Water film-driven Mn (oxy)(hydr)oxide nanocoating growth on rhodochrosite

Luong, N. Tan; Ilton, Eugene S.; Shchukarev, Andrey; Boily, Jean-François

doi:10.1016/j.gca.2022.05.019

Cited by 6 publications

(3 citation statements)

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“…1–3 These films can affect chemical, structural, and functional properties of minerals in unique ways. 2–7 Understanding mineralogical transformations in water films can especially be useful in addressing phenomena related to atmospheric chemistry, catalysis, electrochemistry, geochemistry, and surface science. 8–12…”

Section: Introductionmentioning

confidence: 99%

“…[1][2][3] These films can affect chemical, structural, and functional properties of minerals in unique ways. [2][3][4][5][6][7] Understanding mineralogical transformations in water films can especially be useful in addressing phenomena related to atmospheric chemistry, catalysis, electrochemistry, geochemistry, and surface science. [8][9][10][11][12] Periclase (MgO; magnesia) is an ideal hydrophilic mineral 13,14 for tracking water film-driven transformations, 6,15 as its rock salt structure can readily transform to brucite nanosheets (MgO + H 2 O → Mg(OH) 2 ) (Fig.…”

Section: Introductionmentioning

confidence: 99%

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MgO nanocube hydroxylation by nanometric water films

2023

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

MgO nanocube hydroxylation by nanometric water films

2023

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“…Mineral nanoparticles capture air moisture in the form of water films that can be only a few monolayers (MLs) thick. − These form nanoscale hydration environments that can alter the composition, structure, and functional properties of materials in unique, yet still misunderstood, ways. − In particular, knowledge of (nano)coating growth within the confines of these films is essential to understand how exposure to air moisture alters mineral reactivity. This knowledge is of especial importance to atmospheric chemistry, catalysis, electrochemistry, environmental chemistry, geochemistry, and surface science …”

Section: Introductionmentioning

confidence: 99%

Water Film-Driven Brucite Nanosheet Growth and Stacking

Luong

Boily

2023

Langmuir

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Thin water films that form by the adhesion and condensation of air moisture on minerals can initiate phase transformation reactions with broad implications in nature and technology. We here show important effects of water film coverages on reaction rates and products during the transformation of periclase (MgO) nanocubes to brucite [Mg(OH) 2 ] nanosheets. Using vibrational spectroscopy, we found that the first minutes to hours of Mg(OH) 2 growth followed first-order kinetics, with rates scaling with water loadings. Growth was tightly linked to periclase surface hydration and to the formation of a brucite precursor solid, akin to poorly stacked/ dislocated nanosheets. These nanosheets were the predominant forms of Mg(OH) 2 growth in the 2D-like hydration environments of sub-monolayer water films, which formed below ∼50% relative humidity (RH). From molecular simulations, we infer that reactions may have been facilitated near surface defects where sub-monolayer films preferentially accumulated. In contrast, the 3D-like hydration environment of multilayered water films promoted brucite nanoparticle formation by enhancing Mg(OH) 2 nanosheet growth and stacking rates and yields. From the structural similarity of periclase and brucite to other metal (hydr)oxide minerals, this concept of contrasting nanosheet growth should even be applicable for explaining water film-driven mineralogical transformations on other related nanominerals.

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