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Molecular-scale mechanisms of CO2 mineralization in nanoscale interfacial water films

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Abstract

The calamitous impacts of unabated carbon emission from fossil-fuel-burning energy infrastructure call for accelerated development of large-scale CO2 capture, utilization and storage technologies that are underpinned by a fundamental understanding of the chemical processes at a molecular level. In the subsurface, rocks rich in divalent metals can react with CO2, permanently sequestering it in the form of stable metal carbonate minerals, with the CO2–H2O composition of the post-injection pore fluid acting as a primary control variable. In this Review, we discuss mechanistic reaction pathways for aqueous-mediated carbonation with carbon mineralization occurring in nanoscale adsorbed water films. In the extreme of pores filled with a CO2-dominant fluid, carbonation reactions are confined to angstrom to nanometre-thick water films coating mineral surfaces, which enable metal cation release, transport, nucleation and crystallization of metal carbonate minerals. Although seemingly counterintuitive, laboratory studies have demonstrated facile carbonation rates in these low-water environments, for which a better mechanistic understanding has come to light in recent years. The overarching objective of this Review is to delineate the unique underlying molecular-scale reaction mechanisms that govern CO2 mineralization in these reactive and dynamic quasi-2D interfaces. We highlight the importance of understanding unique properties in thin water films, such as how water dielectric properties, and consequently ion solvation and hydration behaviour, can change under nanoconfinement. We conclude by identifying important frontiers for future work and opportunities to exploit these fundamental chemical insights for decarbonization technologies in the twenty-first century.

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Fig. 1: CO2 emissions and storage potentials.
Fig. 2: Thermophysical properties of CO2 and reaction environments.
Fig. 3: Carbonation kinetics in water-rich versus wet supercritical CO2 fluids.
Fig. 4: Aqueous carbonation reaction mechanism.
Fig. 5: Properties of nanoconfined water.
Fig. 6: The mechanistic picture of carbon mineralization in humidified CO2.
Fig. 7: Reactivity of the forsterite (Mg2SiO4) carbonation system in adsorbed water nanofilms.

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Acknowledgements

This material is based on work supported by the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences (BES), Chemical Sciences, Geosciences, and Biosciences Division through its Geosciences programme at Pacific Northwest National Laboratory (PNNL) and at the University of California Irvine through an Early Career award to M.J.A.Q. (DE-SC0022301). H.T.S. acknowledges support from D. Damiani (DOE HQ) and the Carbon Utilization and Storage Partnership (CUSP). J.P.K acknowledges support from the John and Jane Wold Centennial Chair in Energy and from a Nielson Energy Fellowship. Any opinions, findings, conclusions or recommendations expressed in this material are those of the authors and do not necessarily reflect those of the funding agency.

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Glossary

Flood basalts

Voluminous lava flow outpourings that cover large swathes of continental or oceanic crust.

Mafic rock

A dark coloured ferromagnesian rock, such as basalt.

Ultramafic rock

Rock with >18% MgO and low silica content, often <45% SiO2 and predominantly composed of olivine ((Mg, Fe)2SiO4) and pyroxene ((Mg, Fe)SiO3) minerals.

Supercritical CO2

(scCO2). Carbon dioxide phase with simultaneous gas-like and liquid-like properties at conditions greater than 31 °C and 73.8 bar.

Forsterite

(Mg2SiO4). An endmember composition of olivine ((Mg, Fe)2SiO4).

Serpentinization

A series of hydration reactions that occur when mafic or ultramafic rocks are exposed to circulating aqueous fluids at <400 °C.

Long-range proton transfer (proton wire)

Sequential proton transfer between a proton donor (acid) and a proton acceptor (base) mediated by water and/or other ionizable molecules.

Charge accumulation model

A model that predicts the surface charge created via bond termination, adsorption of ionic species from the solution and the dissolution of constituent ions into the solvent.

Electrochemical impedance spectroscopy

An electrochemical technique to monitor charge carrier electromigration and diffusive polarization associated with mass transport within the electrical double layer, and is useful for probing mineral–fluid interfaces at the laboratory or field scale.

Reactivity threshold

The tipping point in relative humidity and subsequent water film thickness separating regimes of rapid and persistent reactivity (for example, carbonation of substrate silicate minerals) from those characterized by negligible and/or highly impeded discontinuous reactivity.

Thermogravimetric mass spectrometry

A technique to measure sample weight change as a function of temperature while relating evolved gases to weight loss steps, and is useful for determining, identifying and quantifying carbonate mineral assemblages.

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Abdolhosseini Qomi, M.J., Miller, Q.R.S., Zare, S. et al. Molecular-scale mechanisms of CO2 mineralization in nanoscale interfacial water films. Nat Rev Chem 6, 598–613 (2022). https://doi.org/10.1038/s41570-022-00418-1

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