α-RuCl3/polymer nanocomposites

The first group of intercalative nanocoraposites with transition metal halides

Lei Wang, Melissa Rocci-Lane, Paul Brazis, Carl R. Kannewurf, Young Il Kim, Woo Lee, Jin Ho Choy, Mercouri G Kanatzidis

Research output: Contribution to journalArticle

83 Citations (Scopus)

Abstract

Different types of polymers can be intercalated into α-RuCl3 with different synthetic methodologies. Polyaniline/α-RuCl3 nanocomposite was prepared by the in situ redox intercalative polymerization method, in which α-RuCl3 was exposed to an aniline/acetonilrile solution in open air. Water- soluble polymers such as poly(ethylene oxide), poly(vinyl pyrrolidone), and polyethylenimine were intercalated by an encapsulative precipitation method using monolayer suspensions of α-RuCl3. A modification of this method led to insertion of polypyrrole. Monolayer suspensions of α-RuCl3 can be prepared from Li(x)RuCl3 (x ~ 0.2). The latter is produced by the reaction of α-RuCl3 with 0.2 equiv of LiBH4. The polymer insertion is topotactic and does not cause structural changes to the host. The metal chloride layers in these materials possess mixed valency. The reduction and polymer intercalation of α-RuCl3 alters the intralayer and interlayer Ru3+ (low spin d5) magnetic coupling, so that interesting magnetic properties appear in the nanocomposites. In addition, the reduction brings in free hopping electrons to the RuCl3 layers and the polymer intercalation builds up new electronic or ionic conducting channels in the galleries, so that the charge transport properties are changed dramatically. For example, Li(x)RuCl3 shows an electrical conductivity 3 orders of magnitude higher than pristine α- RuCl3 at room temperature and Li(x)(PEO)(y)RuCl3 has an ion conductivity comparable with the best (lithium salt)-polymer electrolytes. For a comprehensive understanding of the structure of the representative nanocomposite Li(x)(PEO)(y)RuCl3, the arrangement of polymer chains inside the galleries was explored with analysis of its one-dimensional (001) X-ray diffraction pattern. Calculated electron density maps along the stacking c- axis lead to a structural model that fills each gallery with two layers of polymer chains exhibiting a conformation found in type-II PEO-HgCl2. The most consistent PEO arrangement in the gallery generates oxygen-rich channels in the middle of the gallery in which the Li ions can reside. The new nanocomposites were characterized with thermogravimetric analysis, infrared spectroscopy, powder X-ray diffraction, magnetic measurements, as well as electrical and ionic conductivity and thermopower measurements.

Original languageEnglish
Pages (from-to)6629-6640
Number of pages12
JournalJournal of the American Chemical Society
Volume122
Issue number28
DOIs
Publication statusPublished - Jul 19 2000

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Metal halides
Nanocomposites
Transition metals
Polymers
Metals
Polyethylene oxides
Electric Conductivity
Intercalation
X-Ray Diffraction
Monolayers
Suspensions
Electrons
Ions
Pyrrolidinones
Polyethyleneimine
Ethylene Oxide
Magnetic couplings
Mercuric Chloride
Structural Models
Thermoelectric power

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

α-RuCl3/polymer nanocomposites : The first group of intercalative nanocoraposites with transition metal halides. / Wang, Lei; Rocci-Lane, Melissa; Brazis, Paul; Kannewurf, Carl R.; Kim, Young Il; Lee, Woo; Choy, Jin Ho; Kanatzidis, Mercouri G.

In: Journal of the American Chemical Society, Vol. 122, No. 28, 19.07.2000, p. 6629-6640.

Research output: Contribution to journalArticle

Wang, Lei ; Rocci-Lane, Melissa ; Brazis, Paul ; Kannewurf, Carl R. ; Kim, Young Il ; Lee, Woo ; Choy, Jin Ho ; Kanatzidis, Mercouri G. / α-RuCl3/polymer nanocomposites : The first group of intercalative nanocoraposites with transition metal halides. In: Journal of the American Chemical Society. 2000 ; Vol. 122, No. 28. pp. 6629-6640.
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abstract = "Different types of polymers can be intercalated into α-RuCl3 with different synthetic methodologies. Polyaniline/α-RuCl3 nanocomposite was prepared by the in situ redox intercalative polymerization method, in which α-RuCl3 was exposed to an aniline/acetonilrile solution in open air. Water- soluble polymers such as poly(ethylene oxide), poly(vinyl pyrrolidone), and polyethylenimine were intercalated by an encapsulative precipitation method using monolayer suspensions of α-RuCl3. A modification of this method led to insertion of polypyrrole. Monolayer suspensions of α-RuCl3 can be prepared from Li(x)RuCl3 (x ~ 0.2). The latter is produced by the reaction of α-RuCl3 with 0.2 equiv of LiBH4. The polymer insertion is topotactic and does not cause structural changes to the host. The metal chloride layers in these materials possess mixed valency. The reduction and polymer intercalation of α-RuCl3 alters the intralayer and interlayer Ru3+ (low spin d5) magnetic coupling, so that interesting magnetic properties appear in the nanocomposites. In addition, the reduction brings in free hopping electrons to the RuCl3 layers and the polymer intercalation builds up new electronic or ionic conducting channels in the galleries, so that the charge transport properties are changed dramatically. For example, Li(x)RuCl3 shows an electrical conductivity 3 orders of magnitude higher than pristine α- RuCl3 at room temperature and Li(x)(PEO)(y)RuCl3 has an ion conductivity comparable with the best (lithium salt)-polymer electrolytes. For a comprehensive understanding of the structure of the representative nanocomposite Li(x)(PEO)(y)RuCl3, the arrangement of polymer chains inside the galleries was explored with analysis of its one-dimensional (001) X-ray diffraction pattern. Calculated electron density maps along the stacking c- axis lead to a structural model that fills each gallery with two layers of polymer chains exhibiting a conformation found in type-II PEO-HgCl2. The most consistent PEO arrangement in the gallery generates oxygen-rich channels in the middle of the gallery in which the Li ions can reside. The new nanocomposites were characterized with thermogravimetric analysis, infrared spectroscopy, powder X-ray diffraction, magnetic measurements, as well as electrical and ionic conductivity and thermopower measurements.",
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