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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
From organometallic zinc and copper complexes to highly active colloidal catalysts for the conversion of CO2 to methanol
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
2155-5435
2895-2902
Brown, Neil J.
0082266a-cc1e-4f87-9226-5f86ea13e891
García-Trenco, Andrés
864c34d4-113c-4cea-9c7a-8dac809cde2d
Weiner, Jonathan
92e8cf6d-8bac-433f-9697-8c2aa968523f
White, Edward R.
f1d77cd3-415a-4b7c-98e9-5a3a042af4d4
Allinson, Matthew
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Chen, Yuxin
10ed4d6c-5aa7-4a27-bf06-71b127c04a09
Wells, Peter
bc4fdc2d-a490-41bf-86cc-400edecf2266
Gibson, Emma K.
738c74e4-ab68-42fe-bda8-9d4a43669b31
Hellgardt, Klaus
257fac2a-4848-44bf-b62b-4a1872f7f8f9
Shaffer, Milo S.P.
f2e7a6d0-2b70-4b2c-bbd2-35e9e11b1ed3
Williams, Charlotte K.
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Brown, Neil J.
0082266a-cc1e-4f87-9226-5f86ea13e891
García-Trenco, Andrés
864c34d4-113c-4cea-9c7a-8dac809cde2d
Weiner, Jonathan
92e8cf6d-8bac-433f-9697-8c2aa968523f
White, Edward R.
f1d77cd3-415a-4b7c-98e9-5a3a042af4d4
Allinson, Matthew
d116814c-c518-45bc-97c3-23a3749752d2
Chen, Yuxin
10ed4d6c-5aa7-4a27-bf06-71b127c04a09
Wells, Peter
bc4fdc2d-a490-41bf-86cc-400edecf2266
Gibson, Emma K.
738c74e4-ab68-42fe-bda8-9d4a43669b31
Hellgardt, Klaus
257fac2a-4848-44bf-b62b-4a1872f7f8f9
Shaffer, Milo S.P.
f2e7a6d0-2b70-4b2c-bbd2-35e9e11b1ed3
Williams, Charlotte K.
3d8bf103-1f37-49e9-bb9f-76c547de6a35

Brown, Neil J., García-Trenco, Andrés, Weiner, Jonathan, White, Edward R., Allinson, Matthew, Chen, Yuxin, Wells, Peter, Gibson, Emma K., Hellgardt, Klaus, Shaffer, Milo S.P. and Williams, Charlotte K. (2015) From organometallic zinc and copper complexes to highly active colloidal catalysts for the conversion of CO2 to methanol. ACS Catalysis, 5 (5), 2895-2902. (doi:10.1021/cs502038y).

Record type: Article

Abstract

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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Accepted/In Press date: 17 February 2015
Published date: 3 April 2015
Organisations: Organic Chemistry: SCF

Identifiers

Local EPrints ID: 400552
URI: https://eprints.soton.ac.uk/id/eprint/400552
ISSN: 2155-5435
PURE UUID: 019e25f9-66c7-4336-aee0-ed9a7b18547a
ORCID for Peter Wells: ORCID iD orcid.org/0000-0002-0859-9172

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Date deposited: 19 Sep 2016 10:32
Last modified: 15 Aug 2019 00:43

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Contributors

Author: Neil J. Brown
Author: Andrés García-Trenco
Author: Jonathan Weiner
Author: Edward R. White
Author: Matthew Allinson
Author: Yuxin Chen
Author: Peter Wells ORCID iD
Author: Emma K. Gibson
Author: Klaus Hellgardt
Author: Milo S.P. Shaffer
Author: Charlotte K. Williams

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