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Free-Energy Landscape of the Dissolution of Gibbsite at High pH.
Shen, Zhizhang; Kerisit, Sebastien N; Stack, Andrew G; Rosso, Kevin M.
Afiliación
  • Shen Z; Physical Sciences Division, Physical & Computational Sciences Directorate , Pacific Northwest National Laboratory , Richland , Washington 99352 , United States.
  • Kerisit SN; Physical Sciences Division, Physical & Computational Sciences Directorate , Pacific Northwest National Laboratory , Richland , Washington 99352 , United States.
  • Stack AG; Chemical Science Division , Oak Ridge National Laboratory , Oak Ridge , Tennessee 37831 , United States.
  • Rosso KM; Physical Sciences Division, Physical & Computational Sciences Directorate , Pacific Northwest National Laboratory , Richland , Washington 99352 , United States.
J Phys Chem Lett ; 9(7): 1809-1814, 2018 Apr 05.
Article en En | MEDLINE | ID: mdl-29575896
The individual elementary reactions involved in the dissolution of a solid into solution remain mostly speculative due to a lack of direct experimental probes. In this regard, we have applied atomistic simulations to map the free-energy landscape of the dissolution of gibbsite from a step edge as a model of metal hydroxide dissolution. The overall reaction combines kink formation and kink propagation. Two individual reactions were found to be rate-limiting for kink formation, that is, the displacement of Al from a step site to a ledge adatom site and its detachment from ledge/terrace adatom sites into the solution. As a result, a pool of mobile and labile adsorbed species, or adatoms, exists before the release of Al into solution. Because of the quasi-hexagonal symmetry of gibbsite, kink site propagation can occur in multiple directions. Overall, our results will enable the development of microscopic mechanistic models of metal oxide dissolution.

Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: J Phys Chem Lett Año: 2018 Tipo del documento: Article País de afiliación: Estados Unidos Pais de publicación: Estados Unidos

Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: J Phys Chem Lett Año: 2018 Tipo del documento: Article País de afiliación: Estados Unidos Pais de publicación: Estados Unidos