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

Heterogeneous Catalysis Of CO₂ Conversion To Methanol On Copper Surfaces.

M. Behrens
Published 2014 · Medicine, Chemistry

Cite This
Download PDF
Analyze on Scholarcy
Share
Among the various valorization reactions of CO2, the Cucatalyzed hydrogenation to methanol belongs to the most promising conversions. Unlike many other approaches, a wellestablished large-scale process that converts synthesis gas (CO, CO2, H2) into methanol is already in operation (approx. 75 Mt/year, currently from fossil sources). In addition to its current role as mainly a base chemical, methanol is also a potential fuel, and a promising storage molecule for the energy sector. Provided a sustainable source of hydrogen becomes available at reasonable costs, this type of chemistry seems feasible to give CO2 molecules from flue gases “a second life” as a synthetic fuel and, thus, to substantially mitigate greenhouse gas emissions already in a shortto medium-term scenario. Given that there are still many open questions even with regard to the conventional syngas process, which has been studied for decades, it is no wonder that this field is currently experiencing a renaissance with many new insights into the structural and functional properties of Cu-based CO2 hydrogenation catalysts and into their mode of operation. In their recent report, Graciani et al. now present copper/ceria as a new promising catalyst system for the methanol synthesis reaction and propose a reaction mechanism based on surface scientific model studies and DFT calculations that deviates from the one that was thought to operate on conventional (Al2O3-promoted) copper/zinc oxide catalysts. Copper/ceria is known to be a powerful catalyst for CO oxidation, water– gas shift and methanol steam reforming, but until now only little attention has been paid to ceria as a promoter in methanol synthesis catalysts. This is astonishing, because there are interesting parallels between the modern view on copper/zinc oxide catalysts and the model that the authors elaborate for copper/ceria. In both systems, there is ample evidence that copper alone, that is, without contact to the support, shows a lower performance than the oxide-containing systems (although there certainly is a distinct activity also of clean copper). In their work, Graciani et al. elegantly show this by comparing the activity of a clean Cu(111) single crystal surface with one on which small ceria islands have been deposited (Figure 1a). The CeOx/Cu(111) was found to be substantially more active— a result that also has been obtained by Fujitani et al. in the copper/zinc oxide system for a ZnOx/Cu(111) model catalyst in a similar experiment. In both cases, the “reducible” nature of the oxide is thought to be important for the synergistic effect in CO2 hydrogenation. This synergistic effect of the oxide is in both Figure 1. Images of advanced surface science models of metal/oxide arrangements that can occur in heterogeneous catalysts. a) STM micrograph of the CeOx/Cu(111) inverse model catalysts studied by Graciani et al. Reprinted with permission from Ref. [3]; b) DFToptimized model of a ZnO bilayer surface phase supported on Cu(111) studied by Schott et al.; c) HRTEM micrograph of an ultrathin FeO surface film on Pt nanoparticles supported on Fe3O4 by Willinger et al.
This paper references
10.1515/green-2012-0025
The Solar Refinery
R. Schlögl (2012)
10.1002/ANGE.201302315
Chemische Aktivität von dünnen Oxidschichten: Starke Träger- Wechselwirkungen ergeben eine neue ZnO-Dünnfilmphase
Vadim Schott (2013)
Angewandte Highlights 4 www.angewandte.org
F. Studt (2013)
10.1039/C3CY00573A
New and revisited insights into the promotion of methanol synthesis catalysts by CO2
O. Martin (2013)
10.1016/S0021-9517(03)00288-4
The influence of ZnO on the differential heat of adsorption of CO on Cu catalysts: a microcalorimetric study
R. N. d'Alnoncourt (2003)
10.1038/nmat3471
Towards stable catalysts by controlling collective properties of supported metal nanoparticles.
G. Prieto (2013)
10.1002/anie.201204995
Towards oil independence through renewable methanol chemistry.
G. Olah (2013)
10.1023/A:1019133832569
On the nature of surface structural changes in Cu/ZnO methanol synthesis catalysts
Nan-Yu Topsøe (1999)
10.1016/S0039-6028(97)00192-1
The kinetics and mechanism of methanol synthesis by hydrogenation of CO2 over a Zn-deposited Cu(111) surface
T. Fujitani (1997)
10.1002/ANGE.201204995
Der Weg in die Unabhängigkeit vom Öl mithilfe einer Chemie auf der Basis von erneuerbarem Methanol
G. Olah (2013)
10.1103/PHYSREVLETT.110.086108
Tuning the reactivity of a Cu/ZnO nanocatalyst via gas phase pressure.
Luis Martínez-Suárez (2013)
10.1126/science.1253057
Highly active copper-ceria and copper-ceria-titania catalysts for methanol synthesis from CO2
J. Graciani (2014)
10.1007/s10562-012-0947-5
CO and CO2 Hydrogenation to Methanol Calculated Using the BEEF-vdW Functional
Felix Studt (2012)
10.1002/anie.201311073
Quantification of zinc atoms in a surface alloy on copper in an industrial-type methanol synthesis catalyst.
Sebastian Kuld (2014)
10.1007/978-3-642-39709-7
Methanol: The Basic Chemical and Energy Feedstock of the Future
M. Bertau (2014)
10.1002/anie.201400290
A case of strong metal-support interactions: combining advanced microscopy and model systems to elucidate the atomic structure of interfaces.
M. Willinger (2014)
10.1002/ANGE.201400290
Metall-Substrat-Wechselwirkung: Kombination von hochauflösender Mikroskopie und Modellsystemen, um die atomare Struktur von Grenzflächen aufzuklären
M. Willinger (2014)
10.1038/nchem.1873
Discovery of a Ni-Ga catalyst for carbon dioxide reduction to methanol.
F. Studt (2014)
10.1002/anie.201302315
Chemical activity of thin oxide layers: strong interactions with the support yield a new thin-film phase of ZnO.
Vadim Schott (2013)
10.1016/J.JCAT.2012.10.028
Mechanistic studies of methanol synthesis over Cu from CO/CO2/H2/H2O mixtures: The source of C in methanol and the role of water
Y. Yang (2013)



This paper is referenced by
10.1021/ACS.JPCC.7B02425
Amine-Functionalized Microporous Organic Nanotube Frameworks Supported Pt and Pd Catalysts for Selective Oxidation of Alcohol and Heck Reactions
Hui Bin Zhang (2017)
10.1016/J.RSER.2016.01.026
Electrochemical conversion of carbon dioxide into renewable fuel chemicals – The role of nanomaterials and the commercialization
I. Ganesh (2016)
10.1039/c6sc04130b
A new class of Cu/ZnO catalysts derived from zincian georgeite precursors prepared by co-precipitation† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c6sc04130b Click here for additional data file.
P. Smith (2017)
10.1002/CHIN.201503250
Heterogeneous Catalysis of CO2 Conversion to Methanol on Copper Surfaces
M. Behrens (2015)
10.1002/cssc.201601361
Interplay between Reaction and Phase Behaviour in Carbon Dioxide Hydrogenation to Methanol.
H. Reymond (2017)
10.1016/J.CATTOD.2016.09.027
What’s new? On the development of sulphidic HT catalysts before the molecular aspects
J. Veen (2017)
10.1016/J.SUSC.2016.04.016
One-dimensional nanoclustering of the Cu(100) surface under CO gas in the mbar pressure range
B. Eren (2016)
10.1007/s10562-015-1529-0
Pd-Promoter/MCM-41: A Highly Effective Bifunctional Catalyst for Conversion of Carbon Dioxide
Y. Song (2015)
10.1016/J.CATTOD.2019.05.040
Selective hydrogenation of CO2 to CH3OH and in-depth DRIFT analysis for PdZn/ZrO2 and CaPdZn/ZrO2 catalysts
A. Malik (2020)
10.1039/C9SE00165D
Conversion of the greenhouse gas CO2 to methanol over supported intermetallic Ga–Ni catalysts at atmospheric pressure: thermodynamic modeling and experimental study
K. Ahmad (2019)
10.2516/OGST/2015034
Solar Production of Fuels from Water and CO2: Perspectives and Opportunities for a Sustainable Use of Renewable Energy
R. Passalacqua (2015)
10.1002/cssc.201900324
Combined CO2 Capture and Hydrogenation to Methanol: Amine Immobilization Enables Easy Recycling of Active Elements.
S. Kar (2019)
10.1039/C7GC01993A
Carbon dioxide-to-methanol single-pot conversion using a C-scorpionate iron(II) catalyst
Ana P. C. Ribeiro (2017)
10.1007/s00894-018-3762-0
Microscopic understanding of electrocatalytic reduction of CO2 on Pd-polyaniline composite: an ab initio study
Amit Sahu (2018)
10.1002/PI.5485
An efficient, heterogeneous, reusable atom transfer radical polymerization catalyst
O. S. Taskin (2018)
10.1039/c6fd00189k
PdZn catalysts for CO2 hydrogenation to methanol using chemical vapour impregnation (CVI).
H. Bahruji (2017)
10.1021/ACSCATAL.5B01755
Hydrogenation of CO2 to Methanol: Importance of Metal–Oxide and Metal–Carbide Interfaces in the Activation of CO2
J. Rodriguez (2015)
10.1039/d0cp02505d
Adsorption and activation of CO2 on Zrn (n = 2-7) clusters.
Megha (2020)
10.1039/C8CP04955F
Core electron binding energies of adsorbates on Cu(111) from first-principles calculations.
J. M. Kahk (2018)
10.1016/j.jcou.2020.03.001
Low-pressure methanol synthesis from CO2 over metal-promoted Ni-Ga intermetallic catalysts
Melis S. Duyar (2020)
10.3390/catal10070773
Recent Progress with Pincer Transition Metal Catalysts for Sustainability
Luca Piccirilli (2020)
10.1021/ACSAMI.6B09975
A Highly Active and Robust Copper-Based Electrocatalyst toward Hydrogen Evolution Reaction with Low Overpotential in Neutral Solution.
Jialei Du (2016)
10.1002/MACP.201500141
Highly Efficient and Reusable Microporous Schiff Base Network Polymer as a Heterogeneous Catalyst for CuAAC Click Reaction
O. S. Taskin (2015)
10.1016/J.JCAT.2018.01.035
Ab initio study of CO 2 hydrogenation mechanisms on inverse ZnO/Cu catalysts
Thomas Reichenbach (2018)
10.3390/CATAL5041846
Catalytic Hydrogenation of CO2 to Methanol: Study of Synergistic Effect on Adsorption Properties of CO2 and H2 in CuO/ZnO/ZrO2 System
C. Huang (2015)
10.1002/ADSC.201801314
Homogeneous Catalytic Hydrogenation of CO2 to Methanol – Improvements with Tailored Ligands
Florian Korbinian Scharnagl (2018)
10.1039/C5EE02657A
Catalytic reduction of CO2 by H2 for synthesis of CO, methanol and hydrocarbons: challenges and opportunities
Marc D. Porosoff (2016)
10.1016/J.SUSC.2018.04.015
Initial oxidation of Cu(100) studied by X-ray photo-electron spectroscopy and density functional theory calculations
Alvaro Posada-Borbón (2018)
10.1063/1.5142586
Formic acid adsorption and decomposition on clean and atomic oxygen pre-covered Cu(100) surfaces.
Guihang Li (2020)
10.1021/ACSCATAL.5B02060
Surface-Bound Intermediates in Low-Temperature Methanol Synthesis on Copper: Participants and Spectators
Yong Yang (2015)
10.1002/cctc.201801472
Cu−Ni−Al Spinel Oxide as an Efficient Durable Catalyst for Methanol Steam Reforming
Yajie Liu (2018)
10.1039/c9re00290a
Chemistry in supercritical fluids for the synthesis of metal nanomaterials
Y. Xu (2019)
See more
Semantic Scholar Logo Some data provided by SemanticScholar