Sonochemical synthesis of mackinawite and the role of Cu addition on phase transformations in the Fe–S system

Zavašnik, Janez; Stanković, Nadežda; Arshad, Muhammad Shahid; Rečnik, Aleksander

doi:10.1007/s11051-013-2223-z

Cited by 13 publications

(18 citation statements)

References 33 publications

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“…However, we found that the c parameter did not decrease monotonically: initially it increased slightly with increasing x and then decreased when x > 0.125. By contrast, the volume of Fe 1-x Cu x S increases as a function of x because of the increase in both a and c, which is consistent with experimental observations for Cu-reacted amorphous FeS nanoparticles (Zavašnik et al 2014). …”

Section: Transition Metal Substitution In Fessupporting

confidence: 90%

“…This greater stability of Sub over I-td is also consistent with structural data. For Cu-reacted FeS nanoparticles, both a and c are larger than for pure FeS (Zavašnik et al 2014). This increase in the lattice parameters with Cu incorporation matches only our Cu-Sub trends (Figs.…”

Section: Deducing Incorporation Mechanismssupporting

confidence: 86%

“…Metal incorporation has been postulated to increase the stability of mackinawite (Takeno and Clark 1967;Zavašnik et al 2014). Our finding of a negative DE f of Co-Sub and Ni-Sub supports this hypothesis, and shows further that the mechanism is substitution, not intercalation.…”

Section: Deducing Incorporation Mechanismssupporting

confidence: 83%

“…This proposal has been widely cited in the literature (Morse and Rickard 2004;Muñoz-Santiburcio et al 2013;Mullet et al 2002;Watson et al 1995;Wolthers et al 2003). Zavašnik et al (2014) observed a significant increase in the unit-cell size (a = 3.76 Å, c = 5.43 Å) for amorphous FeS nanoparticles reacted with Cu (Cu:Fe ratio ≈ 0.1). They conjectured that Cu intercalates into mackinawite leading to the cell expansion.…”

mentioning

confidence: 62%

“…intRoduction Transition-metal-enriched mackinawite (tetragonal FeS) is an excellent system to gain insight into the effects of metal incorporation on sulfide mineral phase transformations and to understand the formation processes of metal sulfide ore deposits (Blain 1978;Lennie and Vaughan 1996;Takeno and Clark 1967;Zôka et al 1972;Zavašnik et al 2014). Structurally, mackinawite comprises edge-sharing sheets of FeS 4 tetrahedra arranged on a tetragonal lattice (P4/nmm symmetry, with a = b = 3.67 Å, c = 5.03 Å) and stacked along the c direction, with stabilization through van der Waals (vdW) interactions (Lennie et al 1995;Rickard et al 2006).…”

mentioning

confidence: 99%

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Transition metal incorporation into mackinawite (tetragonal FeS)

Kwon

Refson

Sposito

2015

American Mineralogist

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Naturally occurring mackinawite (tetragonal FeS) with incorporated transition metals is an important precursor to the formation of metal sulfides in ore deposits, but experimental results have not been sufficient to establish clear trends in the structure and stability of the transition-metal-enriched mineral. Using density functional theory with dispersion corrections, we report the first systematic examination of the relationship between composition and structure for FeS incorporating bivalent transition metals. Our method was validated by successful calculations of the structures of FeS, FeSe, FeSe 1-x S x , Fe 1-x Me x Se (Me = Co, Ni, Cu), and FeNi x Te. Two classes of transition-metal-incorporated FeS structures then were investigated: Fe 1-x Me x S (metal-substituted FeS) and FeMe x S (FeS intercalated by a metal at either a tetrahedral or square-pyramidal interstitial site), where Me = Co, Ni, and Cu, and x ≤ 0.25. We find that incorporated transition metals can both increase and decrease lattice parameters, depending on the metal and how it is incorporated into the FeS structure. As the mole fraction of substituting metal increases, the FeS unit-cell volume decreases for Co, is nearly constant for Ni, but increases for Cu. Metal substitution changes the c lattice parameter, which is sensitive to interactions between the mackinawite sheets, as much as it does the a and b lattice parameters. Upon intercalation, the unit-cell volume and c parameter increase but the a and b parameters decrease. Experimental structural data are consistent with our results for metal-substituted FeS. We determined the thermodynamic stability of metal-incorporated FeS by computing the free energy involved in the metal incorporation reactions as a function of chemical potential of sulfur. The thermodynamic results lead to the general conclusions that metal incorporation into mackinawite most likely occurs via substitution, which may be important to influence phase transformation pathways of mackinawite.

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Section: Transition Metal Substitution In Fessupporting

confidence: 90%

Section: Deducing Incorporation Mechanismssupporting

confidence: 86%

Section: Deducing Incorporation Mechanismssupporting

confidence: 83%