Online citations, reference lists, and bibliographies.
← Back to Search

Counting Of Oxygen Defects Versus Metal Surface Sites In Methanol Synthesis Catalysts By Different Probe Molecules.

Matthias B. Fichtl, J. Schumann, I. Kasatkin, Nikolas Jacobsen, M. Behrens, R. Schlögl, M. Muhler, O. Hinrichsen
Published 2014 · Chemistry, Medicine

Cite This
Download PDF
Analyze on Scholarcy
Different surface sites of solid catalysts are usually quantified by dedicated chemisorption techniques from the adsorption capacity of probe molecules, assuming they specifically react with unique sites. In case of methanol synthesis catalysts, the Cu surface area is one of the crucial parameters in catalyst design and was for over 25 years commonly determined using diluted N2O. To disentangle the influence of the catalyst components, different model catalysts were prepared and characterized using N2O, temperature programmed desorption of H2, and kinetic experiments. The presence of ZnO dramatically influences the N2O measurements. This effect can be explained by the presence of oxygen defect sites that are generated at the Cu-ZnO interface and can be used to easily quantify the intensity of Cu-Zn interaction. N2O in fact probes the Cu surface plus the oxygen vacancies, whereas the exposed Cu surface area can be accurately determined by H2.
This paper references
Catal. Lett
T Genger (1999)
Mechanism of Methanol Synthesis on Cu through CO2 and CO Hydrogenation
L. Grabow (2011)
Catal. Lett
H Wilmer (2002)
Angew. Chem. Int. Ed
S Zander (2013)
Activity and Synergy Effects on a Cu/ZnO(0001) Surface Studied Using First-Principle Thermodynamics.
J. Xiao (2012)
The measurement of copper surface areas by reactive frontal chromatography
G. Chinchen (1987)
Atom-Resolved Imaging of Dynamic Shape Changes in Supported Copper Nanocrystals
P. L. Hansen (2002)
The chemical modification seen in the Cu/ZnO methanol synthesis catalysts
T. Fujitani (2000)
Z. anorg. allg. Chem
M Behrens
Surface structures of atomic hydrogen adsorbed on Cu(1 1 1) surface studied by density-functional-theory calculations
M. Luo (2007)
The effect of ZnO in methanol synthesis catalysts on Cu dispersion and the specific activity
T. Fujitani (1998)
CO2 fixation into methanol at Cu/ZrO2 interface from first principles kinetic Monte Carlo
Qian-Lin Tang (2009)
The role of the oxide component in the development of copper composite catalysts for methanol synthesis.
S. Zander (2013)
The influence of strongly reducing conditions on strong metal-support interactions in Cu/ZnO catalysts used for methanol synthesis.
R. Naumann d’Alnoncourt (2006)
Aktive Zentren an Oxidoberflächen: Die ZnO-katalysierte Methanolsynthese aus CO und H2†
M. Kurtz (2005)
Chemical activity of thin oxide layers: strong interactions with the support yield a new thin-film phase of ZnO.
Vadim Schott (2013)
Temperature-programmed desorption of H2 as a tool to determine metal surface areas of Cu catalysts
M. Muhler (1992)
Über den Einfluss von Sauerstoffdefektstellen auf die katalytische Aktivität von Zinkoxid
S. Polarz (2006)
Transient behavior of Cu/ZnO-based methanol synthesis catalysts
P. C. K. Vesborg (2009)
Effects of zirconia promotion on the activity of Cu/SiO2 for methanol synthesis from CO/H2 and CO2/H2
I. A. Fisher (1997)
Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment
K. Perez (2014)
Der Weg in die Unabhängigkeit vom Öl mithilfe einer Chemie auf der Basis von erneuerbarem Methanol
G. Olah (2013)
A Kinetic Model of Methanol Synthesis
T. Askgaard (1995)
J. Am. Chem. Soc
M Behrens (2013)
New and revisited insights into the promotion of methanol synthesis catalysts by CO2
O. Martin (2013)
Dissociative hydrogen adsorption on palladium requires aggregates of three or more vacancies
T. Mitsui (2003)
Die Rolle der Oxidkomponente für die Entwicklung von Kupfer‐Komposit‐Katalysatoren zur Synthese von Methanol
S. Zander (2013)
Chem. Eng. Technol
O Hinrichsen (2000)
The role of zinc oxide in Cu/ZnO catalysts for methanol synthesis and the water–gas shift reaction
M. S. Spencer (1999)
Active sites on oxide surfaces: ZnO-catalyzed synthesis of methanol from CO and H2.
M. Kurtz (2005)
Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment 2012
T Kandemir
Scientific Bases for the Preparation of Heterogeneous Catalysts
E. Gaigneaux (2002)
Catal. Sci. Tech
M Peter (2012)
Kinetic Implications of Dynamical Changes in Catalyst Morphology during Methanol Synthesis over Cu/ZnO Catalysts
C. V. Ovesen (1997)
The Active Site of Methanol Synthesis over Cu/ZnO/Al2O3 Industrial Catalysts
M. Behrens (2012)
Chemische Aktivität von dünnen Oxidschichten: Starke Träger- Wechselwirkungen ergeben eine neue ZnO-Dünnfilmphase
Vadim Schott (2013)
On the role of oxygen defects in the catalytic performance of zinc oxide.
S. Polarz (2006)
Dynamical Changes in Cu/ZnO/Al2O3 Catalysts
H. Wilmer (2002)
J. Catal
H Wilmer (2003)
Studies in Surface Science and Catalysis
B. Delmon (1988)
Towards oil independence through renewable methanol chemistry.
G. Olah (2013)
Coverage and structure of deuterium on Cu(111)
Geunseop Lee (1996)
The adsorption of atomic hydrogen on Cu(111) investigated by reflection-absorption infrared spectroscopy, electron energy loss spectroscopy and low energy electron diffraction
E. Mccash (1989)
Performance improvement of nanocatalysts by promoter-induced defects in the support material: methanol synthesis over Cu/ZnO:Al.
M. Behrens (2013)
Catal. Lett
M Peter
In Situ Investigations of Structural Changes in Cu/ZnO Catalysts
J. Grunwaldt (2000)
Tuning the reactivity of a Cu/ZnO nanocatalyst via gas phase pressure.
Luis Martínez-Suárez (2013)

This paper is referenced by
Methanol synthesis revisited: The nature of the active site of Cu in industrial Cu/ZnO/Al2O3 catalyst and Cu-Zn synergy
Makarand R. Gogate (2019)
Urea-derived Cu/ZnO catalyst being dried by supercritical CO2 for low-temperature methanol synthesis
Peipei Zhang (2020)
From organometallic zinc and copper complexes to highly active colloidal catalysts for the conversion of CO2 to methanol
N. Brown (2015)
Defect-enriched iron fluoride-oxide nanoporous thin films bifunctional catalyst for water splitting
X. Fan (2018)
Review on Copper and Palladium Based Catalysts for Methanol Steam Reforming to Produce Hydrogen
Xinhai Xu (2017)
Evolution of zincian malachite synthesis by low temperature co-precipitation and its catalytic impact on the methanol synthesis
Leon Zwiener (2019)
Component ratio dependent Cu/Zn/Al structure sensitive catalyst in CO2/CO hydrogenation to methanol
M. Sadeghinia (2018)
Water-gas shift reaction over a novel Cu-ZnO/HAP formulation: Enhanced catalytic performance in mobile fuel cell applications
Z. Boukha (2018)
Oriented Isomorphous Substitution: An Efficient and Alternative Route to Fabricate the Zn Rich Phase Pure (Cu1−x,Znx)2(OH)2CO3 Precursor Catalyst for Methanol Synthesis
H. Zheng (2020)
Influence of the Zn/Zr ratio in the support of a copper-based catalyst for the synthesis of methanol from CO2
Valentin L’hospital (2020)
Bridging the Time Gap: A Copper/Zinc Oxide/Aluminum Oxide Catalyst for Methanol Synthesis Studied under Industrially Relevant Conditions and Time Scales.
T. Lunkenbein (2016)
Structure and activity of Cu/ZnO catalysts co-modified with aluminium and gallium for methanol synthesis
R. Guil-López (2020)
Effect of zinc source on the ethanol synthesis from syngas over a slurry CuZnAl catalyst
J. Liu (2020)
The Mechanism of CO and CO2 Hydrogenation to Methanol over Cu‐Based Catalysts
Felix Studt (2015)
Surface Alloy or Metal–Cation Interaction‐The State of Zn Promoting the Active Cu Sites in Methanol Synthesis Catalysts
D. Großmann (2017)
N2O decomposition over CuO/CeO2 catalyst: New insights into reaction mechanism and inhibiting action of H2O and NO by operando techniques
Maxim Zabilskiy (2016)
Cu−Zn Alloy Formation as Unfavored State for Efficient Methanol Catalysts
E. Frei (2020)
Cu/ZnO nanocatalysts in response to environmental conditions: surface morphology, electronic structure, redox state and CO2 activation.
Luis Martínez-Suárez (2014)
Impact of the Oxygen Vacancies on Copper Electronic State and Activity of Cu‐Based Catalysts in the Hydrogenation of Methyl Acetate to Ethanol
Yushan Xi (2019)
The Temperature-Programmed Desorption of H2 from Cu/ZrO2
J. Schittkowski (2016)
Dynamic Behavior of CuZn Nanoparticles under Oxidizing and Reducing Conditions
Christian Holse (2015)
The Mechanism of Interfacial CO2 Activation on Al Doped Cu/ZnO
Maria Heenemann (2020)
Direct conversion of syngas to DME: synthesis of new Cu-based hybrid catalysts using Fehling’s solution, elimination of the calcination step
S. Asthana (2017)
The Cu–ZnO synergy in methanol synthesis from CO2, Part 1: Origin of active site explained by experimental studies and a sphere contact quantification model on Cu + ZnO mechanical mixtures
A. Valant (2015)
Promoting Strong Metal Support Interaction: Doping ZnO for Enhanced Activity of Cu/ZnO:M (M = Al, Ga, Mg) Catalysts
Julia Schumann (2015)
Hydrogenation/oxidation triggered highly efficient reversible color switching of organic molecules
Xiao Zhou (2017)
Strong metal-oxide interactions induce bifunctional and structural effects for Cu catalysts
Y. Zhu (2018)
State of the art and perspectives in heterogeneous catalysis of CO2 hydrogenation to methanol.
Jiawei Zhong (2020)
CO 2 reduction over Cu-ZnGaMO (M = Al, Zr) catalysts prepared by a sol-gel method: Unique performance for the RWGS reaction
X. Liu (2017)
Facile Synthesis of Cu@CeO2 and Its Catalytic Behavior for the Hydrogenation of Methyl Acetate to Ethanol
Y. Wang (2017)
Preparation of active Cu/ZnO-based catalysts for methanol synthesis
C. Jeong (2016)
Promoting the Synthesis of Methanol: Understanding the Requirements for an Industrial Catalyst for the Conversion of CO2.
M. Behrens (2016)
See more
Semantic Scholar Logo Some data provided by SemanticScholar