Issue 17, 2017

Colloidal Cu/ZnO catalysts for the hydrogenation of carbon dioxide to methanol: investigating catalyst preparation and ligand effects

Abstract

The production of methanol from CO2 hydrogenation is a promising potential route to a renewable liquid fuel and renewable energy vector. Herein, three distinct routes to make colloidal catalysts based on mixtures of Cu(0) and ZnO nanoparticles (NPs) and using low-temperature organometallic procedures are reported. The colloids are surface coordinated by a phosphinate ligand: dioctylphosphinate ([DOPA]), which delivers a high solubility in organic solvents. Further, the synthetic routes allow fine control of the ZnO:Cu and ligand loadings. The catalysts are prepared by mixing small NPs (2 nm) of either Cu(0) or air-stable Cu2O NPs with ZnO NPs (3 nm), or by the synthesis of Cu(0) in presence of ZnO NPs (ZnO: 2 nm, Cu: 6 nm). The resulting colloidal catalysts are applied in the liquid phase hydrogenation of CO2 to methanol (210 °C, 50 bar, 3 : 1 molar ratio of CO2 : H2). The catalysts typically exhibit 3 times higher rates when compared to a heterogeneous Cu–ZnO–Al2O3 commercial catalyst (21 vs. 7 mmolMeOH gCuZnO−1 h−1). The characterisation of the post-catalysis colloids show clear Cu/ZnO interfaces (HR-TEM), which are formed under reducing conditions, as well as differences in the Cu(0) NP size (from 3 to 7 nm) and nanoscale restructuring of the catalysts. The combination of characterisation and catalytic results indicate that the activity is mostly dictated by the Cu(0) particle size and ligand loading. Smaller Cu(0) NPs exhibited lower turnover frequency (TOF) values, whereas higher ligand loadings ([DOPA]:(Cu + Zn) of 0.2–1.1) lead to smaller Cu(0) NPs and reduce the formation of Cu/ZnO interfaces. UV-vis spectroscopy reveals that the Cu(0) NPs are more stable to oxidation under air after catalysis than beforehand, potentially due to migration of ZnO onto the Cu surface whilst under catalytic conditions.

Graphical abstract: Colloidal Cu/ZnO catalysts for the hydrogenation of carbon dioxide to methanol: investigating catalyst preparation and ligand effects

Associated articles

Supplementary files

Article information

Article type
Paper
Submitted
13 Jun 2017
Accepted
26 Jul 2017
First published
11 Aug 2017
This article is Open Access
Creative Commons BY license

Catal. Sci. Technol., 2017,7, 3842-3850

Colloidal Cu/ZnO catalysts for the hydrogenation of carbon dioxide to methanol: investigating catalyst preparation and ligand effects

S. D. Pike, A. García-Trenco, E. R. White, A. H. M. Leung, J. Weiner, M. S. P. Shaffer and C. K. Williams, Catal. Sci. Technol., 2017, 7, 3842 DOI: 10.1039/C7CY01191A

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements