Skip to main content
U.S. Department of Energy
Office of Scientific and Technical Information

A new class of Cu/ZnO catalysts derived from zincian georgeite precursors prepared by co-precipitation

Journal Article · · Chemical Science
DOI:https://doi.org/10.1039/c6sc04130b· OSTI ID:1624944

Zincian georgeite, an amorphous copper–zinc hydroxycarbonate, has been prepared by co-precipitation using acetate salts and ammonium carbonate. Incorporation of zinc into the georgeite phase and mild ageing conditions inhibits crystallisation into zincian malachite or aurichalcite. This zincian georgeite precursor was used to prepare a Cu/ZnO catalyst, which exhibits a superior performance to a zincian malachite derived catalyst for methanol synthesis and the low temperature water–gas shift (LTS) reaction. Furthermore, the enhanced LTS activity and stability in comparison to that of a commercial Cu/ZnO/Al2O3 catalyst, indicates that the addition of alumina as a stabiliser may not be required for the zincian georgeite derived Cu/ZnO catalyst. The enhanced performance is partly attributed to the exclusion of alkali metals from the synthesis procedure, which are known to act as catalyst poisons. The effect of residual sodium on the microstructural properties of the catalyst precursor was investigated further from preparations using sodium carbonate.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Organization:
Engineering and Physical Sciences Research Council (EPSRC); Johnson Matthey; USDOE Office of Science (SC); National Science Foundation (NSF)
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1624944
Journal Information:
Chemical Science, Journal Name: Chemical Science Journal Issue: 3 Vol. 8; ISSN 2041-6520; ISSN CSHCBM
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

References (51)

Relations between Synthesis and Microstructural Properties of Copper/Zinc Hydroxycarbonates journal May 2003
Performance Improvement of Nanocatalysts by Promoter-Induced Defects in the Support Material: Methanol Synthesis over Cu/ZnO:Al journal April 2013
Stable amorphous georgeite as a precursor to a high-activity catalyst journal February 2016
In situ EDXRD study of the chemistry of aging of co-precipitated mixed Cu,Zn hydroxycarbonates – consequences for the preparation of Cu/ZnO catalysts journal January 2012
A model-based precipitation study of copper-based catalysts journal April 2015
Formation of a ZnO Overlayer in Industrial Cu/ZnO/Al 2 O 3 Catalysts Induced by Strong Metal-Support Interactions journal February 2015
Continuous Coprecipitation of Catalysts in a Micromixer: Nanostructured Cu/ZnO Composite for the Synthesis of Methanol journal August 2003
Rational Design of Nanostructured Copper–Zinc Oxide Catalysts for the Steam Reforming of Methanol journal January 2004
Heterogeneous Catalysis of CO 2 Conversion to Methanol on Copper Surfaces journal October 2014
Formation of a ZnO Overlayer in Industrial Cu/ZnO/Al 2 O 3 Catalysts Induced by Strong Metal-Support Interactions journal February 2015
The Potential of Microstructural Optimization in Metal/Oxide Catalysts: Higher Intrinsic Activity of Copper by Partial Embedding of Copper Nanoparticles journal April 2010
Relations Between Synthesis and Microstructural Properties of Copper/Zinc Hydroxycarbonates. journal August 2003
Minerals as Model Compounds for Cu/ZnO Catalyst Precursors: Structural and Thermal Properties and IR Spectra of Mineral and Synthetic (Zincian) Malachite, Rosasite and Aurichalcite and a Catalyst Precursor Mixture journal April 2009
Raman spectroscopic study of azurite and malachite at 298 and 77 K journal January 2002
Structural Effects of Cu/Zn Substitution in the Malachite-Rosasite System  journal April 2010
How to Prepare a Good Cu/ZnO Catalyst or the Role of Solid State Chemistry for the Synthesis of Nanostructured Catalysts: How to Prepare a Good Cu/ZnO Catalyst journal October 2013
Methanol Synthesis journal September 2012
Methanol Synthesis journal May 1992
Water-gas shift reaction: finding the mechanistic boundary journal January 1995
Georgeite and azurite as precursors in the preparation of co-precipitated copper/zinc oxide catalysts journal June 1992
Activity and structure-sensitivity of the water-gas shift reaction over CuZnAl mixed oxide catalysts journal October 1995
Methanol synthesis journal December 1995
Optimization of preparation conditions and improvement of stability of Cu/ZnO-based multicomponent catalysts for methanol synthesis from CO2 and H2 journal October 1998
Preparation of a coprecipitated Cu/ZnO catalyst for the methanol synthesis from CO2 — effects of the calcination and reduction conditions on the catalytic performance journal February 2001
Residual sodium effect on the catalytic activity of Cu/ZnO/Al2O3 in methanol synthesis from CO2 hydrogenation journal November 1998
Ambient temperature carbon monoxide oxidation using copper manganese oxide catalysts: Effect of residual Na+ acting as catalyst poison journal January 2003
Continuous precipitation of Cu/ZnO/Al2O3 catalysts for methanol synthesis in microstructured reactors with alternative precipitating agents journal January 2013
Design and preparation of high-surface-area Cu/ZnO/Al2O3 catalysts using a modified co-precipitation method for the water-gas shift reaction journal July 2013
Comparative study of Cu/ZnO catalysts derived from different precursors as a function of aging journal February 2008
Towards ‘greener’ catalyst manufacture: Reduction of wastewater from the preparation of Cu/ZnO/Al2O3 methanol synthesis catalysts journal October 2013
Multi-component and multi-phase population balance model: The case of Georgeite formation as methanol catalyst precursor phase journal April 2014
Effect of precipitate aging on the microstructural characteristics of Cu/ZnO catalysts for methanol steam reforming journal November 2005
Correlations between synthesis, precursor, and catalyst structure and activity of a large set of CuO/ZnO/Al2O3 catalysts for methanol synthesis journal September 2008
Meso- and nano-structuring of industrial Cu/ZnO/(Al2O3) catalysts journal October 2009
Microkinetic analysis and mechanism of the water gas shift reaction over copper catalysts journal July 2011
Effects of oxide carriers on surface functionality and process performance of the Cu–ZnO system in the synthesis of methanol via CO2 hydrogenation journal April 2013
Catalytic behavior of ternary Cu/ZnO/Al2O3 systems prepared by homogeneous precipitation in water-gas shift reaction journal September 2007
The effect of the precursor ageing on properties of the Cu/ZnO/Al2O3 catalyst for low temperature water–gas shift (LT-WGS) journal October 2014
Aurichalcite – An SEM and Raman spectroscopic study journal August 2007
Optimization of preparation conditions and improvement of stability of Cu/ZnO-based multicomponent catalysts for methanol synthesis from CO2 and H2 book January 1998
Promoting Strong Metal Support Interaction: Doping ZnO for Enhanced Activity of Cu/ZnO:M (M = Al, Ga, Mg) Catalysts journal April 2015
Co-precipitated Copper Zinc Oxide Catalysts for Ambient Temperature Carbon Monoxide Oxidation: Effect of Precipitate Aging Atmosphere on Catalyst Activity journal January 2003
Deactivation of Copper Metal Catalysts for Methanol Decomposition, Methanol Steam Reforming and Methanol Synthesis journal April 2003
Copper–zinc oxide catalysts. Activity in relation to precursor structure and morphology journal January 1989
Characterization of precursors to methanol synthesis catalysts Cu/ZnO system
  • Millar, Graeme J.; Holm, Ivan H.; Uwins, Philippa J. R.
  • Journal of the Chemical Society, Faraday Transactions, Vol. 94, Issue 4 https://doi.org/10.1039/a703954i
journal January 1998
Knowledge-based development of a nitrate-free synthesis route for Cu/ZnO methanol synthesis catalysts via formate precursors journal January 2011
New and revisited insights into the promotion of methanol synthesis catalysts by CO2 journal January 2013
The Active Site of Methanol Synthesis over Cu/ZnO/Al2O3 Industrial Catalysts journal April 2012
Georgeite, a new amorphous copper carbonate from the Carr Boyd Mine, Western Australia journal March 1979
The synthesis and composition of georgeite and its reactions to form other secondary copper(II) carbonates journal June 1991
The Importance of the Aging Time to Prepare Cu/ZnO/Al 2 O 3 Catalyst with High Surface Area in Methanol Synthesis journal May 2010

Cited By (8)

Capsule‐Structured Copper–Zinc Catalyst for Highly Efficient Hydrogenation of Carbon Dioxide to Methanol journal October 2019
Capsule‐Structured Copper–Zinc Catalyst for Highly Efficient Hydrogenation of Carbon Dioxide to Methanol journal November 2019
Flash-Calcined CuZnAl-LDH as High-Activity LT-WGS Catalyst: Flash-Calcined CuZnAl-LDH as High-Activity LT-WGS Catalyst journal March 2019
The effect of Cu–Zn distribution in zincian malachite on the formation of individual CuO and ZnO particles journal February 2019
Bimetallic catalysts for green methanol production via CO 2 and renewable hydrogen: a mini-review and prospects journal January 2018
Synthesis of ZnO and Cu-doped ZnO Nanocrystalline by Solution Combustion Method and Their Catalytic Effects on Thermal Behavior of KClO 4 journal August 2019
Synthesis of ZnO and Cu-doped ZnO Nanocrystalline by Solution Combustion Method and Their Catalytic Effects on Thermal Behavior of KClO4 text January 2019
Synthesis of ZnO and Cu-doped ZnO Nanocrystalline by Solution Combustion Method and Their Catalytic Effects on Thermal Behavior of KClO4 text January 2019

Figures / Tables (13)