Trivalent manganese on vacancies triggers rapid transformation of layered to tunneled manganese oxides (TMOs): Implications for occurrence of TMOs in low-temperature environment

Yang, Peng; Lee, Seung‐Yeol; Post, Jeffrey E.; Xu, Huifang; Wang, Qian; Xu, Wenqian; Zhu, Mengqiang

doi:10.1016/j.gca.2018.08.014

Cited by 36 publications

(90 citation statements)

References 80 publications

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“…The combined synchrotron XRD/PDF is also sensitive to study the interlayer species in the vernadite structure. The combined methods will be useful for determining other crystal structures of poorly crystallized nanominerals (Lee et al, 2016;Yang et al 2018).…”

Section: Discussionmentioning

confidence: 99%

The structure and crystal chemistry of vernadite in ferromanganese crusts

Lee

et al. 2019

Acta Crystallogr Sect B

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The structure and crystal chemistry of vernadite in ferromanganese crusts from the Magellan Seamount in the north-west Pacific Ocean have been investigated using synchrotron X-ray diffraction (XRD), X-ray pair distribution function (PDF) and high-resolution transmission electron microscopy (TEM). XRD patterns of vernadite mainly show two strong diffraction peaks at 2.42-2.43 Å and 1.41 Å without or with a broad (001) diffraction peak, indicating thin layer nanophases along the c-direction. TEM images show flat and curved sheet-like nanocrystals with (001) layer thickness of $7.2 Å and $9.6 Å , and their interstratified structure. PDF patterns of the vernadite are similar to those from synthetic -MnO 2 and defective birnessite, suggesting a phyllomanganate framework. Combined XRD/PDF patterns suggest that vernadite in the outer part is associated with a higher density interlayer species at triple-edge sharing sites. The proportion of the 10 Å phase increases from the outer (young) part to the inner (old) part of the Mn crusts due to aging and sorption of Mn, Co and Ni from ambient seawater. This study suggests that this combined method of synchrotron radiation XRD/PDF and high-resolution TEM is a powerful tool to determine atomic structures of poorly crystallized nano-minerals. The mixture model of vernadite structure will help to understand the partitioning and distribution of trace elements in the ferromanganese crusts.

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Section: Discussionmentioning

confidence: 99%

The structure and crystal chemistry of vernadite in ferromanganese crusts

Lee

et al. 2019

Acta Crystallogr Sect B

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“…cations from layer to interlayer or layer kinking at these structurally weak points contribute to building tunnel walls (Grangeon et al, 2008(Grangeon et al, , 2014Atkins et al, 2014Atkins et al, , 2016Yang et al, 2018). In the present case, the ordered distribution of Mn(III) cations in rows parallel to the b axis and separated from each other along the a axis by two rows of Mn(IV) creates a structurally weak point favorable to the formation of tunnels walls (Atkins et al, 2014;Grangeon et al, 2014).…”

Section: The Role Of Mn(iii) and Interlayer Species During The Transfmentioning

confidence: 68%

Transformation of Ni-containing birnessite to tectomanganate: Influence and fate of weakly bound Ni(II) species

Lanson

Feng

et al. 2020

Geochimica et Cosmochimica Acta

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The geochemical behavior of nickel, an essential trace metal element, strongly depends on its interactions with Mn oxides. Interactions between the phyllomanganate birnessite and sorbed or structurally incorporated Ni have been extensively documented together with the fate of Ni along the transformation of these layered species to tunnel Mn oxides (tectomanganates). By contrast, interactions of phyllomanganates with weakly bound Ni species (hydrated Ni, Ni (hydr)oxides), that possibly prevail in natural Ni-rich (>10% NiO) manganates received little attention and the influence of these Ni species on the phyllomanganate-to-tectomanganate transformation remains essentially unknown. Within this framework, a set of phyllomanganate precursors with contrasting contents of Ni were prepared and subjected to a reflux process mimicking the natural phyllomanganate-to-tectomanganate conversion. Layered precursors and reflux products were characterized with a combination of diffractometric, spectroscopic, thermal, and chemical methods. Ni is essentially present as hydrated Ni(II) and Ni(II) (hydr)oxides in layered precursors with no detectable Ni sorbed at layer vacancy sites or structurally incorporated. Despite the high content (~1/3) of Jahn-Teller distorted Mn(III) octahedra in these layered precursors, which is known to be favorable to their conversion to tectomanganates, polymerization of Ni(OH) 2 in phyllomanganate interlayers is kinetically favored during reflux process. Asbolane, a phyllomanganate with an incompleteisland-likeoctahedral layer of metal (hydr)oxides, is thus formed rather than todorokite, a common tectomanganate with a uniform 3×3 tunnel structure. A nitric acid treatment, aiming at the dissolution of the island-like interlayer Ni(OH) 2 layer, allows an easy and unambiguous differentiation between asbolane and todorokite, which is unaffected by the treatment. Both compounds exhibit indeed similar periodicities and can be confused when using X-ray diffraction, despite contrasting intensity ratios. Ni(OH) 2 polymerization hampers the formation of tectomanganates and likely contributes to the prevalence of phyllomanganates over tectomanganates in natural environments. Most Ni is retained during the reflux process, part of Ni (~20%) being likely structurally incorporated in the reaction products, thus enhancing the sequestration of Ni in Mn oxides.

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“…1(d)). 31,32 Tectomanganate conversion as the material is heated and dehydrated is substantiated by the reduction of Mn L /Mn L (2.85, 4.95Å) and reciprocal increase of Mn L /Mn IL (3.45, 5.32 A) correlations, appearing clearly in the difference PDF (Fig. 6).…”

Section: Powder Diffraction Inferencementioning

confidence: 88%

“…6), suggesting lateral coherence of the atomic structure is maintained which is consistent with an interlayer condensation mechanism. 32 (5) Increasing the 3D polymerization of the MnO 6 framework up to $30% in these nanostructured occs increases the kinetic barrier to Na intercalation, as indicated by the rate dependence of the electrode specic capacitance. We note that the population of interlayer Mn 3+ and intralayer Mn-vacancies is controlled in the starting material by equilibration of d-MnO 2 occs at a particular pH.…”

Section: Summary Of Findingsmentioning

confidence: 99%

“…Because of this structural proximity, interconversion between these structures is common. [30][31][32][33][34] The sensitivity of Mn species to environmental factors results in the ready oxidation and reduction of manganates. Coupled with the Jahn-Teller distortion of Mn 3+ O 6 , these changes to the Mn electronic conguration result in straindriven alterations to the edge-shared MnO 6 network.…”

Section: Introductionmentioning

confidence: 99%

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Hierarchical porosityvialayer-tunnel conversion of macroporous δ-MnO₂nanosheet assemblies

et al. 2020

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Trivalent manganese on vacancies triggers rapid transformation of layered to tunneled manganese oxides (TMOs): Implications for occurrence of TMOs in low-temperature environment

Cited by 36 publications

References 80 publications

The structure and crystal chemistry of vernadite in ferromanganese crusts

The structure and crystal chemistry of vernadite in ferromanganese crusts

Transformation of Ni-containing birnessite to tectomanganate: Influence and fate of weakly bound Ni(II) species

Hierarchical porosityvialayer-tunnel conversion of macroporous δ-MnO₂nanosheet assemblies

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Trivalent manganese on vacancies triggers rapid transformation of layered to tunneled manganese oxides (TMOs): Implications for occurrence of TMOs in low-temperature environment

Cited by 36 publications

References 80 publications

The structure and crystal chemistry of vernadite in ferromanganese crusts

The structure and crystal chemistry of vernadite in ferromanganese crusts

Transformation of Ni-containing birnessite to tectomanganate: Influence and fate of weakly bound Ni(II) species

Hierarchical porosityvialayer-tunnel conversion of macroporous δ-MnO2nanosheet assemblies

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Hierarchical porosityvialayer-tunnel conversion of macroporous δ-MnO₂nanosheet assemblies