Synthesis and Structure of Pb[C<sub>2</sub>O<sub>5</sub>]: An Inorganic Pyrocarbonate Salt

Spahr, Dominik; König, Jannes; Bayarjargal, Lkhamsuren; Luchitskaia, Rita; Milman, Victor; Perlov, A. Ya.; Liermann, Hanns‐Peter; Winkler, Björn

doi:10.1021/acs.inorgchem.2c01507

Cited by 14 publications

(42 citation statements)

References 64 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…The C–O bonds of the [C 2 O 5 ] 2– -groups with the shared oxygen atom are longer (1.35(1) Å) than the C–O bonds between the carbon atoms and the terminal oxygen atoms (1.24(1) Å). Similar distortions have been found in the two other known pyrocarbonates. , …”

Section: Resultssupporting

confidence: 84%

“…These values are similar to the bulk moduli of other pyrocarbonates. (Pb[C 2 O 5 ]: K 0 = 31 GPa and Sr[C 2 O 5 ]: K 0 = 40(3) GPa, K p = 5.4(2)). , We have also computed full sets of phonon dispersion curves at selected pressures and found no dynamic instabilities.…”

Section: Resultsmentioning

confidence: 90%

“…Our DFT model of Al 2)). 9,10 We have also computed full sets of phonon dispersion curves at selected pressures and found no dynamic instabilities.…”

Section: Dft Calculations Of Al 2 [Co 3 ] 3 and Al 2 [C 2 O 5 ][Co 3 ]mentioning

confidence: 94%

“…8 Recently, yet another group of carbonates, the inorganic pyrocarbonate salts Sr[C 2 O 5 ] and Pb[C 2 O 5 ] have been synthesized at ∼ 30 GPa and structurally characterized. 9,10 Characteristic for these pyrocarbonates is the presence of C 2 O 5 2− -groups, formed by the oxygen-sharing of two [CO 3 ] 2−groups. Pyrocarbonates have not yet been recovered at ambient conditions, and little is known about their stabilities and properties.…”

Section: ■ Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Anhydrous Aluminum Carbonates and Isostructural Compounds

Bayarjargal,

Spahr,

Milman

et al. 2023

Inorg. Chem.

Self Cite

View full text Add to dashboard Cite

We synthesized the inorganic anhydrous aluminum carbonates Al2[C2O5][CO3]2 and Al2[CO3]3 by reacting Al2O3 with CO2 at high pressures and temperatures and characterized them by Raman spectroscopy. Their structures were solved by X-ray diffraction. Al2[CO3]3 forms at around 24–28 GPa, while Al2[C2O5][CO3]2 forms above 38(3) GPa. The distinguishing feature of the new Al2[C2O5][CO3]2-structure type is the presence of pyrocarbonate [C2O5]2–-groups, trigonal [CO3]2groups, and octahedrally coordinated trivalent cations. Al2[CO3]3 has isolated [CO3]2–-groups. Both Al-carbonates can be recovered under ambient conditions. Density functional theory calculations predict that CO2 will react with Fe2O3, Ti2O3, Ga2O3, In2O3, and MgSiO3 at high pressures to form compounds which are isostructural to Al2[C2O5][CO3]2. MgSi[C2O5][CO3]2 is predicted to be stable at pressures relative to abundant mantle minerals in the presence of CO2. This structure type allows the incorporation of four elements (Mg, Si, Fe, and Al) abundant in the Earth’s mantle in octahedral coordination and provides an alternative phase with novel carbon speciation for carbon storage in the deep Earth.

show abstract

Section: Resultssupporting

confidence: 84%

Section: Resultsmentioning

confidence: 90%

“…Our DFT model of Al 2)). 9,10 We have also computed full sets of phonon dispersion curves at selected pressures and found no dynamic instabilities.…”

Section: Dft Calculations Of Al 2 [Co 3 ] 3 and Al 2 [C 2 O 5 ][Co 3 ]mentioning

confidence: 94%

Section: ■ Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Anhydrous Aluminum Carbonates and Isostructural Compounds

Bayarjargal,

Spahr,

Milman

et al. 2023

Inorg. Chem.

Self Cite

View full text Add to dashboard Cite

show abstract

“…During the reviewing process, a high‐pressure – high‐temperature experimental study of the inorganic pyrocarbonate PbC 2 O 5 salt synthesis was published by Spahr et al [31] . The experimental high‐pressure phase of PbC 2 O 5 crystallizes in the monoclinic P 2 1 /c space group at 30 GPa, a result which validates our ab initio crystal structure prediction and P–T diagram calculation.…”

Section: Resultssupporting

confidence: 82%

High‐Pressure Crystal Structures of Pb₂CO₄ and PbC₂O₅ with Tetrahedral [CO₄] and Pyrocarbonate [C₂O₅] atomic groups

et al. 2022

View full text Add to dashboard Cite

The search of the stable intermediate compounds in the system PbO−CO2 have been performed using crystal structure prediction technique in the pressure range of 0–50 GPa. Stable structures were found for the compositions Pb2CO4 and PbC2O5. The earlier known oxy‐carbonate Pb2CO4‐P212121 was shown to transform at 10 GPa into another oxy‐carbonate Pb2CO4‐Pnma and than at 22 GPa – into the sp3‐hybridized orthocarbonate with the same symmetry. PbC2O5 became thermodynamically stable at almost 10 GPa in the form of the pyrocarbonate structure P21/c. At 35–45 GPa, PbC2O5‐P21/c transforms into PbC2O5‐Fdd2 with the framework of [CO4] tetrahedra. Another energetically favorable, although dynamically unstable, pyrocarbonate structure PbC2O5‐Ptrue1‾ was found in the narrow pressure interval around 10 GPa. We suggest that some analogue of this structure can appear in experiment. One structure, sp3‐hybridized Pb2CO4‐Pnma, is dynamically and thermally stable at ambient pressure, and therefore can be decompressed and extracted from the high‐pressure environment.

show abstract

Crystal structures and P–T phase diagrams of SrC2O5 and BaC2O5

Sagatova,

Gavryushkin,

Sagatov

et al. 2023

J Comput Chem

View full text Add to dashboard Cite

In this study, we present the results of a search for new stable structures of SrCO and BaCO in the pressure range of 0–100 GPa based on the density functional theory and crystal structure prediction approaches. We have shown that the recently synthesized pyrocarbonate structure SrCO‐ is thermodynamically stable for both SrCO and BaCO. Thus, SrCO‐ is stable relative to decomposition reaction above 10 GPa, while the lower‐pressure stability limit for BaCO‐ is 5 GPa, which is the lowest value for the formation of pyrocarbonates. For SrCO, the following polymorphic transitions were found with increasing pressure: at 40 GPa and 1000 K, at 90 GPa and 1000 K. SrCO‐ and SrCO‐ are characterized by the framework and layered structures of [CO] tetrahedra, respectively. For BaCO, with increasing pressure, decomposition of BaCO‐ into BaCO and CO is observed at 34 GPa without any polymorphic transitions.

show abstract

Synthesis and Structure of Pb[C₂O₅]: An Inorganic Pyrocarbonate Salt

Cited by 14 publications

References 64 publications

Anhydrous Aluminum Carbonates and Isostructural Compounds

Anhydrous Aluminum Carbonates and Isostructural Compounds

High‐Pressure Crystal Structures of Pb₂CO₄ and PbC₂O₅ with Tetrahedral [CO₄] and Pyrocarbonate [C₂O₅] atomic groups

Crystal structures and P–T phase diagrams of SrC2O5 and BaC2O5

Contact Info

Product

Resources

About

Synthesis and Structure of Pb[C2O5]: An Inorganic Pyrocarbonate Salt

Cited by 14 publications

References 64 publications

Anhydrous Aluminum Carbonates and Isostructural Compounds

Anhydrous Aluminum Carbonates and Isostructural Compounds

High‐Pressure Crystal Structures of Pb2CO4 and PbC2O5 with Tetrahedral [CO4] and Pyrocarbonate [C2O5] atomic groups

Crystal structures and P–T phase diagrams of SrC2O5 and BaC2O5

Contact Info

Product

Resources

About

Synthesis and Structure of Pb[C₂O₅]: An Inorganic Pyrocarbonate Salt

High‐Pressure Crystal Structures of Pb₂CO₄ and PbC₂O₅ with Tetrahedral [CO₄] and Pyrocarbonate [C₂O₅] atomic groups