Carbonation of MgO Single Crystals: Implications for Direct Air Capture of CO2

Peng Yang; Jacquelyn N. Bracco; Gabriela Camacho Meneses; Ke Yuan; Joanne E. Stubbs; Mavis D. Boamah; Matthew Brahlek; Michel Sassi; Peter J. Eng; Matthew G. Boebinger; Albina Borisevich; Anna K. Wanhala; Zheming Wang; Kevin M. Rosso; Andrew G. Stack; Juliane Weber

doi:10.1021/acs.est.4c09713

Carbonation of MgO Single Crystals: Implications for Direct Air Capture of CO₂

Peng Yang, Jacquelyn N. Bracco, Gabriela Camacho Meneses, Ke Yuan, Joanne E. Stubbs, Mavis D. Boamah, Matthew Brahlek, Michel Sassi, Peter J. Eng, Matthew G. Boebinger, Albina Borisevich, Anna K. Wanhala, Zheming Wang, Kevin M. Rosso, Andrew G. Stack, Juliane Weber

Research output: Contribution to journal › Article › peer-review

1 Scopus citations

Abstract

Direct air capture (DAC) may be feasible to remove carbon dioxide (CO₂) from the atmosphere at the gigaton scale, holding promise to become a major contributor to climate change mitigation. Mineral looping using magnesium oxide (MgO) is potentially an economical, efficient, and sustainable pathway to gigaton-scale DAC. The hydroxylation and carbonation of MgO determine the efficiency of the looping process, but their rates and mechanisms remain uncertain. In this work, MgO single crystals were reacted in air or CO₂ at varying humidities and characterized by X-ray scattering, microscopy, and vibrational spectroscopy. Results show that the hydroxylation formed a brucite (Mg(OH)₂)-like layer immediately after crystal cleaving. Concurrently, the carbonation formed hydrated magnesium carbonate phases, including barringtonite (MgCO₃·2H₂O) and nesquehonite (MgCO₃·2H₂O), in the layer. Rapid initial growth of the layer is also manifested in short-range bending/warping of nanocrystallites, resulting in multiple orientations of the same phases on the surface. The layer growth slowed down over time, indicating surface passivation. The formation of barringtonite and nesquehonite with 1:1 CO₃/Mg ratio indicates an efficient carbonation when compared to other magnesium carbonate phases of lower ratio. Our results are essential for understanding surface passivation mechanisms and tackling the passivation issue of mineral looping DAC technology.

Original language	English
Pages (from-to)	3484-3494
Number of pages	11
Journal	Environmental Science and Technology
Volume	59
Issue number	7
DOIs	https://doi.org/10.1021/acs.est.4c09713
State	Published - Feb 25 2025

Funding

This work was mainly supported by the U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences (BES), Materials Sciences and Engineering Division. TEM characterization was conducted as part of a user project at the Center for Nanophase Materials Sciences (CNMS), which is a U.S. Department of Energy, Office of Science User Facility, at Oak Ridge National Laboratory. We would like to thank James Kolopus for providing the MgO samples used in this study, if not stated otherwise. Jefferey Baxter is acknowledged for FIB sample preparation. XRR and GIXRD measurements were conducted at GeoSoilEnviroCARS (The University of Chicago, Beamline 13-ID-C), Advanced Photon Source (APS), Argonne National Laboratory. GeoSoilEnviroCARS is supported by the National Science Foundation-Earth Sciences (EAR-1634415). J.E.S, A.K.W., and P.J.E. received further support from the Department of Energy-GeoScience (DE-SC0019108) for beamline support at GeoSoilEnviroCARS. M.D.B., M.S., Z.W., and K.M.R. acknowledge support from the DOE BES, Chemical Sciences, Geosciences, and Biosciences Division through its Geosciences program at Pacific Northwest National Laboratory (FWP # 56674) for vSFG measurements and work on the manuscript. This research used resources of the Advanced Photon Source, a U.S. Department of Energy Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract DE-AC02-06CH11357. The vSFG was performed using the Environmental and Molecular Sciences Laboratory (EMSL), a national scientific user facility at Pacific Northwest National Laboratory (PNNL) sponsored by the DOE\u2019s Office of Biological and Environmental Research. PNNL is a multiprogram national laboratory operated by Battelle Memorial Institute under contract no. DE-AC05-76RL01830 for the DOE.

Keywords

MgO
carbon dioxide
decarbonization
direct air capture
mineral looping technology
surface carbonation

Access to Document

10.1021/acs.est.4c09713

Cite this

Yang, P., Bracco, J. N., Camacho Meneses, G., Yuan, K., Stubbs, J. E., Boamah, M. D., Brahlek, M., Sassi, M., Eng, P. J., Boebinger, M. G., Borisevich, A., Wanhala, A. K., Wang, Z., Rosso, K. M., Stack, A. G., & Weber, J. (2025). Carbonation of MgO Single Crystals: Implications for Direct Air Capture of CO₂. Environmental Science and Technology, 59(7), 3484-3494. https://doi.org/10.1021/acs.est.4c09713

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title = "Carbonation of MgO Single Crystals: Implications for Direct Air Capture of CO2",

abstract = "Direct air capture (DAC) may be feasible to remove carbon dioxide (CO2) from the atmosphere at the gigaton scale, holding promise to become a major contributor to climate change mitigation. Mineral looping using magnesium oxide (MgO) is potentially an economical, efficient, and sustainable pathway to gigaton-scale DAC. The hydroxylation and carbonation of MgO determine the efficiency of the looping process, but their rates and mechanisms remain uncertain. In this work, MgO single crystals were reacted in air or CO2 at varying humidities and characterized by X-ray scattering, microscopy, and vibrational spectroscopy. Results show that the hydroxylation formed a brucite (Mg(OH)2)-like layer immediately after crystal cleaving. Concurrently, the carbonation formed hydrated magnesium carbonate phases, including barringtonite (MgCO3·2H2O) and nesquehonite (MgCO3·2H2O), in the layer. Rapid initial growth of the layer is also manifested in short-range bending/warping of nanocrystallites, resulting in multiple orientations of the same phases on the surface. The layer growth slowed down over time, indicating surface passivation. The formation of barringtonite and nesquehonite with 1:1 CO3/Mg ratio indicates an efficient carbonation when compared to other magnesium carbonate phases of lower ratio. Our results are essential for understanding surface passivation mechanisms and tackling the passivation issue of mineral looping DAC technology.",

keywords = "MgO, carbon dioxide, decarbonization, direct air capture, mineral looping technology, surface carbonation",

author = "Peng Yang and Bracco, {Jacquelyn N.} and {Camacho Meneses}, Gabriela and Ke Yuan and Stubbs, {Joanne E.} and Boamah, {Mavis D.} and Matthew Brahlek and Michel Sassi and Eng, {Peter J.} and Boebinger, {Matthew G.} and Albina Borisevich and Wanhala, {Anna K.} and Zheming Wang and Rosso, {Kevin M.} and Stack, {Andrew G.} and Juliane Weber",

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Yang, P, Bracco, JN, Camacho Meneses, G, Yuan, K, Stubbs, JE, Boamah, MD, Brahlek, M, Sassi, M, Eng, PJ, Boebinger, MG , Borisevich, A, Wanhala, AK, Wang, Z, Rosso, KM, Stack, AG & Weber, J 2025, 'Carbonation of MgO Single Crystals: Implications for Direct Air Capture of CO₂', Environmental Science and Technology, vol. 59, no. 7, pp. 3484-3494. https://doi.org/10.1021/acs.est.4c09713

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T1 - Carbonation of MgO Single Crystals

T2 - Implications for Direct Air Capture of CO2

AU - Yang, Peng

AU - Bracco, Jacquelyn N.

AU - Camacho Meneses, Gabriela

AU - Yuan, Ke

AU - Stubbs, Joanne E.

AU - Boamah, Mavis D.

AU - Brahlek, Matthew

AU - Sassi, Michel

AU - Eng, Peter J.

AU - Boebinger, Matthew G.

AU - Borisevich, Albina

AU - Wanhala, Anna K.

AU - Wang, Zheming

AU - Rosso, Kevin M.

AU - Stack, Andrew G.

AU - Weber, Juliane

PY - 2025/2/25

Y1 - 2025/2/25

N2 - Direct air capture (DAC) may be feasible to remove carbon dioxide (CO2) from the atmosphere at the gigaton scale, holding promise to become a major contributor to climate change mitigation. Mineral looping using magnesium oxide (MgO) is potentially an economical, efficient, and sustainable pathway to gigaton-scale DAC. The hydroxylation and carbonation of MgO determine the efficiency of the looping process, but their rates and mechanisms remain uncertain. In this work, MgO single crystals were reacted in air or CO2 at varying humidities and characterized by X-ray scattering, microscopy, and vibrational spectroscopy. Results show that the hydroxylation formed a brucite (Mg(OH)2)-like layer immediately after crystal cleaving. Concurrently, the carbonation formed hydrated magnesium carbonate phases, including barringtonite (MgCO3·2H2O) and nesquehonite (MgCO3·2H2O), in the layer. Rapid initial growth of the layer is also manifested in short-range bending/warping of nanocrystallites, resulting in multiple orientations of the same phases on the surface. The layer growth slowed down over time, indicating surface passivation. The formation of barringtonite and nesquehonite with 1:1 CO3/Mg ratio indicates an efficient carbonation when compared to other magnesium carbonate phases of lower ratio. Our results are essential for understanding surface passivation mechanisms and tackling the passivation issue of mineral looping DAC technology.

AB - Direct air capture (DAC) may be feasible to remove carbon dioxide (CO2) from the atmosphere at the gigaton scale, holding promise to become a major contributor to climate change mitigation. Mineral looping using magnesium oxide (MgO) is potentially an economical, efficient, and sustainable pathway to gigaton-scale DAC. The hydroxylation and carbonation of MgO determine the efficiency of the looping process, but their rates and mechanisms remain uncertain. In this work, MgO single crystals were reacted in air or CO2 at varying humidities and characterized by X-ray scattering, microscopy, and vibrational spectroscopy. Results show that the hydroxylation formed a brucite (Mg(OH)2)-like layer immediately after crystal cleaving. Concurrently, the carbonation formed hydrated magnesium carbonate phases, including barringtonite (MgCO3·2H2O) and nesquehonite (MgCO3·2H2O), in the layer. Rapid initial growth of the layer is also manifested in short-range bending/warping of nanocrystallites, resulting in multiple orientations of the same phases on the surface. The layer growth slowed down over time, indicating surface passivation. The formation of barringtonite and nesquehonite with 1:1 CO3/Mg ratio indicates an efficient carbonation when compared to other magnesium carbonate phases of lower ratio. Our results are essential for understanding surface passivation mechanisms and tackling the passivation issue of mineral looping DAC technology.

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