Opposing effects of humidity on rhodochrosite surface oxidation
Rhodochrosite (MnCO3) is a model mineral representing carbonate aerosol particles containing redox-active elements that can influence particle surface reconstruction in humid air, thereby affecting the heterogeneous transformation of important atmospheric constituents such as nitric oxides, sulfur d...
| Veröffentlicht in: | Langmuir : the ACS journal of surfaces and colloids. - 1992. - 31(2015), 8 vom: 03. März, Seite 2366-71 |
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| Format: | Online-Aufsatz |
| Sprache: | English |
| Veröffentlicht: |
2015
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| Zugriff auf das übergeordnete Werk: | Langmuir : the ACS journal of surfaces and colloids |
| Schlagworte: | Journal Article |
| Zusammenfassung: | Rhodochrosite (MnCO3) is a model mineral representing carbonate aerosol particles containing redox-active elements that can influence particle surface reconstruction in humid air, thereby affecting the heterogeneous transformation of important atmospheric constituents such as nitric oxides, sulfur dioxides, and organic acids. Using in situ atomic force microscopy, we show that the surface reconstruction of rhodochrosite in humid oxygen leads to the formation and growth of oxide nanostructures. The oxidative reconstruction consists of two consecutive processes with distinctive time scales, including a long waiting period corresponding to slow nucleation and a rapid expansion phase corresponding to fast growth. By varying the relative humidity from 55 to 78%, we further show that increasing humidity has opposing effects on the two processes, accelerating nucleation from 2.8(±0.2) × 10(-3) to 3.0(±0.2) × 10(-2) h(-1) but decelerating growth from 7.5(±0.3) × 10(-3) to 3.1(±0.1) × 10(-3) μm(2) h(-1). Through quantitative analysis, we propose that nanostructure nucleation is controlled by rhodochrosite surface dissolution, similar to the dissolution-precipitation mechanism proposed for carbonate mineral surface reconstruction in aqueous solution. To explain nanostructure growth in humid oxygen, a new Cabrera-Mott mechanism involving electron tunneling and solid-state diffusion is proposed |
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| Beschreibung: | Date Completed 21.05.2015 Date Revised 03.03.2015 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
| ISSN: | 1520-5827 |
| DOI: | 10.1021/la504465y |