgoose

et al. 2008

Sensors and Actuators B: Chemical

187

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“…Temperature-programmed reaction, reduction and/or desorption methods were also used extensively to see into the adsorption/desorption/reaction of hydrogen, one of the principle required reactants in methanol synthesis, and the manner in which the active catalyst was formed via reduction using the same gas. − Here we will consider but two of the several such studies that were reported in the 1980s. , These studies revolved around either the uptake of hydrogen during reduction or its subsequent desorption from the reduced catalysts. Furthermore, in both of these studies, a wide range of CZA compositions were investigated, and attempts were made to correlate these uptake/desorption measurements with measurements of catalytic reactivity from mixtures of CO/H 2 or H 2 /CO 2 feeds .…”

Section: –1989mentioning

confidence: 99%

The Enigma of Methanol Synthesis by Cu/ZnO/Al₂O₃-Based Catalysts

Beck,

Newton,

van de Water

et al. 2024

Chem. Rev.

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The activity and durability of the Cu/ZnO/Al 2 O 3 (CZA) catalyst formulation for methanol synthesis from CO/CO 2 /H 2 feeds far exceed the sum of its individual components. As such, this ternary catalytic system is a prime example of synergy in catalysis, one that has been employed for the large scale commercial production of methanol since its inception in the mid 1960s with precious little alteration to its original formulation. Methanol is a key building block of the chemical industry. It is also an attractive energy storage molecule, which can also be produced from CO 2 and H 2 alone, making efficient use of sequestered CO 2 . As such, this somewhat unusual catalyst formulation has an enormous role to play in the modern chemical industry and the world of global economics, to which the correspondingly voluminous and ongoing research, which began in the 1920s, attests. Yet, despite this commercial success, and while research aimed at understanding how this formulation functions has continued throughout the decades, a comprehensive and universally agreed upon understanding of how this material achieves what it does has yet to be realized. After nigh on a century of research into CZA catalysts, the purpose of this Review is to appraise what has been achieved to date, and to show how, and how far, the field has evolved. To do so, this Review evaluates the research regarding this catalyst formulation in a chronological order and critically assesses the validity and novelty of various hypotheses and claims that have been made over the years. Ultimately, the Review attempts to derive a holistic summary of what the current body of literature tells us about the fundamental sources of the synergies at work within the CZA catalyst and, from this, suggest ways in which the field may yet be further advanced.

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“…The presence of gaseous CO^ was found to retard the reduction of CU2O to metallic copper. Binary ZnO-CuO catalysts also formed an inter mediate CUgO phase during reduction (Himelfarb et al, 1983). The reduction rate was dependent on CuO crystallite size and CuO dispersion in these mixed metal oxides.…”

Section: Recently Binary and Ternary Methanol Catalysts Have Been Extmentioning

confidence: 98%

In situ characterization of adsorbed species on methanol synthesis catalysts by FT-IR spectroscopy

Edwards¹

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Catalyst Characterization X-Ray diffraction X-Ray photoelectron and Auger electron spectroscopies Surface area and micropore distribution RESULTS OF CATALYST CHARACTERIZATION Cation Composition of the Binary Oxides X-Ray Powder Diffraction Guinier X-Ray 32 Surface Oxidation States 35 Surface Area and Micropore Distribution 44 DISCUSSION OF RESULTS 48 PART II. CHEMISORPTION ON METHANOL SYNTHESIS CATALYSTS 52 LITERATURE REVIEW 53 Adsorption on Zinc Oxide 53 Adsorption on Copper and Copper Oxide 61 iii Adsorption on Alumina and Chromia 65 Adsorption on Mixed Metal Oxides 67 Fourier Transform Infrared Spectroscopy 68 EXPERIMENTAL APPARATUS AND METHODS 70 Fourier Transform Infrared Spectrometer 70 Infrared Photoacoustic Spectroscopy 72 Sample Preparation for Transmission Infrared Studies 74 RESULTS OF ATMOSPHERIC ADSORPTION 76 Adsorption on Zinc Oxide 76 Adsorption on Binary Oxides 86 Adsorption on Ternary Oxides 145 Photoacoustic Spectra 175 DISCUSSION OF RESULTS 187 PART III. IN SITU CHARACTERIZATION OF METHANOL SYNTHESIS CATALYSTS LITERATURE REVIEW Thermodynamics Kinetics Reaction Mechanisms High Pressure Spectroscopic Cells EXPERIMENTAL APPARATUS AND METHODS Reactor System High pressure section Atmospheric section Vacuum section High Pressure Infrared Cell 232 Gas Chromatography 235 iv Safety Considerations 239 RESULTS OF ÇN SITU CHARACTERIZATION 241 Catalytic Reactivity Binary catalysts Ternary catalysts Infrared Spectra at High Pressure Gaseous carbon monoxide Species on zinc oxide Species on binary catalysts Species on ternary catalysts. 266 DISCUSSION OF RESULTS 279

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Oxidation states of copper during reduction of cupric oxide in methanol catalysts

Cited by 37 publications

References 8 publications

The use of copper(II) oxide nanorod bundles for the non-enzymatic voltammetric sensing of carbohydrates and hydrogen peroxide

The use of copper(II) oxide nanorod bundles for the non-enzymatic voltammetric sensing of carbohydrates and hydrogen peroxide

The Enigma of Methanol Synthesis by Cu/ZnO/Al₂O₃-Based Catalysts

In situ characterization of adsorbed species on methanol synthesis catalysts by FT-IR spectroscopy

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Oxidation states of copper during reduction of cupric oxide in methanol catalysts

Cited by 37 publications

References 8 publications

The use of copper(II) oxide nanorod bundles for the non-enzymatic voltammetric sensing of carbohydrates and hydrogen peroxide

The use of copper(II) oxide nanorod bundles for the non-enzymatic voltammetric sensing of carbohydrates and hydrogen peroxide

The Enigma of Methanol Synthesis by Cu/ZnO/Al2O3-Based Catalysts

In situ characterization of adsorbed species on methanol synthesis catalysts by FT-IR spectroscopy

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The Enigma of Methanol Synthesis by Cu/ZnO/Al₂O₃-Based Catalysts