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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CO2 Hydrogenation over Copper/ZnO Single-Atom Catalysts: Water-Promoted Transient Synthesis of Methanol.
Wenlong Wu,Yanan Wang,Lei Luo,Menglin Wang,Zhongling Li,Yue-Fang Chen,Zhiqi Wang,Jingbo Chai,Ze Cen,Yongliang Shi,Jinshuang Zhao,Jie Zeng,Hongliang Li +12 more
TL;DR: In this paper , the authors demonstrated that either too low or too high contents of water hampered the methanol synthesis over Cu/ZnO based catalysts, and the optimal content of water was 0.11 vol.
Journal ArticleDOI
Accelerating photo-thermal CO2 reduction to CO, CH4 or methanol over metal/oxide semiconductor catalysts
Kristijan Lorber,Petar Djinović +1 more
TL;DR: In this article , transition metal nanoparticles (Ni, Cu, and Ru) dispersed over oxide semiconductors were used as photo catalysts in reverse water gas shift reaction (RWGS), methane dry reforming, methanol synthesis, and Sabatier reactions.
Journal ArticleDOI
Manganese Oxide as a Promoter for Copper Catalysts in CO2 and CO Hydrogenation
Remco Dalebout,Laura Barberis,Nienke L. Visser,Jessi E. S. van der Hoeven,Ad M. J. van der Eerden,Joseph A. Stewart,Florian Meirer,Krijn P. de Jong,Petra E. de Jongh +8 more
TL;DR: In this article , the role of manganese oxide as a promoter in Cu catalysts supported on graphitic carbon during hydrogenation of CO2 and CO. This work reveals fundamental differences in the promoting effect of MnOx and ZnOx and contributes to a better understanding of reducible oxide promoters in Cu-based hydrogenation catalysts.
Journal ArticleDOI
Engineering nanoscale H supply chain to accelerate methanol synthesis on ZnZrOx
Kyung Mi Lee,Paulo C. D. Mendes,Hyun-Sook Jeon,Yizhen Song,Maxim Park Dickieson,Uzma Anjum,Luwei Chen,Tsung Cheng Yang,Chia-Min Yang,Minkee Choi,Sergey M. Kozlov,Ning Yan +11 more
TL;DR: In this paper , the authors proposed a strategy to promote a ZnZrOx methanol synthesis catalyst by incorporating hydrogen activation and delivery functions through optimized integration of ZnRox and Pd supported on carbon nanotube (Pd/CNT).
Journal ArticleDOI
A CFD study on the performance of CO<sub>2</sub> methanation in a water-permeable membrane reactor system
TL;DR: In this article , a water-permeable membrane reactor is proposed to promote CO 2 methanation with in situ removal of H 2 O. A two-dimensional CFD simulation model is built up and the effects of GHSV, H 2O permeance and CO 2 /H 2 permeation selectivity are investigated.
References
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Resolving surface chemical states in XPS analysis of first row transition metals, oxides and hydroxides: Sc, Ti, V, Cu and Zn
TL;DR: Biesinger et al. as mentioned in this paper proposed a more consistent and effective approach to curve fitting based on a combination of standard spectra from quality reference samples, a survey of appropriate literature databases and/or a compilation of literature references and specific literature references where fitting procedures are available.
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The Active Site of Methanol Synthesis over Cu/ZnO/Al2O3 Industrial Catalysts
Malte Behrens,Felix Studt,Igor Kasatkin,Stefanie Kühl,Michael Hävecker,Frank Abild-Pedersen,Stefan Zander,Frank Girgsdies,Patrick Kurr,Benjamin-Louis Kniep,Michael Tovar,Richard W. Fischer,Jens K. Nørskov,Jens K. Nørskov,Robert Schlögl +14 more
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.
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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.