Non-injection synthesis of monodisperse Cu-Fe-S nanocrystals and their size dependent properties

Grzegorz Gąbka , Piotr Bujak , Jan Żukrowski , Damian Zabost , Kamil Kotwica , Karolina Malinowska , Andrzej Ostrowski , Ireneusz Wielgus , Wojciech Lisowski , Janusz W. Sobczak , Marek Przybylski , Adam Proń


It is demonstrated that ternary Cu-Fe-S nanocrystals differing in composition (from Cu-rich to Fe-rich), structure (chalcopyrite or high bornite) and size can be obtained from a mixture of CuCl, FeCl3, thiourea and oleic acid (OA) in oleylamine (OLA) using the heating up procedure. This new preparation method yields the smallest Cu-Fe-S nanocrystals ever reported to date (1.5 nm for high bornite structure and 2.7 nm for chalcopyrite one). A comparative study of nanocrystals of the same composition (Cu1.6Fe1.0S2.0) but different in size (2.7 nm and 9.3 nm) revealed a pronounced quantum confinement effect, confirmed by three different techniques: UV-vis spectroscopy, cyclic voltammetry and Mössbauer spectroscopy. The optical band gap increased from 0.60 eV in the bulk material to 0.69 eV in nanocrystals of 9.3 nm size and to 1.39 eV in nanocrystals of 2.7 nm. The same trend was observed in electrochemical band gaps, derived from cyclic voltammetry studies (band gaps of 0.74 eV and 1.54 eV). The quantum effect was also manifested in Mössbauer spectroscopy by an abrupt change of the spectrum from quadrupole doublet to a Zeeman sextet below 10 K, which could be interpreted in terms well defined energy states in these nanoparticles, resulting from the quantum confinement. Mössbauer spectroscopic data confirmed in addition the results of XPS spectroscopy implying the co-existence of Fe(III) and Fe(II) in the synthesized nanocrystals. Organic shell composition was investigated by NMR spectroscopy (after dissolution of the inorganic core) and by IR. Both methods identified oleylamine (OLA) and 1-octadecene (ODE) as surfacial ligands, the latter being formed in situ via an elimination-hydrogenation reaction occurring between OLA and the nanocrystal surface.
Author Grzegorz Gąbka (FC / CPCT)
Grzegorz Gąbka,,
- Chair Of Polymer Chemistry And Technology
, Piotr Bujak (FC / CPCT)
Piotr Bujak,,
- Chair Of Polymer Chemistry And Technology
, Jan Żukrowski - [AGH University of Science and Technology (AGH)]
Jan Żukrowski,,
- Akademia Górniczo-Hutnicza
, Damian Zabost (FC / CPCT)
Damian Zabost,,
- Chair Of Polymer Chemistry And Technology
, Kamil Kotwica (FC / CPCT)
Kamil Kotwica,,
- Chair Of Polymer Chemistry And Technology
, Karolina Malinowska - [University of Warsaw (UW)]
Karolina Malinowska,,
- Uniwersytet Warszawski
, Andrzej Ostrowski (FC / CICSST)
Andrzej Ostrowski,,
- Chair Of Inorganic Chemistry And Solid State Technology
, Ireneusz Wielgus (FC / CPCT)
Ireneusz Wielgus,,
- Chair Of Polymer Chemistry And Technology
, Wojciech Lisowski - [Institute of Physical Chemistry Polish Academy of Sciences (IChF PAN)]
Wojciech Lisowski,,
- Instytut Chemii Fizycznej Polskiej Akademii Nauk
, Janusz W. Sobczak - [Institute of Physical Chemistry Polish Academy of Sciences (IChF PAN) [Polish Academy of Sciences (PAN)]]
Janusz W. Sobczak,,
- Instytut Chemii Fizycznej Polskiej Akademii Nauk
et al.`
Journal seriesPhysical Chemistry Chemical Physics, ISSN 1463-9076
Issue year2016
Publication size in sheets0.5
ASJC Classification1606 Physical and Theoretical Chemistry; 3100 General Physics and Astronomy
Languageen angielski
c6cp01887d.pdf 2.88 MB
Score (nominal)40
Score sourcejournalList
ScoreMinisterial score = 40.0, 24-08-2020, ArticleFromJournal
Ministerial score (2013-2016) = 40.0, 24-08-2020, ArticleFromJournal
Publication indicators WoS Citations = 11; Scopus Citations = 11; GS Citations = 19.0; Scopus SNIP (Source Normalised Impact per Paper): 2016 = 1.117; WoS Impact Factor: 2016 = 4.123 (2) - 2016=4.242 (5)
Citation count*20 (2020-11-23)
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* presented citation count is obtained through Internet information analysis and it is close to the number calculated by the Publish or Perish system.
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