Structure and properties of vanadium(V)-doped hexagonal turbostratic birnessite and its enhanced scavenging of Pb2+ from solutions

Yin, Hui; Feng, Xionghan; Tan, Wenfeng; Koopal, L.K.; Hu, Tiandou; Zhu, Mengqiang; Liu, Fan

doi:10.1016/j.jhazmat.2015.01.068

Cited by 31 publications

(20 citation statements)

References 62 publications

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“…The smaller sheet size can contribute to the more disordered stacking and fewer stacked sheets. Similar results were obtained for the synthesis of birnessite in the presence of vanadate . The sheet size decrease is caused by the chemical adsorption of the oxyanions on the edge sites, , inhibiting particle growth of the sheets (Scheme A) .…”

Section: Discussionsupporting

confidence: 73%

“…The control sample has five characteristic peaks of birnessite at ∼7.23, 3.61, 2.45, 1.41, and 1.22 Å. , The first two peaks correspond to the basal reflections (001) and (002), respectively. The remaining peaks are broadened by convolution of multiple reflections and can be indexed to (11, 20), (31, 02) and (22, 40), respectively . The products with P/Mn ≤ 0.3, Si/Mn ≤ 0.2, or S/Mn ≤ 1 possess these characteristic XRD peaks, indicating they are birnessite.…”

Section: Resultsmentioning

confidence: 99%

“…KOH washing removed the adsorbed oxyanions, resulting in increases of sheet sizes, which may occur via the oriented attachment. This study provides a method for synthesizing small particle size of birnessite with high concentration of stabile Mn(III), which may enhance birnessite catalytic activity for water oxidation and benefit other applications as well. ,,, In addition, the oxyanions used in the synthesis are economically viable and environmentally benign compared to vanadate used in a previous study …”

Section: Discussionmentioning

confidence: 98%

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Synthesis of Birnessite in the Presence of Phosphate, Silicate, or Sulfate

Wang

Liao

et al. 2016

Inorg. Chem.

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Layered manganese (Mn) oxides, such as birnessite, are versatile materials in industrial applications and common minerals mediating elemental cycling in natural environment. Many of birnessite properties are controlled by Mn(III) concentration and particle sizes. Thus, it is important to synthesize birnessite nanoparticles with controlled Mn(III) concentrations and sizes so that one can tune its properties for many applications. Birnessite was synthesized in the presence of oxyanions (phosphate, silicate, or sulfate) during reductive precipitation of KMnO by HCl and characterized using multiple synchrotron X-ray techniques, electron microscopy, and diffuse reflectance UV-vis spectroscopy. Results indicate that all three anions decrease MnO sheet sizes, attributed to oxyanion adsorption on edges of the sheets, inhibiting their lateral growth. As a result of decreased sizes, sheets undergo significant structural contraction. Meanwhile, Mn(III) concentration significantly increases with increasing oxyanion/Mn ratio. The increased Mn(III) concentration, along with the decreased size, enlarges both direct and indirect band gaps of birnessite. Phosphate imposes the strongest influence, followed by silicate and then by sulfate, consistent with their decreasing adsorption affinity. Reacting with 1 M KOH solution effectively removed the adsorbed oxyanions while leading to increased sheet sizes, probably due to oriented attachment-driven particle growth mechanisms. The results have important implications for developing highly performed birnessite materials, for example, small size Mn(III)-rich birnessite for photochemical and catalytic applications, as well as for understanding chemical compositional variations of naturally occurring birnessite.

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Section: Discussionsupporting

confidence: 73%

Section: Resultsmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 98%

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Synthesis of Birnessite in the Presence of Phosphate, Silicate, or Sulfate

Wang

Liao

et al. 2016

Inorg. Chem.

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“…A DES complex can evolve into a triple-edge-sharing complex (TES) and incorporate progressively into the MnO 2 layer during the crystal growth. The identification of some of the surface species (INC, TCS, DCS, and DES) has led to accelerating research aimed to understand their thermodynamic stability − and how the mineral structure, layer size, and chemical composition control the metal sorption selectivity and capacity per specific surface area. ,,− …”

Section: Introductionmentioning

confidence: 99%

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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“…Manganese oxides (MnO x ), especially layered phyllomanganates, are important metal oxides in terrestrial and oceanic environments [1][2][3]. Because of the high surface area, negative surface charge, vacancy sites, and high oxidative potential, phyllomanganates have a strong tendency to interact with and strongly influence the fate and transport of trace metals, such as Ni [4][5][6][7][8], Co [6,[8][9][10][11][12][13], Pb [7,[14][15][16][17][18], Cu [6,19,20], Zn [4,7,17,[21][22][23], and Cd [24,25]. Phyllomanganates can interact with metals in different ways (e.g., sorption, coprecipitation, incorporation), which in turn can affect the property and reactivity of the host mineral phases.…”

Section: Introductionmentioning

confidence: 99%

Zinc Presence during Mineral Formation Affects the Sorptive Reactivity of Manganese Oxide

Zhao

Liu

et al. 2018

Soil Systems

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The sorptive reactivity of layered manganese (Mn) oxides is controlled by their layer and interlayer structure, which can be affected by processes such as metal coprecipitation. This study investigated the effects of Zn coprecipitation on the sorptive reactivity of δ-MnO 2 , a common layered Mn oxide mineral. Selected cation (i.e., Cd) and anion (i.e., phosphate and arsenate) species were used to probe the changes in δ-MnO 2 sorptive reactivity. Cd uptake by δ-MnO 2 was suppressed by Zn coprecipitation but total metal uptake (Cd and Zn) was enhanced, indicating more available vacancy sites (e.g., smaller particle size and higher vacancy site density) in Zn-coprecipitated δ-MnO 2. Phosphate and arsenate sorption on δ-MnO 2 was significantly enhanced by Zn-coprecipitation, and the enhancement was more effective compared to Zn sorption on pure δ-MnO 2. X-ray diffraction and X-ray adsorption spectroscopy analysis did not detect the formation of surface precipitations and/or ternary complexes. The enhanced anion sorption on Zn-coprecipitated δ-MnO 2 was likely due to the compensation of negative surface charge by sorbed Zn, as well as the structural modifications introduced by Zn coprecipitation. Results from this study can provide a better understanding on the interactions between metal-coprecipitated Mn oxides and other species in natural environments.

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Structure and properties of vanadium(V)-doped hexagonal turbostratic birnessite and its enhanced scavenging of Pb2+ from solutions

Cited by 31 publications

References 62 publications

Synthesis of Birnessite in the Presence of Phosphate, Silicate, or Sulfate

Synthesis of Birnessite in the Presence of Phosphate, Silicate, or Sulfate

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

Zinc Presence during Mineral Formation Affects the Sorptive Reactivity of Manganese Oxide

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