Journal of Materials Science

, Volume 54, Issue 13, pp 9426–9441 | Cite as

Electrochemically active dispersed tungsten oxides obtained from tungsten hexacarbonyl in supercritical carbon dioxide

  • Alexander Yu. Nikolaev
  • Alexander A. Khokhlov
  • Eduard E. Levin
  • Sergey S. Abramchuk
  • Elena P. Kharitonova
  • Marat O. GallyamovEmail author
Chemical routes to materials


Electrochemically active nanocrystalline tungsten oxide was synthesized in supercritical carbon dioxide from tungsten hexacarbonyl at 150 °C and 400 bar in the presence of oxygen (partial pressure of 15 bar). The supercritical fluid is a solvent for the precursor (i.e., this is a sc solvothermal synthesis route), whereas the admixed gaseous oxygen serves as an oxidizer, promoting thermal decomposition of the precursor. During the substrate-free synthesis, 200–500 nm aggregates are formed. They consist of smaller grains having the size of about 100 nm. Therefore, a certain structural hierarchy is detected. The electrochemical activity of the as-synthesized particulate material is pronouncedly increasing during both potential cycling and exposure in an aqueous aerated electrolyte. After such a hydration/oxidation process, the electrochemical response of the material shows rather fast and reversible recharging of the entire tungsten-containing phase. This is an indication of facilitated proton transport in bulk of the tungsten oxide phase synthesized in the supercritical carbon dioxide with subsequent hydration/oxidation. Quite differently, the material synthesized at the same temperature only in compressed oxygen (partial pressure of 15 bar) without any presence of supercritical carbon dioxide is highly crystalline one. It does not demonstrate any significant electrochemical rechargeability; neither is the response improving with hydration/oxidation.



The authors are grateful to Yu.A. Velikodny for measuring XRD patterns. The reported study was mainly funded by RFBR according to the research Projects Nos. 13-03-01096_a and 18-29-06036_mk. Research contributions of A.A.Kh. and S.S.A. as reported in this publication were also supported by Centre for Electrochemical Energy of Skolkovo Institute of Science and Technology. A.Yu.N. and M.O.G. also acknowledge the support from Russian Academy of Sciences within the Basic Research Program of the Division of Chemistry and Materials Sciences (Program No. OKh-3).

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interests.


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© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  1. 1.A.N. Nesmeyanov Institute of Organoelement Compounds of Russian Academy of SciencesMoscowRussian Federation
  2. 2.Faculty of Physics and Faculty of ChemistryM.V. Lomonosov Moscow State UniversityMoscowRussian Federation

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