Pyrite Formation via Kinetic Intermediates through Low-Temperature Solid-State Metathesis.
The preparation of materials with limited phase stabilities yet high kinetic activation barriers is challenging. Knowledge of their possible formation pathways aids in addressing these challenges. Metathesis reactions present an approach to circumvent these barriers; however, solid-state metathesis...
| Publicado en: | Journal of the American Chemical Society Vol. 136; no. 44; pp. 15654 - 15660 |
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| Autores principales: | , |
| Formato: | Artículo |
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American Chemical Society
11/5/2014
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| Acceso en línea: | Ver este registro en EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=99719934&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 99719934 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 11/5/2014 vid: 136 iid: 44 pid: 997 pub: American Chemical Society artinfo: ui: 99719934 10.1021/ja5081647 ppf: 15654 ppct: 6 formats: tig: atl: Pyrite Formation via Kinetic Intermediates through Low-Temperature Solid-State Metathesis. aug: au: Martinolich, Andrew J. Neilson, James R. affil: Department of Chemistry, Colorado State University, Fort Collins, Colorado 80523-1872, United States su: Pyrites Metathesis reactions Iron Nickel Zinc sug: subj: Pyrites Metathesis reactions Iron Nickel Zinc ab: The preparation of materials with limited phase stabilities yet high kinetic activation barriers is challenging. Knowledge of their possible formation pathways aids in addressing these challenges. Metathesis reactions present an approach to circumvent these barriers; however, solid-state metathesis reactions are often too rapid from extensive self-heating to understand the reaction. The stoichiometric reaction of MCl salts (M = Mn, Fe, Co, Ni, Cu, Zn) with NaS enables the formation of pyrite (FeS), CoS, and NiS at low temperatures (250–350 °C). NaS has the same polyanionic dimer as found in the pyrite structure, which would suggest the possibility of a facile ion-exchange reaction. However, from high-resolution synchrotron X-ray diffraction and differential scanning calorimetry, the energetic driving force does not appear to result solely from NaCl formation but also from formation of intermediate and pyrite phases. It is apparent that the reaction proceeds through polyanionic disproportionation and formation of a low-density alkali-rich intermediate, followed by anionic comproportionation and atomic rearrangement into the pyrite phase. These results have profound implications for the use of low-temperature metathesis in achieving materials by design. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2014 holdings: @attributes: islocal: N |
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