Solid State Chemistry @Aalto
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Introduction

Rhenium(IV) oxide (ReO2), or also known as rhenium dioxide, is a binary transition metal oxide with the lowest oxidation state (+4) of the different rhenium oxides. In normal conditions this specific oxide is found in the form of an odorless gray-black powder(1,4)solid

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citeIDRheniumBasics

"Rhenium oxide" American Elements, 25.2.2023. https://www.americanelements.com/rhenium-oxide-12036-09-8

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citeIDPubChem

"Rhenium(IV) oxide" PubChem Identifier: CID 82847. https://pubchem.ncbi.nlm.nih.gov/compound/Rhenium_IV_-oxide

, which is significantly different from the other colorful oxides that rhenium forms. ReO2 has very minor safety hazards(4)

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which has caused it to be mainly used as a catalyst or addition to superconducting ceramics(2)

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citeIDRutile2005

A. L. Ivanovskii, T. I. Chupakhina, V. G. Zubkov, A.P. Tyutyunnik, V.N. Krasilnikov, G.V. Bazuev, S. V. Okatov, A. I. Lichenstein, Structure and electronic properties of new rutile-like rhenium (IV) dioxide ReO2, Physics Letters A, 2005, 348, 66-70 (https://doi.org/10.1016/j.physleta.2005.08.025)

.

Synthesis

There are a couple of ways to synthesize rhenium(IV) oxide.

The first way is through comproportionating, where the oxide is formed from two different rhenium compounds that have different oxidation states. The reaction can be seen in the following equation:
2 Re2O7 + 3 Re → 7 ReO2

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citeIDSynthesisHandbook1963

G. Glemser, Handbook of Preparative Inorganic Chemistry, Academic Press, New York, 1963.


Single crystals can also be synthesized from chemical transport by utilizing iodine in the following reaction

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citeIDRheniumSynthesis1955

C. L. Rulfs, R. J. Meyer, Rhenium(IV) compounds: Synthesis and Properties. Analytical Chemistry. 1955, 77, 4505-4507 (https://doi.org/10.1021/ja01622a018)

:

ReO2 + I2 ⇌ ReO2I2

Another very common way of synthesis is using perrhenate compounds and acids. The solutions are bought to their boiling points and rhenium(IV) oxide or rhenium metal can be extracted through filtration as a result (1,5)

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Structure

Rhenium(IV) oxide has three different structures that it can formbe formed under different conditions. The first is a tetragonal phase with a rutile (TiO2)-type structure (space group P42/mnm, Z = 2). The second is an orthorhombic phase with a PbO2-type structure (space group Pbcn, Z =4). The last is a monoclinic phase with a MoO2-type structure (space group P121/c1, Z = 4). The monoclinic and orthorhombic structures have been known for a long time, while the rutile structure has been a rather more recent discovery. The monoclinic and orthorhombic structure have been known since around the 1960's, but the rutile structure was discovered in 2005.

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The monoclinic structure is metastable and transforms to the orthorhombic structure above 460ºC (5,6).

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citeIDMonoclinic2004

H. P. S. Corrêa, I. P. Cavalcante, L. G. Martinez, C. G. P. Orlando, M. T. D. Orlando, Refinement of monoclinic ReO2 structure from XRD by Rietveld method, Brazilian Journal of Physics, 2004, 34 (https://doi.org/10.1590/S0103-97332004000600013)

The rutile structure formation requires annealing at 420ºC under an argon atmosphere to form
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. Below are pictures of each of the different crystal structures.

Figure 2. Crystal structure of tetragonal ReO2 (Figure: Niklas Suominen. Data from ICSD (154021), visualized with Vesta).

Figure 3. Crystal structure of orthorhombic ReO2 2 (Figure: Niklas Suominen. Data from ICSD (24060), visualized with Vesta).

Figure 4. Crystal structure of monoclinic ReO2 2 (Figure: Niklas Suominen. Data from ICSD (151412), visualized with Vesta).

Properties

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Rhenium(IV) oxide Historically the main application of rhenium(IV) oxide has been a catalyst in oxidation reactions

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citeIDCatalyst2002

Y. H. Yuan, Y. Iwasawa, Performance and Characterization of Supported Rhenium Oxide Catalysts for Selective Oxidation of Methanol to Methylal, The Journal of Physical Chemistry B, 2002, 106, 4441-4449 (https://doi.org/10.1021/jp013770l)

. In addition, it has been used as an additional component in superconducting ceramic fabrication

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citeIDCeramics1998

S. Piñol, A. Sin, A. Calleja, J. Fontcuberta, X. Obradors, Synthesis of Hg1−XRexBa2Ca2Cu3O8+x Pure Phase at Normal Pressures, Journal of Superconductivity, 1998, 11, 125-126 (https://doi.org/10.1023/A:1022679206829)

. Rhenium(IV) oxide can also be used to protect underlying dielectric and barrier layers or ferroelectric capacitors as some examples

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. These applications have been known for a while now and new applications haven't really been found for this specific oxide.

Rhenium(IV) oxide isn't water soluble and it doesn't have hygroscopic properties, which is a reason why it has been used to protect dielectric layers for example(2)as mentioned previously

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. Below are the XRD patterns for all of the different crystal structures that rhenium(IV) oxide exhibits. 

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Figure 5. XRD patterns for all of the different crystal structures. The rutile-structure is on the left, orthorhombic in the center and monoclinic on the right rutile crystal structure. (Data from ICSD (154021)).

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Figure 6. XRD patterns for the orthorhombic crystal structure. (Data from ICSD (24060)).

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Figure 7. XRD patterns for the monoclinic crystal structure. (Data from ICSD (151412)).


References

  • "Rhenium oxide" American Elements, 25.2.2023. https://www.americanelements.com/rhenium-oxide-12036-09-8
    • Ivanovskii, A.L. et al. Structure and electronic properties of new rutile-like rhenium (IV) dioxide ReO2. Physics Letters A. 348, 2005, pp. 66-70. DOI: 10.1016/j.physleta.2005.08.025. 

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     Figure 1. Rhenium(IV) oxide

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    Properties of ReO2 

    Molar mass218.206 g/mol
    Density11.4 g/cm3
    Melting point1000ºC (decomposition)
    Magnetic susceptibility+44.0·10−6 cm3/mol

    Table 1. Properties of ReO2 

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    citeIDRheniumWiki

    "Rhenium(IV) oxide" Wikipedia, Wikimedia Foundation, 25.2.2023 https://en.wikipedia.org/wiki/Rhenium(IV)_oxide

  • "Rhenium(IV) oxide" PubChem Identifier: CID 82847. https://pubchem.ncbi.nlm.nih.gov/compound/Rhenium_IV_-oxide
  • Rulfs, C.L. & Meyer, R.J. Rhenium(IV) compounds: Synthesis and Properties. Analytical Chemistry. 1955, pp. 4505-4507. DOI: 10.1021/ja01622a018
  • Corrêa, H.P.S et al. Refinement of monoclinic ReO2 structure from XRD by Rietveld method. Brazilian Journal of Physics. 2004. DOI: 10.1590/S0103-97332004000600013

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     Figure 1. Rhenium(IV) oxide(1).

    Properties of ReO2 (3,4)Molar mass218.206 g/molDensity11.4 g/cm3Melting point1000ºC (decomposition)Magnetic susceptibility+44.0·10−6 cm3/mol

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    Crystal structureCrystal classSpace groupLattice parameters (Å)Formula units
    RutileTetragonalP42/mnm

    a = b = 4.79825

    c = 2.80770

    		Z = 2

    Orthorhombic

    		OrthorhombicPbcn

    a = 4.8094

    b = 5.6433

    c = 4.6007

    		Z = 4
    MonoclinicMonoclinicP121/c1

    a = 5.615

    b = 4.782

    c = 5.574

    		Z = 4

    Table 2. The structural properties of each of the different possible crystal structures (Data from ICSD (154021), (24060) and (151412))