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Hydrogen Induced Structure and Property Changes in Eu3Si4
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
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(English)Manuscript (preprint) (Other academic)
Abstract [en]

Hydrides Eu3Si4H2+x were obtained by exposing the Zintl phase Eu3Si4 to a hydrogen atmosphere at a pressure of 30 bar and temperatures from 25 to 300 °C. Structural analysis using powder X-ray diffraction (PXRD) data suggested that hydrogenations in a temperature range 25 – 200 ºC afford a uniform hydride phase with an orthorhombic structure (Immm, a ≈ 4.40 Å, b ≈ 3.97 Å, c ≈ 19.8 Å), whereas at 300 ºC mixtures of two orthorhombic phases with c ≈ 19.86 and ≈19.58 Å were obtained. The assignment of a composition Eu3Si4H2+x is based on first principles DFT calculations, which indicated a distinct crystallographic site for H to be occupied in the Eu3Si4 structure. In this position, H atoms are coordinated in a tetrahedral fashion by Eu atoms. The resulting hydride Eu3Si4H2 is stable by -0.46 eV/H atom with respect to Eu3Si4 and gaseous H2. Deviations between the lattice parameters of the DFT optimized Eu3Si4H2 structure and the ones extracted from PXRD patterns point to the presence of additional H in interstitials also involving Si atoms. Subsequent DFT modeling of compositions Eu3Si4H3 and Eu3Si4H4 showed considerably better agreement to the experimental unit cell volumes. However, the ordered monoclinic model structures do not provide a good match to the experimental, orthorhombic, PXRD patterns. It was then concluded that the hydrides of Eu3Si4 have a composition Eu3Si4H2+x (x < 2) and are disordered with respect to H in Si2Eu3 interstitials. Hydrides Eu3Si4H2+x decompose at temperatures above 300 °C in a dynamic vacuum into unidentified products. Thus the hydrogenation of Eu3Si4H2+x is not reversible. From magnetic measurements the Curie-Weiss constant and effective magnetic moment of Eu3Si4H2+x were obtained. The former indicates antiferromagnetic interactions, the latter attains a value of ~8 mB which is typical for compounds containing Eu2+ 4f7 ions.  

Keyword [en]
Zintl phases. metal hydrides
National Category
Materials Chemistry
Research subject
Materials Chemistry
Identifiers
URN: urn:nbn:se:su:diva-141585OAI: oai:DiVA.org:su-141585DiVA: diva2:1087585
Available from: 2017-04-07 Created: 2017-04-07 Last updated: 2017-04-27Bibliographically approved
In thesis
1. Hydrogen incorporation in Zintl phases and transition metal oxides- new environments for the lightest element in solid state chemistry
Open this publication in new window or tab >>Hydrogen incorporation in Zintl phases and transition metal oxides- new environments for the lightest element in solid state chemistry
2017 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This PhD thesis presents investigations of hydrogen incorporation in Zintl phases and transition metal oxides. Hydrogenous Zintl phases can serve as important model systems for fundamental studies of hydrogen-metal interactions, while at the same time hydrogen-induced chemical structure and physical property changes provide exciting prospects for materials science. Hydrogen incorporation in transition metal oxides leads to oxyhydride systems in which O and H together form an anionic substructure. The H species in transition metal oxides may be highly mobile, making these materials interesting precursors toward other mixed anion systems. 

Zintl phases consist of an active metal, M (alkali, alkaline earth or rare earth) and a more electronegative p-block metal or semimetal component, E (Al, Ga, Si, Ge, etc.). When Zintl phases react with hydrogen, they can either form polyanionic hydrides or interstitial hydrides, undergo full hydrogenations to complex hydrides, or oxidative decomposition to more E-rich Zintl phases. The Zintl phases investigated here comprised the CaSi2, Eu3Si4, ASi (A= K, Rb) and GdGa systems which were hydrogenated at various temperature, H2 pressure, and dwelling time conditions. For CaSi2, a regular phase transition from the conventional 6R to the rare 3R took place and no hydride formation was observed. In contrast, GdGa and Eu3Si4 were very susceptible to hydrogen uptake. Already at temperatures below 100 ºC the formation of hydrides GdGaH2-x and Eu3Si4H2+x was observed. The magnetic properties of the hydrides (antiferromagnetic) differ radically from that of the Zintl phase precursor (ferromagnetic). Upon hydrogenating ASi at temperatures around 100 oC, silanides ASiH3 formed which contain discrete complex ion units SiH3-. The much complicated β – α order-disorder phase transition in ASiH3 was evaluated with neutron powder diffraction (NPD), 2H NMR and heat capacity measurements. 

A systematic study of the hydride reduction of BaTiO3 leading to perovskite oxyhydrides BaTiO3-xHx was done. A broad range of reducing agents including NaH, MgH2, CaH2, LiAlH4 and NaBH4 was employed and temperature and dwelling conditions for hydride reduction examined. Samples were characterized by X-ray powder diffraction (XRPD), thermal gravimetric analysis and 1H NMR. The concentration of H that can be incorporated in BaTiO3-xHx was found to be very low, which is in contrast with earlier reports. Instead hydride reduction leads to a high concentration of O vacancies in the reduced BaTiO3. The highly O-deficient, disordered, phases - BaTiO3-xHy(x-y) with x up to 0.6 and y in a range 0.05 – 0.2 and (x-y) > y – are cubic and may represent interesting materials with respect to electron and ion transport as well as catalysis.

Place, publisher, year, edition, pages
Stockholm: Department of Materials and Environmental Chemistry (MMK), Stockholm University, 2017. 86 p.
Keyword
Zintl phases, metal hydrides, transition metal oxyhydrides, XRPD, NPD, Rietveld refinement
National Category
Materials Chemistry
Research subject
Materials Chemistry
Identifiers
urn:nbn:se:su:diva-141588 (URN)978-91-7649-789-0 (ISBN)978-91-7649-790-6 (ISBN)
Public defence
2017-05-29, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 13:00 (English)
Opponent
Supervisors
Note

At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 3: Manuscript. Paper 5: Manuscript.

Available from: 2017-05-04 Created: 2017-04-07 Last updated: 2017-04-27Bibliographically approved

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Nedumkandathil, RejiHäussermann, Ulrich
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