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
Reads0
Chats0
TLDR
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
Citations
More filters
Journal ArticleDOI
Induced activation of the commercial Cu/ZnO/Al2O3 catalyst for the steam reforming of methanol
Didi Li,Fang Xu,Xuan Tang,Sheng Dai,Tiancheng Pu,Xianglin Liu,Pengfei Tian,Fuzhen Xuan,Zhi Ping Xu,Israel E. Wachs,Minghui Zhu +10 more
Journal ArticleDOI
Following the structure of copper-zinc-alumina across the pressure gap in carbon dioxide hydrogenation
Arik Beck,Maxim Zabilskiy,Mark A. Newton,Olga V. Safonova,Marc Willinger,Jeroen A. van Bokhoven,Jeroen A. van Bokhoven +6 more
TL;DR: In this paper, the state and evolution of the catalyst is defined by its environment, and the structure of the catalysts shows a strong pressure dependence, especially below 1 bar, which is a general problem in catalysis.
Journal ArticleDOI
The state of zinc in methanol synthesis over a Zn/ZnO/Cu(211) model catalyst
P. Amann,Bernhard Klötzer,David Degerman,Norbert Köpfle,Thomas Götschi,Patrick Lömker,Christoph Rameshan,Kevin Ploner,Djuro Bikaljevic,Hsin-Yi Wang,Markus Soldemo,Mikhail Shipilin,Christopher M. Goodwin,Jörgen Gladh,Joakim Halldin Stenlid,M. Börner,Christoph Schlueter,and Svante Nilsson +17 more
TL;DR: In this paper , the authors used x-ray photoelectron spectroscopy at 180 to 500 millibar to probe the nature of Zn and reaction intermediates during CO2/CO hydrogenation over Zn/ZnO/Cu(211), where the temperature is sufficiently high for the reaction to rapidly turn over, thus creating an almost adsorbate-free surface.
Journal ArticleDOI
Modulating the Electronic Metal‐Support Interactions in Single‐Atom Pt <sub>1</sub> −CuO Catalyst for Boosting Acetone Oxidation
TL;DR: In this paper , the electronic metal-support interactions (EMSIs) are tuned for single-atom catalysts (SACs) in order to improve the catalytic performance of SACs.
Journal ArticleDOI
Methanol Synthesis from CO2/CO Mixture on Cu-Zn Catalysts from Microkinetics-Guided Machine Learning Pathway Search.
TL;DR: In this paper , a microkinetics-guided machine learning pathway search was developed to explore thousands of reaction pathways for CO2 and CO hydrogenations on thermodynamically favorable Cu-Zn surface structures.
References
More filters
Journal ArticleDOI
Quantifying the promotion of Cu catalysts by ZnO for methanol synthesis
Sebastian Kuld,Max Thorhauge,Hanne Falsig,Christian Fink Elkjær,Stig Helveg,Ib Chorkendorff,Jens Sehested +6 more
TL;DR: Results demonstrate the size-dependent activities of nanoparticles as a general means to design synergetic functionality in binary nanoparticle systems and reveal a strong interdependency of the methanol synthesis activity and the Zn coverage.
Journal ArticleDOI
Synthesis, characterization and activity pattern of Cu–ZnO/ZrO2 catalysts in the hydrogenation of carbon dioxide to methanol
Francesco Arena,Katia Barbera,G. Italiano,Giuseppe Bonura,Lorenzo Spadaro,Francesco Frusteri +5 more
TL;DR: In this article, a reverse co-precipitation under ultrasound irradiation has led to Cu-ZnO/ZrO 2 catalysts with a remarkable development of total surface area (SA BET, 120-180 m 2 /g) and very high dispersion (3-58%) and exposure (MSA 9-63 m 2/g) of the active Cu phase.
Journal ArticleDOI
The Mechanism of CO and CO2 Hydrogenation to Methanol over Cu-Based Catalysts
Felix Studt,Felix Studt,Malte Behrens,Malte Behrens,Edward L. Kunkes,Nygil Thomas,Nygil Thomas,Stefan Zander,Andrey Tarasov,Julia Schumann,Elias Frei,Joel B. Varley,Joel B. Varley,Frank Abild-Pedersen,Frank Abild-Pedersen,Jens K. Nørskov,Jens K. Nørskov,Robert Schlögl,Robert Schlögl +18 more
TL;DR: In this article, the authors show how the presence or absence of the Zn promoter dramatically changes not only the activity, but also unexpectedly the reaction mechanism itself, and propose two different sites for methanol synthesis, Zn-promoted and unpromoted.
Journal ArticleDOI
Formation of a ZnO Overlayer in Industrial Cu/ZnO/Al2O3 Catalysts Induced by Strong Metal–Support Interactions
TL;DR: For the first time, clear evidence for the formation of metastable "graphite-like" ZnO layers during reductive activation is provided and might contribute to the understanding of synergistic effects between the components of the Cu/ZnO/Al2 O3 catalysts.
Journal ArticleDOI
Mechanistic studies of methanol synthesis over Cu from CO/CO2/H2/H2O mixtures: The source of C in methanol and the role of water
TL;DR: This paper showed that the dominant source of C in the methanol product gradually shifts from CO 2 to CO as the temperature is lowered, with formate playing a spectator co-adsorbate role.