Direct synthesis of ethanol over a Cu–Zn catalyst in the liquid phase

Simon, Michel; Mortreux, André; Petit, François

doi:10.1039/c39880001445

Cited by 5 publications

(5 citation statements)

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“…The groups of Fischer and Schüth have pioneered the application of colloidal solutions of nanoparticles (Cu and/or ZnO) as high-activity catalysts for such solution phase syn-gas to methanol processes . Simon et al reported, as early as 1988 that the reaction between Cu(acac) 2 and Et 2 Zn in the presence of 1,3-butadiene in an organic solvent formed an efficient syn-gas catalyst system with a high selectivity for ethanol and methanol formation . Corker and Evans used EXAFS to investigate the precatalyst solution.…”

Section: Introductionmentioning

confidence: 99%

“…11 Simon et al reported, as early as 1988 that the reaction between Cu(acac) 2 and Et 2 Zn in the presence of 1,3-butadiene in an organic solvent formed an efficient syn-gas catalyst system with a high selectivity for ethanol and methanol formation. 12 Corker and Evans used EXAFS to investigate the precatalyst solution. They proposed it comprised a mixture of colloidal copper and an oxozinc cluster compound (of undefined structure and stoichiometry); however, detailed characterization of the cluster and changes to the system during and after catalysis were not carried out.…”

Section: ■ Introductionmentioning

confidence: 99%

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From Organometallic Zinc and Copper Complexes to Highly Active Colloidal Catalysts for the Conversion of CO₂ to Methanol

et al. 2015

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A series of zinc oxide and copper(0) colloidal nanocatalysts, produced by a one-pot synthesis, are shown to catalyze the hydrogenation of carbon dioxide to methanol. The catalysts are produced by the reaction between diethyl zinc and bis(carboxylato/phosphinato)copper(II) precursors. The reaction leads to the formation of a precatalyst solution, characterized using various spectroscopic (NMR, UV–vis spectroscopy) and X-ray diffraction/absorption (powder XRD, EXAFS, XANES) techniques. The combined characterization methods indicate that the precatalyst solution contains copper(0) nanoparticles and a mixture of diethyl zinc and an ethyl zinc stearate cluster compound [Et4Zn5(stearate)6]. The catalysts are applied, at 523 K with a 50 bar total pressure of a 3:1 mixture of H2/CO2, in the solution phase, quasi-homogeneous, hydrogenation of carbon dioxide, and they show high activities (>55 mmol/gZnOCu/h of methanol). The postreaction catalyst solution is characterized using a range of spectroscopies, X-ray diffraction techniques, and transmission electron microscopy (TEM). These analyses show the formation of a mixture of zinc oxide nanoparticles, of size 2–7 nm and small copper nanoparticles. The catalyst composition can be easily adjusted, and the influence of the relative loadings of ZnO/Cu, the precursor complexes and the total catalyst concentration on the catalytic activity are all investigated. The optimum system, comprising a 55:45 loading of ZnO/Cu, shows equivalent activity to a commercial, activated methanol synthesis catalyst. These findings indicate that using diethyl zinc to reduce copper precursors in situ leads to catalysts with excellent activities for the production of methanol from carbon dioxide.

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Section: Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

From Organometallic Zinc and Copper Complexes to Highly Active Colloidal Catalysts for the Conversion of CO₂ to Methanol

et al. 2015

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“…Simon et al reported that Cu-Zn prepared by chemical deposition produced methanol and ethanol for liquid-phase CO hydrogenation [3]. Similarly, Matsuda et al prepared Cu-based ultrafine particles (UFP) by the liquid-phase chemical deposition and demonstrated that the catalytic activity of the Cu-Zn UFP was considerably higher than that of a coprecipitated Cu-Zn [5].…”

Section: Resultsmentioning

confidence: 98%

“…To date, much work has been done for liquid-phase CO hydrogenation; however, most of them involved Fischer-Tropsch (FT) synthesis [1,2]. Studies of the liquid-phase synthesis of alcohols [3][4][5] were relatively scarce.…”

Section: Introductionmentioning

confidence: 99%

Liquid-phase CO hydrogenation over silica-supported transition metal and Cu−Zn−Cr oxide catalysts

Ohyama

1997

React Kinet Catal Lett

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“…One example of this was the activation of [Cu(acac)2] by ZnEt2 (1 : 1),24 which forms an ethanol synthesis catalyst. 25 The adjacency of these two metals in the periodic table allows the fates of both to be followed readily by XAS. The copper was found to form locally ordered fcc colloidal particles.…”

Section: Spectroscopic Characterisation Of Homogeneous Transition Met...mentioning

confidence: 99%

Tilden lecture: shining light on metal catalysts

Evans¹

1997

Chem. Soc. Rev.

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Direct synthesis of ethanol over a Cu–Zn catalyst in the liquid phase

Cited by 5 publications

References 3 publications

From Organometallic Zinc and Copper Complexes to Highly Active Colloidal Catalysts for the Conversion of CO₂ to Methanol

From Organometallic Zinc and Copper Complexes to Highly Active Colloidal Catalysts for the Conversion of CO₂ to Methanol

Liquid-phase CO hydrogenation over silica-supported transition metal and Cu−Zn−Cr oxide catalysts

Tilden lecture: shining light on metal catalysts

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Direct synthesis of ethanol over a Cu–Zn catalyst in the liquid phase

Cited by 5 publications

References 3 publications

From Organometallic Zinc and Copper Complexes to Highly Active Colloidal Catalysts for the Conversion of CO2 to Methanol

From Organometallic Zinc and Copper Complexes to Highly Active Colloidal Catalysts for the Conversion of CO2 to Methanol

Liquid-phase CO hydrogenation over silica-supported transition metal and Cu−Zn−Cr oxide catalysts

Tilden lecture: shining light on metal catalysts

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Product

Resources

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From Organometallic Zinc and Copper Complexes to Highly Active Colloidal Catalysts for the Conversion of CO₂ to Methanol

From Organometallic Zinc and Copper Complexes to Highly Active Colloidal Catalysts for the Conversion of CO₂ to Methanol