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Cu/M:ZnO (M = Mg, Al, Cu) colloidal nanocatalysts for the solution hydrogenation of carbon dioxide to methanol

Leung, AHM; Garcia-Trenco, A; Phanopoulos, A; Regoutz, A; Schuster, ME; Pike, SD; Shaffer, MSP; (2020) Cu/M:ZnO (M = Mg, Al, Cu) colloidal nanocatalysts for the solution hydrogenation of carbon dioxide to methanol. Journal of Materials Chemistry A , 8 (22) pp. 11282-11291. 10.1039/d0ta00509f. Green open access

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Abstract

Doped-ZnO nanoparticles, capped with dioctylphosphinate ligands, are synthesised by the controlled hydrolysis of a mixture of organometallic precursors. Substitutional doping of the wurtzite ZnO nanoparticles with 5 mol% Mg(II), Al(III) and Cu(I) is achieved by the addition of sub-stoichiometric amounts of the appropriate dopant [(n-butyl)(sec-butyl)magnesium, triethylaluminium or mesitylcopper] to diethylzinc in the precursor mixture. After hydrolysis, the resulting colloidal nanoparticles (sizes of 2–3 nm) are characterised by powder X-ray crystallography, transmission electron microscopy, inductively-coupled plasma optical emission spectrometry and X-ray photoelectron spectroscopy. A solution of the doped-ZnO nanoparticles and colloidal Cu(0) nanoparticles [M:ZnO : Cu = 1 : 1] are applied as catalysts for the hydrogenation of CO2 to methanol in a liquid-phase continuous flow stirred tank reactor [210 °C, 50 bar, CO2 : H2 = 1 : 3, 150 mL min−1, mesitylene, 20 h]. All the catalyst systems display higher rates of methanol production and better stability than a benchmark heterogeneous catalyst, Cu–ZnO–Al2O3 [480 μmol mmolmetal−1 h−1], with approximately twice the activity for the Al(III)-doped nanocatalyst. Despite outperforming the benchmark catalyst, Mg(II) doping is detrimental towards methanol production in comparison to undoped ZnO. X-Ray photoelectron spectroscopy and transmission electron microscopy analysis of the most active post-catalysis samples implicate the migration of Al(III) to the catalyst surface, and this surface enrichment is proposed to facilitate stabilisation of the catalytic ZnO/Cu interfaces.

Type: Article
Title: Cu/M:ZnO (M = Mg, Al, Cu) colloidal nanocatalysts for the solution hydrogenation of carbon dioxide to methanol
Open access status: An open access version is available from UCL Discovery
DOI: 10.1039/d0ta00509f
Publisher version: https://doi.org/10.1039/d0ta00509f
Language: English
Additional information: This version is the author accepted manuscript. For information on re-use, please refer to the publisher’s terms and conditions.
Keywords: Science & Technology, Physical Sciences, Technology, Chemistry, Physical, Energy & Fuels, Materials Science, Multidisciplinary, Chemistry, Materials Science, ZINC-OXIDE NANOPARTICLES, COPPER-BASED CATALYSTS, LIQUID-PHASE METHANOL, ZNO THIN-FILMS, ACTIVE-SITE, ORGANOMETALLIC PRECURSORS, ADMITTANCE SPECTROSCOPY, CO2 HYDROGENATION, CU/ZNO CATALYSTS, SHAPE-CONTROL
UCL classification: UCL
UCL > Provost and Vice Provost Offices > UCL BEAMS
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Chemistry
URI: https://discovery.ucl.ac.uk/id/eprint/10107212
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