Thermal decomposition of [M(NH3)6][Fe(CN)6] (M = Ir, Rh) in different atmospheres. Crystal structure of [Rh(NH3)6][Fe(CN)6]

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Abstract

The double complex salt [Rh(NH3)6][Fe(CN)6] is structurally characterized. The thermal behavior of the salt [Rh(NH3)6][Fe(CN)6] in reducing (He/H2), inert (He) and oxidizing (Ar/O2) atmospheres is studied in detail. The intermediate product of the decomposition of double complex salts [M(NH3)6][Fe(CN)6] (M = Ir, Rh) is an X-ray amorphous polymer compound with the gross composition FeM(CN)5. The final product of the decomposition of [Rh(NH3)6][Fe(CN)6] in reducing and inert atmospheres is an ordered FeRh alloy. In an oxidizing atmosphere, a solid solution of Fe2O3 and Rh2O3 oxides is predominantly formed. The obtained data allow us to consider double complex salts as precursors for obtaining iron-iridium and iron-rhodium alloys or oxide systems based on them.

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About the authors

A. A. Popov

Nikolaev Institute of Inorganic Chemistry SB RAS

Author for correspondence.
Email: apopov@niic.nsc.ru
Russian Federation, 3 Lavrentyev Ave., Novosibirsk, 630090

P. E. Plyusnin

Nikolaev Institute of Inorganic Chemistry SB RAS

Email: apopov@niic.nsc.ru
Russian Federation, 3 Lavrentyev Ave., Novosibirsk, 630090

P. Yu. Tyapkin

Institute of Solid State Chemistry and Mechanochemistry SB RAS

Email: apopov@niic.nsc.ru
Russian Federation, Novosibirsk, 630128

T. S. Sukhikh

Nikolaev Institute of Inorganic Chemistry SB RAS

Email: apopov@niic.nsc.ru
Russian Federation, 3 Lavrentyev Ave., Novosibirsk, 630090

L. S. Kibis

Boreskov Institute of Catalysis SB RAS

Email: apopov@niic.nsc.ru
Russian Federation, 5 Lavrentyev Ave., Novosibirsk, 630090

S. V. Korenev

Nikolaev Institute of Inorganic Chemistry SB RAS

Email: apopov@niic.nsc.ru
Russian Federation, 3 Lavrentyev Ave., Novosibirsk, 630090

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Supplementary files

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2. Fig. 1. Structure of the cation and anion in the DCS [Rh(NH3)6][Fe(CN)6] with a hydrogen bond (dotted line).

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3. Fig. 2. Thermal analysis curves and mass spectrometric curves of the release of gaseous decomposition products of DKS [Rh(NH3)6][Fe(CN)6] in a reducing (He/H2) atmosphere.

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4. Fig. 3. Diffraction patterns of the decomposition products of DKS [Rh(NH3)6][Fe(CN)6] at 1200°C in a reducing (1) and inert (2) atmosphere.

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5. Fig. 4. Thermal analysis curves and mass spectrometric curves of the release of gaseous decomposition products of DKS [Rh(NH3)6][Fe(CN)6] in an inert (He) atmosphere.

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6. Fig. 5. Thermal analysis curves and mass spectrometric curves of the release of gaseous decomposition products of DKS [Rh(NH3)6][Fe(CN)6] in an oxidizing (Ar/O2) atmosphere.

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7. Fig. 6. Diffraction pattern of the decomposition product of DKS [Rh(NH3)6][Fe(CN)6] at 500°C in an oxidizing atmosphere (Ar/O2) (1); diffraction patterns of Fe2O3 (ICDD PDF-2 #33-0664) (2); Rh2O3 (ICDD PDF-2 #41-0541) (3); Rh (ICDD PDF-2 #05-0685) (4).

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8. Fig. 7. IR spectra of intermediate products of decomposition of DKS [Rh(NH3)6][Fe(CN)6] in a reducing atmosphere at 350°C (1) and in an oxidizing atmosphere at 290°C (2).

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9. Fig. 8. XPS spectra of N1s, Ir4f, Fe2p and O1s recorded for the DCS [Ir(NH3)6][Fe(CN)6] and its decomposition products in a reducing (He/H2) atmosphere at different temperatures: 1 – initial DCS, 2 – 420°C, 3 – 650°C.

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10. Fig. 9. Mössbauer spectra of the DCS [Ir(NH3)6][Fe(CN)6] (a) and [Rh(NH3)6][Fe(CN)6] (b) and intermediate products FeIr(CN)5 (c) and FeRh(CN)5 (d).

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11. Supplementary materials
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12. Fig. S1. Calibration dependence of the specific atomic volume of Fe-Rh alloys on the Rh content, constructed on the basis of literature data. 1 – body-centered cubic Fe1–xRhx alloy; 2 – ordered FeRh alloy (space group Pm–3m); 3 – face-centered cubic Rh1–yFey alloy; 4 – calibration dependence. Data are taken from [28–30].

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