Time-Resolved Investigation of Cobalt Oxidation by Mn(III)-Rich δ-MnO<sub>2</sub>Using Quick X-ray Absorption Spectroscopy

Simanova, Anna A.; Peña, J. Theodore

doi:10.1021/acs.est.5b01088

Cited by 70 publications

(76 citation statements)

References 66 publications

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“…These observations challenge the TCS-INC pathway for the incorporation of Ni in the layer of natural phyllomanganates, and suggest that it is incorporated instead on the edges of the octahedral layers during the crystal growth (DES-INC pathway). That layer edge sites have higher surface reactivity toward Ni is consistent with the faster rates of oxidation of As(III) to As(V), 56 and of Co(II) to Co(III), 72,93 on the layer edge sites of δ-MnO2 and birnessite relative to vacancy sites. fluctuates between tetragonally elongated octahedral (Jahn-Teller distortion, JT), square pyramidal (five-fold), and trigonal bipyramidal (five-fold) coordination, with an average number estimated to 5.7 H2O molecules.…”

Section: Introductionsupporting

confidence: 60%

Nature of High- and Low-Affinity Metal Surface Sites on Birnessite Nanosheets

Manceau

Steinmann

2021

ACS Earth Space Chem.

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Birnessite nanosheets (δ-MnO2) are key reactive nanoparticles that regulate metal cycling in terrestrial and marine settings, yet there is no molecular explanation for the sorption selectivity of metals which controls their enrichment. This fundamental question was addressed by optimizing the structure of the Ni, Cu, Zn, and Pb surface complexes on δ-MnO2 and by calculating the Gibbs free energy change (ΔG) of the sorption reactions with density functional theory. The sorption selectivity follows the order Pb > Cu > Ni > Zn, in good agreement with experimental data. Cu, Ni, and Zn bind preferentially to layer edges at low surface coverage forming double-edge-sharing (DES) complexes, whereas Pb binds extensively with high selectivity over the three transition metals to both layer edges (DES bonding) and to basal planes forming triple-corner-sharing (TCS) complexes. Pb has similar affinity for the DES and TCS sites at pH 5 and a higher affinity for the TCS sites at circumneutral pH. The Pb DES and TCS complexes are both dehydrated at the δ-MnO2-water interface and feature a trigonal pyramidal geometry with three surface O atoms. The high stability of the two new complexes arises from the hybridization between the Pb 6s/6p and the O 2p states, forming a strongly covalent Pb-O/OH bond at the δ-MnO2 surface. The quantum chemical results provide mechanistic and energetics insight on metal uptake on δ-MnO2 that extends what extended X-ray absorption fine structure (EXAFS) spectroscopy alone can provide.

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Section: Introductionsupporting

confidence: 60%

Nature of High- and Low-Affinity Metal Surface Sites on Birnessite Nanosheets

Manceau

Steinmann

2021

ACS Earth Space Chem.

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“…In contrast and consistent with previous reports (Manceau et al, 1997;Yu et al, 2012;Kwon et al, 2013;Simanova and Pena, 2015;Yin et al, 2015), Co(II) is readily oxidized by birnessite during the formation of initial layered precursors with Co(III)…”

Section: Negative Influence Of Ni and Co On The Phyllo-to-tectomangansupporting

confidence: 91%

“…In an effort to disentangle the mobility, (bio)availability, and fate of these elements in different geological settings, structural interactions of phyllomanganates with such foreign elements, and more especially with transition metals, have thus attracted the attention of the scientific community over the last few decades (Manceau et al, 1997(Manceau et al, , 2002(Manceau et al, , 2014Ohta and Kawabe, 2001;Lanson et al, 2002a;Marcus et al, 2004;Toner et al, 2006;Peacock and Sherman, 2007a,b;Peacock, 2009;Peña et al, 2010;Roque-Rosell et al, 2010;Sherman and Peacock, 2010;Yin et al, 2011a,b;Kwon et al, 2013;Yu et al, 2013;Burlet and Vanbrabant, 2015;. In most studies, foreign elements were structurally substituted for Mn(IV) in the MnO 6 octahedra or sorbed as inner-sphere complexes either at vacant layer sites and/or at particle edges (Manceau et al, 1997;Yin et al, 2011aYin et al, , 2015Yu et al, 2013;Ohnuki et al, 2015;Simanova and Pena, 2015;Qin et al, 2018). Similar to other transition metals, presence of Ni(II) forming inner-sphere complexes species at vacancy or edge sites and/or structurally incorporated in phyllomanganate layers has been extensively documented (Manceau et al, 2002(Manceau et al, , 2007aPeacock and Sherman, 2007a,b;Grangeon et al, 2008;Peña et al, 2010;Yin et al, 2012Yin et al, , 2014Kwon et al, 2013;.…”

Section: Introductionmentioning

confidence: 99%

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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“…[9][10][11][12][13][14][15][16] as well as adsorbs and oxidizes elements such AsĲIII), CoĲII), and CrĲIII). [17][18][19][20][21][22] Manganese oxides are also considered as promising oxidants for a broad range of organic compounds including antibacterial agents, endocrine disruptors, and other pharmaceuticals. 8 In addition, the sorption and redox properties of birnessite have been investigated in technical systems for their potential use in remediation strategies 7,23,24 or as water oxidation catalysts.…”

Section: Introductionmentioning

confidence: 99%

Crystal growth and aggregation in suspensions of δ-MnO₂nanoparticles: implications for surface reactivity

Marafatto

Lanson

Peña

2018

Environ. Sci.: Nano

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a Birnessite (layer-type Mn oxide) is a key reactive phase in soils and sediments and its sorption and oxidative properties render it attractive for use in technical applications. The most widely used synthetic analog of natural and biogenic birnessite in laboratory studies is nanocrystalline δ-MnO 2 . However, a wide range of physicochemical properties have been reported in the literature for δ-MnO 2 . In this study, we produced several batches of δ-MnO 2 and identified the mechanisms leading to significant variations in particle size, as probed by X-ray diffraction (3 to 7 nm), dynamic light scattering (85 to 501 nm) and N 2 Ĳg) BET specific surface area (SSA: 119 to 259 m 2 g −1) measurements. Both the coherent scattering domain (CSD) size in the ab plane and the wet-aggregate size decreased with increasing suspension pH and Na content, which is consistent with base-catalyzed oxidation and nucleation at high pH and growth by oriented attachment at low pH. The increase in the CSD size upon sample acidification but not basification provides further evidence for OA as a crystal growth mechanism. Finally, the sample SSA was not related to the crystallite size, but instead was inversely correlated to the suspension pH and Na : Mn content. The surface charge and counter-cation content of δ-MnO 2 control the aggregate structure, where low pH (low Na : Mn) favored high surface area structures and high pH (high Na : Mn) favored low surface area structures. The reversibility of SSA upon the acidification or basification of parent suspensions and the crystal growth only upon suspension acidification confirmed that the primary crystallite size and the aggregate/agglomerate size are highly sensitive to solution chemistry and surface charge and has direct implications for δ-MnO 2 nanoparticle reactivity towards organic and inorganic contaminants in environmental systems that can encompass a dynamic range of pH values and ionic compositions.

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Time-Resolved Investigation of Cobalt Oxidation by Mn(III)-Rich δ-MnO₂Using Quick X-ray Absorption Spectroscopy

Cited by 70 publications

References 66 publications

Nature of High- and Low-Affinity Metal Surface Sites on Birnessite Nanosheets

Nature of High- and Low-Affinity Metal Surface Sites on Birnessite Nanosheets

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

Crystal growth and aggregation in suspensions of δ-MnO₂nanoparticles: implications for surface reactivity

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Time-Resolved Investigation of Cobalt Oxidation by Mn(III)-Rich δ-MnO2Using Quick X-ray Absorption Spectroscopy

Cited by 70 publications

References 66 publications

Nature of High- and Low-Affinity Metal Surface Sites on Birnessite Nanosheets

Nature of High- and Low-Affinity Metal Surface Sites on Birnessite Nanosheets

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

Crystal growth and aggregation in suspensions of δ-MnO2nanoparticles: implications for surface reactivity

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Time-Resolved Investigation of Cobalt Oxidation by Mn(III)-Rich δ-MnO₂Using Quick X-ray Absorption Spectroscopy

Crystal growth and aggregation in suspensions of δ-MnO₂nanoparticles: implications for surface reactivity