10.1021/acs.jpcc.9b08005.s001
Chao Qi
Chao
Qi
Mohammad Khalkhali
Mohammad
Khalkhali
James S. Grundy
James S.
Grundy
Jing Liu
Jing
Liu
Jonathan Malainey
Jonathan
Malainey
Qingxia Liu
Qingxia
Liu
Unraveling Polymorphic Pyrrhotite Electrochemical
Oxidation by Underlying Electronic Structures
American Chemical Society
2019
Fe 9 S 10
Unraveling Polymorphic Pyrrhotite Electrochemical Oxidation
oxygen atoms
pyrrhotite
OH
bond
oxygen abundance difference
ion mass spectrometry
S 3 p band center
H 2 O
DFT
oxidation rate difference
Fe 7 S 8
Electronic Structures Metal sulfide oxidation
electrochemical oxidation rate
2019-10-18 20:43:26
Journal contribution
https://acs.figshare.com/articles/journal_contribution/Unraveling_Polymorphic_Pyrrhotite_Electrochemical_Oxidation_by_Underlying_Electronic_Structures/10005365
Metal sulfide oxidation
is a common, yet poorly understood, phenomenon
that significantly affects surface properties. In this paper, we studied
the electrochemical oxidation of polymorphic pyrrhotites (Fe<sub>1–<i>x</i></sub>S) to gain insights into the relationship between
their electrochemical oxidation rate and electronic structures. Surface
composition of oxidized pyrrhotites, as shown by time-of-flight secondary
ion mass spectrometry (ToF-SIMS) and X-ray photoelectron spectroscopy (XPS),
suggested that one key step for pyrrhotite oxidation is the outward
diffusion of metal cations to form polysulfide and oxides. This diffusion
process involves the rupture of Fe–S bonds and, hence, depends
on the Fe–S bond strength. According to the ToF-SIMS, the Fe–S
bond strength in the defective layer (>100 nm), the layer right
underneath
the polysulfide layer (∼20 nm), was modified by the incorporation
of oxygen atoms, which mainly existed in the form of OH<sup>–</sup> and H<sub>2</sub>O. It was found that oxygen anions are much more
abundant in the defective layer of monoclinic pyrrhotite (Fe<sub>7</sub>S<sub>8</sub>) than that of hexagonal pyrrhotite (Fe<sub>9</sub>S<sub>10</sub>), resulting in a much weaker Fe–S bond with the former
than the latter. The oxygen abundance difference can be explained
by their electronic structures. Density functional theory (DFT) calculation
showed that monoclinic pyrrhotite (Fe<sub>7</sub>S<sub>8</sub>) get
a higher Fe <i>3d</i> and S <i>3p</i> band center
than hexagonal pyrrhotite (Fe<sub>9</sub>S<sub>10</sub>). Therefore,
monoclinic pyrrhotite could incorporate oxygen atoms easier than hexagonal
pyrrhotite. This presented a clear relation between polymorphic pyrrhotite
electronic structures and their electrochemical oxidation rate and
also fundamentally explained why the sulfides with a slight bulk metal–sulfur
bond strength difference could demonstrate a significant oxidation
rate difference.