Optimal Location of Vanadium in Muscovite and Its Geometrical and Electronic Properties by DFT Calculation

Zheng, Qiushi; Zhang, Yimin; Liu, Tao; Huang, Jing; Xue, Nan; Shi, Qihua

doi:10.3390/min7030032

Cited by 26 publications

(17 citation statements)

References 33 publications

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“…The changes in V mineral chemistry in deep time, particularly related to redox state and the incorporation of hydrogen, are likely influenced by the exclusive presence of meteoritic sources at >4.0 Ga, the transition to massive volcanic sulfide deposits and igneous sources from 4.0 to 2.9 Ga, evolving tectonic processes that resulted in porphyry development and involvement of water in mineral formation from 2.9 to 2.6 Ga, and finally the expanding oxidizing conditions from <2.5 to 1.6 Ga (Figures , and ; Table S3). The elements V and Al have a strong association in geologic time evidenced by the common substitution of V for Al in clays, particularly illite and muscovite (Meunier, ; Pan & Fleet, ; Zheng et al, ). Al is also an important mineral‐forming element with V throughout the mineral record, forming minerals predominately with V(III) at ≥1.6 Ga and increasingly with V(V) and V(IV) at <1.6 Ga (Figures and ).…”

Section: Discussionmentioning

confidence: 99%

The evolving redox chemistry and bioavailability of vanadium in deep time

et al. 2020

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The incorporation of metal cofactors into protein active sites and/or active regions expanded the network of microbial metabolism during the Archean eon. The bioavailability of crucial metal cofactors is largely influenced by earth surface redox state, which impacted the timing of metabolic evolution. Vanadium (V) is a unique element in geo–bio‐coevolution due to its complex redox chemistry and specific biological functions. Thus, the extent of microbial V utilization potentially represents an important link between the geo‐ and biospheres in deep time. In this study, we used geochemical modeling and network analysis to investigate the availability and chemical speciation of V in the environment, and the emergence and changing chemistry of V‐containing minerals throughout earth history. The redox state of V shifted from a more reduced V(III) state in Archean aqueous geochemistry and mineralogy to more oxidized V(IV) and V(V) states in the Proterozoic and Phanerozoic. The weathering of vanadium sulfides, vanadium alkali metal minerals, and vanadium alkaline earth metal minerals were potential sources of V to the environment and microbial utilization. Community detection analysis of the expanding V mineral network indicates tectonic and redox influence on the distribution of V mineral‐forming elements. In reducing environments, energetic drivers existed for V to potentially be involved in early nitrogen fixation, while in oxidizing environments vanadate (VO43-false]false]>) could have acted as a metabolic electron acceptor and phosphate mimicking enzyme inhibitor. The coevolving chemical speciation and biological functions of V due to earth's changing surface redox conditions demonstrate the crucial links between the geosphere and biosphere in the evolution of metabolic electron transfer pathways and biogeochemical cycles from the Archean to Phanerozoic.

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Section: Discussionmentioning

confidence: 99%

The evolving redox chemistry and bioavailability of vanadium in deep time

et al. 2020

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“…The muscovite model in this study was calculated considering the quarter substitution of Si by Al [25]. We optimized the structure with half and all K substituted by H to clarify structural changes after K release.…”

Section: Formation Of the 001 Surface Hydroxylmentioning

confidence: 99%

“…The initial crystal structure of muscovite was taken from the optimized geometrical model of Zheng et al (2017) [25] with a = 5.29 Å, b = 9.12 Å, c = 20.26 Å, and β = 95.83 • . The mean distances and angles in the model match the experimental data within differences less than 3%.…”

Section: Structure Calculationsmentioning

confidence: 99%

Removal Process of Structural Oxygen from Tetrahedrons in Muscovite during Acid Leaching of Vanadium-Bearing Shale

et al. 2018

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Process mineralogy shows that most vanadium in mica-type black shale exists in the octahedral sites of muscovite. The extraction of vanadium mainly occurs in the acid leaching process with participation of H ions. In this work, we firstly analyzed the dissolution rules of elements in acid leaching of muscovite, then adopted the density functional theory (DFT) calculation to accurately visualize the primary process of the surface corrosion of muscovite by H ions. The experimental results show that K releases the fastest and the release of Al is consistent with K. The simulation results find that the H preferentially shifts to the unsaturated structured O of the tetrahedron to form a strong 001 surface hydroxyl after replacing K, as well as relaxing the near Al(Si)-O bonds for the further removal of structural oxygen. Then, the 001 surface hydroxyls more likely participate in the dehydroxylation reaction through the reverse-path mechanism to remove the structural oxygen and break the hexagonal rings of the tetrahedral sheets. Remarkably, the formation and removal of structural water are overall endoergic, meaning that the disintegration of muscovite requires a sustained supply of heat. Further, the octahedral sheets where vanadium exists can be exposed to the acid environment for overall destruction. This detailed atomic migration process in acid leaching of black shale is visualized, which not only illuminates the reaction mechanism of H ions with the muscovite, but also provides guidance for vanadium extraction from black shale and a new concept for the destruction of other minerals.

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“…Vanadium is a significant strategic resource which plays an important role in many fields, such as ferrous and nonferrous alloy production, thermistors, redox flow batteries, catalysts, the chemical industry, and medicine [1][2][3][4][5]. China has very large reserves of stone coal, which is a special vanadium-containing resource for the country.…”

Section: Introductionmentioning

confidence: 99%

Effect of CaF2/CaO Composite Additive on Roasting of Vanadium-Bearing Stone Coal and Acid Leaching Kinetics

et al. 2017

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Abstract:In this paper, the composite additive of CaF 2 /CaO was used to extract vanadium from stone coal, and the effect of roasting and leaching kinetics were studied. The purpose of this manuscript is to realize and improve the vanadium recovery from stone coal using the composite additive. The experimental results indicated that the roasted clinker can be obtained under the conditions of CaF 2 /CaO at a mass ratio of 2:3 and a total additive amount of 10 wt %, a roasting temperature 850 • C, and a roasting time of 90 min. The leaching rate of vanadium can reach 86.74%, which increased by 16.4% compared with that of blank roasting under the conditions including a leaching temperature of 950 • C, a sulfuric acid concentration of 15% (v/v), a leaching time of 2 h, and a ratio of liquid to solid of 3 mL/g. The phase transformation analysis indicated that the muscovite structure was effectively destroyed during the roasting process comparing with no additives, which provided the basis for vanadium dissociation. Roasting can promote the formation of calcium vanadate, which is beneficial to the leaching of vanadium. The vanadium leaching kinetic analysis indicated that the activation energy of the acid leaching reaction decreased from 42.50 KJ/mol in the blank roasting to 22.56 KJ/mol in the calcified roasting, and the reaction order, with respect to the sulfuric acid concentration, decreased from 1.15 to 0.85. Calcified roasting has a better mineral activation than blank roasting, which can accelerate the leaching of vanadium and reduce the dependence on high-temperature and high acid levels in the leaching process.

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Optimal Location of Vanadium in Muscovite and Its Geometrical and Electronic Properties by DFT Calculation

Cited by 26 publications

References 33 publications

The evolving redox chemistry and bioavailability of vanadium in deep time

The evolving redox chemistry and bioavailability of vanadium in deep time

Removal Process of Structural Oxygen from Tetrahedrons in Muscovite during Acid Leaching of Vanadium-Bearing Shale

Effect of CaF2/CaO Composite Additive on Roasting of Vanadium-Bearing Stone Coal and Acid Leaching Kinetics

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