Atypical titration curves for GaAl12 Keggin-ions explained by a joint experimental and simulation approach
- Publikationstyp:
- Zeitschriftenaufsatz
- Metadaten:
-
- Autoren
- Marialore Sulpizi
- Johannes Luetzenkirchen
- Autoren-URL
- https://www.webofscience.com/api/gateway?GWVersion=2&SrcApp=fis-test-1&SrcAuth=WosAPI&KeyUT=WOS:000435446400042&DestLinkType=FullRecord&DestApp=WOS_CPL
- DOI
- 10.1063/1.5024201
- eISSN
- 1089-7690
- Externe Identifier
- Clarivate Analytics Document Solution ID: GJ5TT
- PubMed Identifier: 29907055
- ISSN
- 0021-9606
- Ausgabe der Veröffentlichung
- 22
- Zeitschrift
- JOURNAL OF CHEMICAL PHYSICS
- Artikelnummer
- ARTN 222836
- Datum der Veröffentlichung
- 2018
- Status
- Published
- Titel
- Atypical titration curves for GaAl<sub>12</sub> Keggin-ions explained by a joint experimental and simulation approach
- Sub types
- Article
- Ausgabe der Zeitschrift
- 148
Datenquelle: Web of Science (Lite)
- Andere Metadatenquellen:
-
- Abstract
- <jats:p>Although they have been widely used as models for oxide surfaces, the deprotonation behaviors of the Keggin-ions (MeAl127+) and typical oxide surfaces are very different. On Keggin-ions, the deprotonation occurs over a very narrow pH range at odds with the broad charging curve of larger oxide surfaces. Depending on the Me concentration, the deprotonation curve levels off sooner (high Me concentration) or later (for low Me concentration). The leveling off shows the onset of aggregation before which the Keggin-ions are present as individual units. We show that the atypical titration data previously observed for some GaAl12 solutions in comparison to the originally reported data can be explained by the presence of Ga2Al11 ions. The pKa value of aquo-groups bound to octahedral Ga was determined from ab initio molecular dynamics simulations relative to the pure GaAl12 ions. Using these results within a surface complexation model, the onset of deprotonation of the crude solution is surprisingly well predicted and the ratio between the different species is estimated to be in the proportion 20 (Ga2Al11) : 20 (Al13) : 60 (GaAl12).</jats:p>
- Autoren
- Marialore Sulpizi
- Johannes Lützenkirchen
- DOI
- 10.1063/1.5024201
- eISSN
- 1089-7690
- ISSN
- 0021-9606
- Ausgabe der Veröffentlichung
- 22
- Zeitschrift
- The Journal of Chemical Physics
- Sprache
- en
- Online publication date
- 2018
- Datum der Veröffentlichung
- 2018
- Status
- Published
- Herausgeber
- AIP Publishing
- Herausgeber URL
- http://dx.doi.org/10.1063/1.5024201
- Datum der Datenerfassung
- 2023
- Titel
- Atypical titration curves for GaAl12 Keggin-ions explained by a joint experimental and simulation approach
- Ausgabe der Zeitschrift
- 148
Datenquelle: Crossref
- Abstract
- Although they have been widely used as models for oxide surfaces, the deprotonation behaviors of the Keggin-ions (MeAl<sub>12</sub><sup>7+</sup>) and typical oxide surfaces are very different. On Keggin-ions, the deprotonation occurs over a very narrow pH range at odds with the broad charging curve of larger oxide surfaces. Depending on the Me concentration, the deprotonation curve levels off sooner (high Me concentration) or later (for low Me concentration). The leveling off shows the onset of aggregation before which the Keggin-ions are present as individual units. We show that the atypical titration data previously observed for some GaAl<sub>12</sub> solutions in comparison to the originally reported data can be explained by the presence of Ga<sub>2</sub>Al<sub>11</sub> ions. The pK<sub>a</sub> value of aquo-groups bound to octahedral Ga was determined from ab initio molecular dynamics simulations relative to the pure GaAl<sub>12</sub> ions. Using these results within a surface complexation model, the onset of deprotonation of the crude solution is surprisingly well predicted and the ratio between the different species is estimated to be in the proportion 20 (Ga<sub>2</sub>Al<sub>11</sub>) : 20 (Al<sub>13</sub>) : 60 (GaAl<sub>12</sub>).
- Addresses
- Physics Department, Johannes Gutenberg University, Staudingerweg 7, 55128 Mainz, Germany.
- Autoren
- Marialore Sulpizi
- Johannes Lützenkirchen
- DOI
- 10.1063/1.5024201
- eISSN
- 1089-7690
- Externe Identifier
- PubMed Identifier: 29907055
- Funding acknowledgements
- Deutsche Forschungsgemeinschaft: SU 752/2
- Deutsche Forschungsgemeinschaft: TRR146
- HRLS - Germany: 2DSFG
- Open access
- false
- ISSN
- 0021-9606
- Ausgabe der Veröffentlichung
- 22
- Zeitschrift
- The Journal of chemical physics
- Sprache
- eng
- Medium
- Paginierung
- 222836
- Datum der Veröffentlichung
- 2018
- Status
- Published
- Datum der Datenerfassung
- 2018
- Titel
- Atypical titration curves for GaAl<sub>12</sub> Keggin-ions explained by a joint experimental and simulation approach.
- Sub types
- Journal Article
- Ausgabe der Zeitschrift
- 148
Datenquelle: Europe PubMed Central
- Abstract
- Although they have been widely used as models for oxide surfaces, the deprotonation behaviors of the Keggin-ions (MeAl127+) and typical oxide surfaces are very different. On Keggin-ions, the deprotonation occurs over a very narrow pH range at odds with the broad charging curve of larger oxide surfaces. Depending on the Me concentration, the deprotonation curve levels off sooner (high Me concentration) or later (for low Me concentration). The leveling off shows the onset of aggregation before which the Keggin-ions are present as individual units. We show that the atypical titration data previously observed for some GaAl12 solutions in comparison to the originally reported data can be explained by the presence of Ga2Al11 ions. The pKa value of aquo-groups bound to octahedral Ga was determined from ab initio molecular dynamics simulations relative to the pure GaAl12 ions. Using these results within a surface complexation model, the onset of deprotonation of the crude solution is surprisingly well predicted and the ratio between the different species is estimated to be in the proportion 20 (Ga2Al11) : 20 (Al13) : 60 (GaAl12).
- Autoren
- Marialore Sulpizi
- Johannes Lützenkirchen
- Autoren-URL
- https://www.ncbi.nlm.nih.gov/pubmed/29907055
- DOI
- 10.1063/1.5024201
- eISSN
- 1089-7690
- Ausgabe der Veröffentlichung
- 22
- Zeitschrift
- J Chem Phys
- Sprache
- eng
- Country
- United States
- Paginierung
- 222836
- Datum der Veröffentlichung
- 2018
- Status
- Published
- Datum, an dem der Datensatz öffentlich gemacht wurde
- 2018
- Titel
- Atypical titration curves for GaAl12 Keggin-ions explained by a joint experimental and simulation approach.
- Sub types
- Journal Article
- Ausgabe der Zeitschrift
- 148
Datenquelle: PubMed
- Beziehungen:
-