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| Author | Michiels, R.; Engelmann, Y.; Bogaerts, A. | ||||
| Title | Plasma Catalysis for CO2Hydrogenation: Unlocking New Pathways toward CH3OH | Type | A1 Journal article | ||
| Year | 2020 | Publication | Journal Of Physical Chemistry C | Abbreviated Journal | J Phys Chem C |
| Volume | 124 | Issue | 47 | Pages | 25859-25872 |
| Keywords | A1 Journal article; Engineering sciences. Technology; Plasma Lab for Applications in Sustainability and Medicine – Antwerp (PLASMANT); Movement Antwerp (MOVANT) | ||||
| Abstract | We developed a microkinetic model to reveal the effects of plasma-generated radicals, intermediates, and vibrationally excited species on the catalytic hydrogenation of CO2 to CH3OH on a Cu(111) surface. As a benchmark, we first present the mechanisms of thermal catalytic CH3OH formation. Our model predicts that the reverse water-gas shift reaction followed by CO hydrogenation, together with the formate path, mainly contribute to CH3OH formation in thermal catalysis. Adding plasma-generated radicals and intermediates results in a higher CH3OH turnover frequency (TOF) by six to seven orders of magnitude, showing the potential of plasma-catalytic CO2 hydrogenation into CH3OH, in accordance with the literature. In addition, CO2 vibrational excitation further increases the CH3OH TOF, but the effect is limited due to relatively low vibrational temperatures under typical plasma catalysis conditions. The predicted increase in CH3OH formation by plasma catalysis is mainly attributed to the increased importance of the formate path. In addition, the conversion of plasma-generated CO to HCO* and subsequent HCOO* or H2CO* formation contribute to CH3OH formation. Both pathways bypass the HCOO* formation from CO2, which is the main bottleneck in the process. Hence, our model points toward the important role of CO, but also O, OH, and H radicals, as they influence the reactions that consume CO2 and CO. In addition, our model reveals that the H pressure should not be smaller than ca. half of the O pressure in the plasma as this would cause O* poisoning, which would result in very small product TOFs. Thus, plasma conditions should be targeted with a high CO and H content as this is favorable for CH3OH formation, while the O content should be minimized. | ||||
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| Corporate Author | Thesis | ||||
| Publisher | Place of Publication | Editor | |||
| Language | Wos | 000595545800023 | Publication Date | 2020-11-25 | |
| Series Editor | Series Title | Abbreviated Series Title | |||
| Series Volume | Series Issue | Edition | |||
| ISSN | 1932-7447 | ISBN | Additional Links | UA library record; WoS full record; WoS citing articles | |
| Impact Factor | 3.7 | Times cited  |
Open Access | Not_Open_Access: Available from 15.07.2021 | |
| Notes | Universiteit Antwerpen; Fonds Wetenschappelijk Onderzoek, 1114921N ; H2020 European Research Council, 810182 ; We acknowledge the financial support from the Fund for Scientific Research (FWO-Vlaanderen; grant ID 1114921N) and from the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation programme (grant agreement no. 810182 − SCOPE ERC Synergy project) as well as from the DOC-PRO3 and the TOPBOF projects of the University of Antwerp. | Approved | Most recent IF: 3.7; 2020 IF: 4.536 | ||
| Call Number | PLASMANT @ plasmant @c:irua:173864 | Serial | 6443 | ||
| Permanent link to this record | |||||
| Author | Loenders, B.; Michiels, R.; Bogaerts, A. | ||||
| Title | Is a catalyst always beneficial in plasma catalysis? Insights from the many physical and chemical interactions | Type | A1 Journal Article | ||
| Year | 2023 | Publication | Journal of Energy Chemistry | Abbreviated Journal | Journal of Energy Chemistry |
| Volume | 85 | Issue | Pages | 501-533 | |
| Keywords | A1 Journal Article; Plasma, laser ablation and surface modeling Antwerp (PLASMANT) ; | ||||
| Abstract | Plasma-catalytic dry reforming of CH4 (DRM) is promising to convert the greenhouse gasses CH4 and CO2 into value-added chemicals, thus simultaneously providing an alternative to fossil resources as feedstock for the chemical industry. However, while many experiments have been dedicated to plasma-catalytic DRM, there is no consensus yet in literature on the optimal choice of catalyst for targeted products, because the underlying mechanisms are far from understood. Indeed, plasma catalysis is very complex, as it encompasses various chemical and physical interactions between plasma and catalyst, which depend on many parameters. This complexity hampers the comparison of experimental results from different studies, which, in our opinion, is an important bottleneck in the further development of this promising research field. Hence, in this perspective paper, we describe the important physical and chemical effects that should be accounted for when designing plasma-catalytic experiments in general, highlighting the need for standardized experimental setups, as well as careful documentation of packing properties and reaction conditions, to further advance this research field. On the other hand, many parameters also create many windows of opportunity for further optimizing plasma-catalytic systems. Finally, various experiments also reveal the lack of improvement in plasma catalysis compared to plasma-only, specifically for DRM, but the underlying mechanisms are unclear. Therefore, we present our newly developed coupled plasma-surface kinetics model for DRM, to provide more insight in the underlying reasons. Our model illustrates that transition metal catalysts can adversely affect plasmacatalytic DRM, if radicals dominate the plasma-catalyst interactions. Thus, we demonstrate that a good understanding of the plasma-catalyst interactions is crucial to avoiding conditions at which these interactions negatively affect the results, and we provide some recommendations for improvement. For instance, we believe that plasma-catalytic DRM may benefit more from higher reaction temperatures, at which vibrational excitation can enhance the surface reactions. | ||||
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| Corporate Author | Thesis | ||||
| Publisher | Place of Publication | Editor | |||
| Language | Wos | Publication Date | 2023-06-30 | ||
| Series Editor | Series Title | Abbreviated Series Title | |||
| Series Volume | Series Issue | Edition | |||
| ISSN | 2095-4956 | ISBN | Additional Links | UA library record | |
| Impact Factor | 13.1 | Times cited |
Open Access | Not_Open_Access | |
| Notes | This research was supported by the FWO-SBO project PlasMa- CatDESIGN (FWO grant ID S001619N), the FWO fellowship of R. Michiels (FWO grant ID 1114921N), and the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation programme (grant agreement No 810182 – SCOPE ERC Synergy project). The computational resources and services used in this work were provided by the HPC core facility CalcUA of the Universiteit Antwerpen, and VSC (Flemish Supercomputer Center), funded by the Research Foundation – Flanders (FWO) and the Flemish Government. | Approved | Most recent IF: 13.1; 2023 IF: 2.594 | ||
| Call Number | PLASMANT @ plasmant @c:irua:198159 | Serial | 8806 | ||
| Permanent link to this record | |||||
| Author | Cai, Y.; Michiels, R.; De Luca, F.; Neyts, E.; Tu, X.; Bogaerts, A.; Gerrits, N. | ||||
| Title | Improving Molecule–Metal Surface Reaction Networks Using the Meta-Generalized Gradient Approximation: CO2Hydrogenation | Type | A1 Journal Article | ||
| Year | 2024 | Publication | The Journal of Physical Chemistry C | Abbreviated Journal | J. Phys. Chem. C |
| Volume | 128 | Issue | 21 | Pages | 8611-8620 |
| Keywords | A1 Journal Article; Plasma, laser ablation and surface modeling Antwerp (PLASMANT) ; | ||||
| Abstract | Density functional theory is widely used to gain insights into molecule−metal surface reaction networks, which is important for a better understanding of catalysis. However, it is well-known that generalized gradient approximation (GGA) density functionals (DFs), most often used for the study of reaction networks, struggle to correctly describe both gas-phase molecules and metal surfaces. Also, GGA DFs typically underestimate reaction barriers due to an underestimation of the selfinteraction energy. Screened hybrid GGA DFs have been shown to reduce this problem but are currently intractable for wide usage. In this work, we use a more affordable meta-GGA (mGGA) DF in combination with a nonlocal correlation DF for the first time to study and gain new insights into a catalytically important surface reaction network, namely, CO2 hydrogenation on Cu. We show that the mGGA DF used, namely, rMS-RPBEl-rVV10, outperforms typical GGA DFs by providing similar or better predictions for metals and molecules, as well as molecule−metal surface adsorption and activation energies. Hence, it is a better choice for constructing molecule−metal surface reaction networks. |
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| Address | |||||
| Corporate Author | Thesis | ||||
| Publisher | Place of Publication | Editor | |||
| Language | Wos | Publication Date | 2024-05-30 | ||
| Series Editor | Series Title | Abbreviated Series Title | |||
| Series Volume | Series Issue | Edition | |||
| ISSN | 1932-7447 | ISBN | Additional Links | ||
| Impact Factor | 3.7 | Times cited |
Open Access | ||
| Notes | H2020 Marie Sklodowska-Curie Actions, 813393 ; Fonds Wetenschappelijk Onderzoek, 1114921N ; H2020 European Research Council, 810182 ; Nederlandse Organisatie voor Wetenschappelijk Onderzoek, 019.202EN.012 ; | Approved | Most recent IF: 3.7; 2024 IF: 4.536 | ||
| Call Number | PLASMANT @ plasmant @ | Serial | 9248 | ||
| Permanent link to this record | |||||