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곽자훈

Kwak, Ja Hun
Molecular Catalysis Lab.
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dc.citation.endPage 6349 -
dc.citation.number 11 -
dc.citation.startPage 6337 -
dc.citation.title ACS CATALYSIS -
dc.citation.volume 5 -
dc.contributor.author Wang, Xiang -
dc.contributor.author Shi, Hui -
dc.contributor.author Kwak, Jahun -
dc.contributor.author Szanyi, Janos -
dc.date.accessioned 2023-12-22T00:37:42Z -
dc.date.available 2023-12-22T00:37:42Z -
dc.date.created 2015-11-25 -
dc.date.issued 2015-11 -
dc.description.abstract The hydrogenation of CO2 was investigated over a wide range of reaction conditions, using two Pd/-Al2O3 catalysts with different Pd loadings (5% and 0.5%) and dispersions (∼11% and ∼100%, respectively). Turnover rates for CO and CH4 formation were both higher over 5% Pd/Al2O3 with a larger average Pd particle size than those over 0.5% Pd/Al2O3 with a smaller average particle size. The selectivity to methane (22-40%) on 5% Pd/Al2O3 was higher by a factor of 2-3 than that on 0.5% Pd/Al2O3. The drastically different rate expressions and apparent energies of activation for CO and CH4 formation led us to conclude that reverse water gas shift and CO2 methanation do not share the same rate-limiting step on Pd and that the two pathways are probably catalyzed at different surface sites. Measured reaction orders in CO2 and H2 pressures were similar over the two catalysts, suggesting that the reaction mechanism for each pathway does not change with particle size. In accordance, the DRIFTS results reveal that the prevalent surface species and their evolution patterns are comparable on the two catalysts during transient and steady-state experiments, switching feed gases among CO2, H2, and CO2 + H2. The DRIFTS and MS results also demonstrate that no direct dissociation of CO2 takes place over the two catalysts and that CO2 has to first react with surface hydroxyls on the oxide support. The thus-formed bicarbonates react with dissociatively adsorbed hydrogen on Pd particles to produce adsorbed formate species (bifunctional catalyst: CO2 activation on the oxide support and H2 dissociation on the metal particles). Formates near the Pd particles (most likely at the metal/oxide interface) can react rapidly with adsorbed H to produce CO, which then adsorbs on the metallic Pd particles. Two types of Pd sites are identified: one has a weak interaction with CO, which easily desorbs into gas phase at reaction temperatures, whereas the other interacts more strongly with CO, which is mainly in multibound forms and remains stable in He flow at high temperatures, but is reactive toward adsorbed H atoms on Pd leading eventually to CH4 formation. 5% Pd/Al2O3 contains a larger fraction of terrace sites favorable for forming these more multibound and stable CO species than 0.5% Pd/Al2O3. Consequently, we propose that the difference in the formation rate and selectivity to CH4 on different Pd particle sizes stems from the different concentrations of the reactive intermediate for the methanation pathway on the Pd surface. © 2015 American Chemical Society -
dc.identifier.bibliographicCitation ACS CATALYSIS, v.5, no.11, pp.6337 - 6349 -
dc.identifier.doi 10.1021/acscatal.5b01464 -
dc.identifier.issn 2155-5435 -
dc.identifier.scopusid 2-s2.0-84946726387 -
dc.identifier.uri https://scholarworks.unist.ac.kr/handle/201301/17889 -
dc.identifier.url http://pubs.acs.org/doi/10.1021/acscatal.5b01464 -
dc.identifier.wosid 000364441300012 -
dc.language 영어 -
dc.publisher AMER CHEMICAL SOC -
dc.title Mechanism of CO2 Hydrogenation on Pd/Al2O3 Catalysts: Kinetics and Transient DRIFTS-MS Studies -
dc.type Article -
dc.description.isOpenAccess FALSE -
dc.relation.journalWebOfScienceCategory Chemistry, Physical -
dc.relation.journalResearchArea Chemistry -
dc.description.journalRegisteredClass scie -
dc.description.journalRegisteredClass scopus -
dc.subject.keywordAuthor CO/CH4 selectivity -
dc.subject.keywordAuthor CO2 reduction -
dc.subject.keywordAuthor particle size -
dc.subject.keywordAuthor Pd/Al2O3 -
dc.subject.keywordAuthor reaction mechanism -
dc.subject.keywordPlus CARBON-DIOXIDE -
dc.subject.keywordPlus SUPPORTED RHODIUM -
dc.subject.keywordPlus LOW-TEMPERATURE -
dc.subject.keywordPlus METHANATION -
dc.subject.keywordPlus SURFACE -
dc.subject.keywordPlus NICKEL -
dc.subject.keywordPlus ADSORPTION -
dc.subject.keywordPlus REDUCTION -
dc.subject.keywordPlus ALUMINA -
dc.subject.keywordPlus OXIDE -

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