Imperial College London

Prof Milo Shaffer

Faculty of Natural SciencesDepartment of Chemistry

Professor of Materials Chemistry



+44 (0)20 7594 5825m.shaffer Website




Mr John Murrell +44 (0)20 7594 2845




M221Royal College of ScienceSouth Kensington Campus






BibTex format

author = {Pike, SD and Garcia-Trenco, A and White, ER and Leung, AHM and Weiner, J and Shaffer, MSP and Williams, CK},
doi = {10.1039/c7cy01191a},
journal = {Catalysis Science and Technology},
pages = {3842--3850},
title = {Colloidal Cu/ZnO catalysts for the hydrogenation of carbon dioxide to methanol: investigating catalyst preparation and ligand effects},
url = {},
volume = {7},
year = {2017}

RIS format (EndNote, RefMan)

AB - 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.
AU - Pike,SD
AU - Garcia-Trenco,A
AU - White,ER
AU - Leung,AHM
AU - Weiner,J
AU - Shaffer,MSP
AU - Williams,CK
DO - 10.1039/c7cy01191a
EP - 3850
PY - 2017///
SN - 2044-4753
SP - 3842
TI - Colloidal Cu/ZnO catalysts for the hydrogenation of carbon dioxide to methanol: investigating catalyst preparation and ligand effects
T2 - Catalysis Science and Technology
UR -
UR -
VL - 7
ER -