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RESEARCH PRODUCT

Exploring the Chemical Reactivity between Carbon Dioxide and Three Transition Metals (Au, Pt, and Re) at High-Pressure, High-Temperature Conditions

Plácida Rodríguez-hernándezD. Martínez-garcíaAndrew DoranC. P. McguireJulio Pellicer-porresRaquel Chuliá-jordánDavid Santamaría-pérezDavid Santamaría-pérezMartin KunzAlfonso MuñozAbby KavnerA. R. Makhluf

subject

Inorganic chemistryAnalytical chemistrychemistry.chemical_element02 engineering and technology010402 general chemistry01 natural sciences7. Clean energyRedoxInorganic ChemistryMetalsymbols.namesakeTransition metalPhase (matter)GraphitePhysical and Theoretical ChemistryRhenium021001 nanoscience & nanotechnology0104 chemical scienceschemistry13. Climate actionvisual_artvisual_art.visual_art_mediumsymbolsOrthorhombic crystal system0210 nano-technologyRaman spectroscopy

description

The role of carbon dioxide, CO2, as oxidizing agent at high pressures and temperatures is evaluated by studying its chemical reactivity with three transition metals: Au, Pt, and Re. We report systematic X-ray diffraction measurements up to 48 GPa and 2400 K using synchrotron radiation and laser-heating diamond-anvil cells. No evidence of reaction was found in Au and Pt samples in this pressure–temperature range. In the Re + CO2 system, however, a strongly–driven redox reaction occurs at P > 8 GPa and T > 1500 K, and orthorhombic β-ReO2 is formed. This rhenium oxide phase is stable at least up to 48 GPa and 2400 K and was recovered at ambient conditions. Raman spectroscopy data confirm graphite as a reaction product. Ab-initio total-energy structural and compressibility data of the β-ReO2 phase shows an excellent agreement with experiments, altogether accurately confirming CO2 reduction P–T conditions in the presence of rhenium metal and the β-ReO2 equation of state.

https://doi.org/10.1021/acs.inorgchem.6b01858