Structural roles of CO2 and [CO3]2− in fully polymerized sodium aluminosilicate melts and glasses

Kubicki, James D.; Stolper, Edward M.

doi:10.1016/0016-7037(94)00317-f

Cited by 43 publications

(18 citation statements)

References 30 publications

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“…We note that the presence of carbonate groups has been reported from IR studies on CO 2 -bearing, high silica, aluminosilicate glasses (28)(29)(30) (13). The peak at 2;400 cm −1 and the high-frequency shoulder at 2;450 cm −1 are assigned to the ν 3 mode of confined and bulk CO 2 , respectively.…”

Section: Resultssupporting

confidence: 62%

Silicon carbonate phase formed from carbon dioxide and silica under pressure

Santoro

Gorelli

Haines

et al. 2011

Proc. Natl. Acad. Sci. U.S.A.

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The discovery of nonmolecular carbon dioxide under high-pressure conditions shows that there are remarkable analogies between this important substance and other group IV oxides. A natural and long-standing question is whether compounds between CO 2 and SiO 2 are possible. Under ambient conditions, CO 2 and SiO 2 are thermodynamically stable and do not react with each other. We show that reactions occur at high pressures indicating that silica can behave in a manner similar to ionic metal oxides that form carbonates at room pressure. A silicon carbonate phase was synthesized by reacting silicalite, a microporous SiO 2 zeolite, and molecular CO 2 that fills the pores, in diamond anvil cells at 18-26 GPa and 600-980 K; the compound was then temperature quenched. The material was characterized by Raman and IR spectroscopy, and synchrotron X-ray diffraction. The experiments reveal unique oxide chemistry at high pressures and the potential for synthesis of a class of previously uncharacterized materials. There are also potential implications for CO 2 segregation in planetary interiors and for CO 2 storage.high-pressure chemistry | material science | optical spectroscopy C arbon dioxide and silicon dioxide are two archetypal, group IV oxides of paramount importance for fundamental and applied chemistry and planetary sciences. CO 2 is the dominant component of the atmosphere of Earth-like planets, exists in icy forms in outer planets and asteroids, plays an important role in volcanic and seismic processes, is used as a supercritical solvent for chemical reactions, and its anthropogenic production is a major environmental issue. SiO 2 is also one of the most abundant components of terrestrial planets, and an important technological material. The chemical relationship between CO 2 and SiO 2 , in particular their reactivity, is thus of interest. Although the two systems are both group IV oxides, they are remarkably different under ambient conditions, because CO 2 is molecular and is held together by C═O double bonds, whereas SiO 2 forms network structures involving single Si─O bonds. These bonding patterns radically change under pressure. Two nonmolecular CO 2 crystalline phases and a glassy form have been discovered above 30 GPa that bear similarities to SiO 2 (1-14). The crystalline phases contain carbon in fourfold coordination by oxygen (1-10, 13, 14), and mixtures of CO 4 and CO 3 units have been found in a glassy form that has been named carbonia (13).A possible approach to favor the chemical reaction between CO 2 and SiO 2 is to select a microporous silica polymorph, such as silicalite. At ambient conditions, silicalite is characterized by a framework of four-, five-, six-, and ten-membered rings of SiO 4 tetrahedra with 5.5-Å pores (15) (Fig. 1, Left Inset). Recently, it has been found that the pores can be completely filled by simple molecules such as CO 2 and Ar under pressure, which prevents pressure-induced amorphization (PIA) and stabilizes the crystalline framework up to at least 25 GPa at room temperature (1...

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Section: Resultssupporting

confidence: 62%

Silicon carbonate phase formed from carbon dioxide and silica under pressure

Santoro

Gorelli

Haines

et al. 2011

Proc. Natl. Acad. Sci. U.S.A.

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“…In the case of the inert atom Ar, E A represents the effective energy barrier for jumps of atoms from one site in the melt structure to another. For the reactive component CO 2 , E A should be more complex and probably contains jumps of CO 2 molecules as well as the interconversion of CO 3 2À into molecular and the back reaction to CO 3 2À (Kubicki and Stolper, 1995). Therefore, the activation energies for CO 2 tot and Ar diffusion are not directly comparable.…”

Section: Temperature Dependence Of Co 2 Tot and Ar Diffusionmentioning

confidence: 94%

Carbon dioxide and argon diffusion in silicate melts: Insights into the CO2 speciation in magmas

Spickenbom

Sierralta

Nowak

2010

Geochimica et Cosmochimica Acta

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“…This deformation may result from sharing one or more of its oxygen atoms with the silicate network. This latter CO 2À 3 complex may correspond to the network carbonate proposed elsewhere (e.g., Kubicki and Stolper, 1995;Brooker et al, 1999).…”

Section: Oxidized Carbon As Co 2àmentioning

confidence: 95%