Operando high-pressure investigation of size-controlled CuZn catalysts for the methanol synthesis reaction.
Núria J. Divins,Núria J. Divins,David Kordus,David Kordus,Janis Timoshenko,Ilya Sinev,Ioannis Zegkinoglou,Arno Bergmann,See Wee Chee,Simon Widrinna,Simon Widrinna,Osman Karslıoğlu,Hemma Mistry,Mauricio Lopez Luna,Jian-Qiang Zhong,Adam S. Hoffman,Alexey Boubnov,J. Anibal Boscoboinik,Marc Heggen,Rafal E. Dunin-Borkowski,Simon R. Bare,Beatriz Roldan Cuenya +21 more
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In this article, the authors apply high-pressure operando spectroscopy methods to well-defined Cu and Cu 0.7Zn0.3 nanoparticles supported on ZnO/Al2O3, γ-Al 2O3 and SiO2 to correlate their structure, composition and catalytic performance.Abstract:
Although Cu/ZnO-based catalysts have been long used for the hydrogenation of CO2 to methanol, open questions still remain regarding the role and the dynamic nature of the active sites formed at the metal-oxide interface. Here, we apply high-pressure operando spectroscopy methods to well-defined Cu and Cu0.7Zn0.3 nanoparticles supported on ZnO/Al2O3, γ-Al2O3 and SiO2 to correlate their structure, composition and catalytic performance. We obtain similar activity and methanol selectivity for Cu/ZnO/Al2O3 and CuZn/SiO2, but the methanol yield decreases with time on stream for the latter sample. Operando X-ray absorption spectroscopy data reveal the formation of reduced Zn species coexisting with ZnO on CuZn/SiO2. Near-ambient pressure X-ray photoelectron spectroscopy shows Zn surface segregation and the formation of a ZnO-rich shell on CuZn/SiO2. In this work we demonstrate the beneficial effect of Zn, even in diluted form, and highlight the influence of the oxide support and the Cu-Zn interface in the reactivity. The nature of the active species over Cu/ZnO catalysts for methanol synthesis remains elusive. Here, the authors shed light on the evolution of the nanoparticle/support interface and correlate its structural and chemical transformations with changes in the catalytic performance.read more
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Journal ArticleDOI
Operando spectroscopic monitoring of active species in CO2 hydrogenation at elevated pressure and temperature : steady-state versus transient analysis
Journal ArticleDOI
Shape-Dependent CO2 Hydrogenation to Methanol over Cu2O Nanocubes Supported on ZnO
David Kordus,Jelena Jelic,Mauricio Lopez-Luna,Núria J. Divins,Janis Timoshenko,See Wee Chee,Clara Rettenmaier,Jutta Kröhnert,Stefanie Kühl,Annette Trunschke,Robert Schlögl,Felix Studt,Beatriz Roldan Cuenya +12 more
TL;DR: In this article, the role of the pre-catalyst shape (cubic vs spherical) in the activity and selectivity of ZnO-supported Cu nanoparticles was investigated during methanol synthesis.
Journal ArticleDOI
Meta-analysis approach for understanding the characteristics of CO2 reduction catalysts for renewable fuel production
TL;DR: In this paper , a comprehensive, structured interpretation of the catalysts' features that enhance their activity in this reaction is interpreted using meta-analysis, which is used to explore experimental data reported in past decades for the accurate design of CO2 reduction catalysts.
Book ChapterDOI
Mechanistic studies toward the rational design of oxide catalysts for carbon dioxide hydrogenation
TL;DR: In this article, a computer-assisted rational design of heterogeneous catalysts has become a central theme of computational studies on industrial catalysis, which may contribute significantly to our impending transition from a fossil fuel-based energy and chemical industry into a renewable energy-based one.
Journal ArticleDOI
High-Order Resonant Peaks and Polarization Dependence of Microphotoluminescence in Whispering-Gallery Mode ZnO Microrod Cavity
TL;DR: In this article, high-order resonance peaks appeared in the visible range and with polarization dependence in the ultraviolet (UV) region of the microphotoluminescence (micro-PL) spectrum in whispering gallery mode (WGM) ZnO microrod cavity have been thoroughly studied at room temperature.
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The Active Site of Methanol Synthesis over Cu/ZnO/Al2O3 Industrial Catalysts
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TL;DR: This work shows how to identify the crucial atomic structure motif for the industrial Cu/ZnO/Al2O3 methanol synthesis catalyst by using a combination of experimental evidence from bulk, surface-sensitive, and imaging methods collected on real high-performance catalytic systems in combination with density functional theory calculations.
Journal ArticleDOI
Atom-Resolved Imaging of Dynamic Shape Changes in Supported Copper Nanocrystals
Poul L. Hansen,Jakob Birkedal Wagner,Stig Helveg,Jens R. Rostrup-Nielsen,Bjerne S. Clausen,Henrik Topsøe +5 more
TL;DR: In situ transmission electron microscopy is used to obtain atom-resolved images of copper nanocrystals on different supports, which are catalysts for methanol synthesis and hydrocarbon conversion processes for fuel cells.
Journal ArticleDOI
Active sites for CO2 hydrogenation to methanol on Cu/ZnO catalysts
Shyam Kattel,Pedro J. Ramírez,Jingguang G. Chen,Jingguang G. Chen,José A. Rodriguez,José A. Rodriguez,Ping Liu,Ping Liu +7 more
TL;DR: A direct comparison between the activity of ZnCu and ZnO/Cu model catalysts for methanol synthesis is reported, highlighting a synergy of Cu andZnO at the interface that facilitates methenol synthesis via formate intermediates.
Journal ArticleDOI
In Situ Investigations of Structural Changes in Cu/ZnO Catalysts
TL;DR: In this article, the structure and catalytic activity of Cu/ZnO methanol synthesis catalysts have been investigated by a further developed in situ method, which combines X-ray diffraction (XRD), Xray absorption fine structure spectroscopy (XAFS), and on-line catalytic measurements by mass spectrometry.