Applied Surface Science 514 (2020) 145876

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Applied Surface Science

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Full Length Article

DFT insights to mercury species mechanism on pure and Mn doped T

Fe3O4(1 1 1) surfaces
⁎,1
Jiamin Chena, Wenxin Zhua, Xiong Changa, Ding Dinga, Tingting Zhanga, Changsong Zhoua, ,
Hao Wua, Hongmin Yanga, Lushi Sunb
a
Engineering Laboratory of Energy System Process Conversion and Emission Reduction Technology of Jiangsu Province, School of Energy and Mechanical Engineering,
Nanjing Normal University, 210042 Nanjing, China
b
State Key Laboratory of Coal Combustion, Huazhong University of Science and Technology, 430074 Wuhan, China

A R T I C LE I N FO A B S T R A C T

Keywords: The interaction between mercury species and Fe3O4(1 1 1), Mn doped Fe3O4(1 1 1) surfaces, with Feoct2- ter-
Mercury mination has been calculated by density functional theory (DFT). Different adsorption sites and placement of
Density functional theory adsorbates, potential catalytic oxidation of Hg0 by the adsorbed Cl atoms on the Mn-doped Fe3O4 surface have
Mn-Fe spinel been considered. The result revealed Hg0 physical and weak chemical adsorption on both pure surface and Mn-
Dissociation
doped surface. Horizontally placed HgCl and HgCl2 were better chemisorbed on the surface. Although complete
Adsorption
dissociation and partial dissociation occurred during the adsorption process of oxidation mercury, configurations
of complete dissociation were more stable than that of partial dissociation. HgCl was chemically adsorbed on
both Fe3O4 (1 1 1) and Mn doped Fe3O4 (1 1 1) surface through breaking into two atoms, and HgCl2 adsorbed
through three ones. Both of the Cl atom and Hg atom tended to bind to the transition metals on the surface.
When Mn and Fe atoms coexisted on the surface, Cl atoms preferred to bind to Mn atoms. Besides, all the
decomposition reaction was exothermic process according to the negative values of adsorption energy.

1. Introduction mercury control in the flue gas. Due to the high cost, secondary pol-
lution and non-recycling of these methods, the search for more cost-
Trace elements emissions such as mercury from coal combustion effective mercury removal methods has never been stopped. Recently,
have enriched in organisms by participating in the ecological cycle on many researchers have been devoted to removing gaseous pollutants
the earth, and seriously threaten the environment and human health including heavy metal ions by using spinel ferrites [19–22]. The spinel
[1–6]. Mercury mainly exists as gaseous element mercury (Hg0), ferrites have advantages of thermal stability, low-cost, and corre-
monovalent and divalent mercury (Hg+ and Hg2+) and particulate sponding magnetic properties [23,24]. Furthermore, the superior cat-
mercury (Hgp) in coal-fired flue gas [7]. Compared with other mercury alytic properties of the materials have attracted more and more re-
species, Hg0 is more difficult to remove. Because it is highly volatile and searchers [25–30]. Active Fe3+-O species was formed by surface Fe2+
hardly solubilize in water [8,9]. When the temperature of flue gas de- activating O2, manganese substitution (Fe3−xMnxO4) influenced the
creased, some elemental mercury would be oxidized to HgCl2 for a large catalytic properties for CO at a higher temperature [25,26]. (Fe3-
amount of chlorine in pulverized coal, and Meiji [10] found that Hg0 xMnx)1-δO4 was found as a kind of promising material to enhance the
and HgCl2 co-exist in the flue gas. Carpi [11] believed that the different adsorption capability of Hg0 for Mn4+ and cationic vacancies existing
concentrations of HCl and other pollutants in coal and flue gas would on the surface after numerous experimental studies [27]. A study of
affect the distribution of Hg0 and Hg2+, and higher concentrations of mercury and sulfur dioxide removal from flue gas before wet electro-
chlorine contributed to more Hg0 being oxidized to divalent mercury, static precipitator (WESP) by taking advantage of Mn-Fe spinel catalyst
which was mainly in the form of mercuric chloride [12–14]. Thus, with low-temperature oxidation was successfully performed. Moreover,
different mercury species were employed in our work to understand the the recycling of the Mn-Fe spinel catalyst was wonderful [22]. How-
adsorption mechanisms of them. Sorbent injection [15,16], catalytic ever, previous research has paid less attention on mechanism studies on
oxidation [14,17,18] and many other methods have been applied for the mercury removal by Mn doped Fe3O4(1 1 1) surface, which is

⁎
Corresponding author at: School of Energy & Mechanical Engineering, NNU, 210042 Nanjing, China.
E-mail address: [email protected] (C. Zhou).
1
Present/permanent address: School of Energy and Mechanical Engineering, Nanjing Normal University, 210042 Nanjing, Jiangsu, China.

https://doi.org/10.1016/j.apsusc.2020.145876
Received 19 September 2019; Received in revised form 11 January 2020; Accepted 22 February 2020
Available online 25 February 2020
0169-4332/ © 2020 Elsevier B.V. All rights reserved.
J. Chen, et al. Applied Surface Science 514 (2020) 145876

Fig. 1. Models of Fe3O4(1 1 1) surface with the Feoct termination. (a) Original Fe3O4(1 1 1) surface; (b) Mnoct doped Fe3O4(1 1 1) surface; (c) Mntet doped
Fe3O4(1 1 1) surface; (d) Mnoct and Mntet doped Fe3O4(1 1 1) surface.

equally important for the modification of catalysts. octahedral sites in spinel, only 50% of the Fe3+ and all Fe2+ occupy
The emergence of density functional theory (DFT) makes the mi- octahedral interstitial sites in this structure [46]. The other Fe3+ take
croscopic and complex quantum chemistry problems simple, and the up tetrahedral sites [47,48]. Fe3O4(1 1 1) was considered as the most
study is effective and easy to implement [31–33]. It has been success- reactive surface of the three main natural growth surfaces [49]. By
fully applied to investigate the mechanisms in molecule interaction on cutting along the direction of the stacking sequence of Fe3O4(1 1 1), a
pure magnetite surfaces or transition metal doped surfaces [34,35]. repetitive structure with six terminations on the surface of Fe3O4 (1 1 1)
Zhou et al. [36–38] studied the co-interaction mechanism between Hg0 could be obtained [50]. The required energy of their five bonds
and H2O2 on Fe3O4(1 1 1), (1 1 0), and (0 0 1) surfaces by DFT method. breaking was higher than others’ two or four more bonds, as a result,
The co-interaction mechanism of carbon monoxide and H2O on Cu the stability of Feoct2- and Fetet1- terminations was higher than other
doped Fe3O4(1 1 1) surface with Fetet- termination was also performed terminations [51]. Feoct2- termination has both Fetet and Feoct atoms,
through DFT study [40,41]. Yang et al. [42] used first-principle cal- which brings about its higher activity, while Fetet1- only has Fetet on its
culations to explore the heterogeneous mechanisms of Hg0 oxidation on first layer [44]. Thus, Feoct2- termination of Fe3O4(1 1 1) was employed
MnFe2O4(1 0 0) surfaces with the existence of HCl. Yang et al. [43] also in this paper. The lattice parameters of the optimized Fe3O4 unit cell
explored Hg0 oxidation mechanisms by calculating Hg0 and HgO re- were consistent with our previous research results [36–39]. In this
action on MnFe2O4(1 0 0) surfaces. Song et al. [44] revealed that Ti paper, the octahedral and tetrahedral iron atoms substituted by Mnoct
dopant played a key role in the oxidation process of nitric oxide by and Mntet on Fe3O4(1 1 1) surface were performed (as shown in Fig. 1).
hydrogen peroxide on modified Fe3O4(1 1 1) surface with Feoct- ter-
mination. As far as we know, mercury species mechanism on pure and 2.2. Methods
Mn doped Fe3O4(1 1 1) surface has rarely been reported.
Transition metals including Co, Mn, Ni, Mo, and Zn doping on the The Cambridge Sequential Total Energy Program (CASTEP) was
Fe3O4(1 1 1) surfaces were calculated by Materials Studio based on used to perform all calculations in this paper [52,53], using the ex-
density functional theory in our preliminary study. As shown in change-correlation functional GGA-PBE to describe the exchange-cor-
Table 1S, compared with their binding energies and geometric para- relation energy [54,55]. The cutoff energy was 380 eV and 3 × 3 × 1
meters, it was found that mercury preferred adsorption on the Mn- k-points mesh was used to integrate the Brillouin zone. The spin po-
doped surface to that on other transition metals. Therefore, the Mn/ larization of the material was set for the magnetism of the material
Fe3O4 (1 1 1) surface was selected to explore the interaction between [37]. To find the most stable configurations, the method of minimizing
HgCl or HgCl2 with the doped surface. This study intends to reveal the total energy was adopted for atom and cell optimization, with a total
reaction mechanism of different mercury species on Mn doped Fe3O4 energy difference of 2 × 10−5 eV/atom, a maximum force tolerance of
(1 1 1) surface through different adsorption sites, adsorption energy, 0.05 eV/Å. The criteria of maximum stress and the maximum dis-
Mulliken charge, charge transfer, and density of states. The results are placement were 0.1 GPa and 0.002 Å, respectively. The three outmost
of great significance for understanding the adsorption mechanism and layers of all models were relaxed and other layers were fixed
guiding the design of adsorbents. throughout the study. 12 Å vacuum region was employed in the z-di-
rection to eliminate the influence of periodic structure on calculation.
Before calculation, Hg, HgCl and HgCl2 were placed in individual cubic
2. Computational models and methods lattices of (10 Å)3 for geometric optimization. The atoms in Hg, HgCl
and HgCl2 were fully relaxed upon the geometry optimization. Si-
2.1. Models multaneously, 1 × 1 × 1 k-points mesh was applied and the rest of the
settings such as the formal spin of Fe atoms were the same as the
The structure of magnetite is a complex ionic crystal, which is previous [38].
formed by Fe2+, Fe3+, and O2− through ionic bonds between them Adsorption energy can be used to estimate the stability of the ad-
[45]. Different from all metal ions with +3 valence occupying sorbed surface, it can be calculated from:

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J. Chen, et al. Applied Surface Science 514 (2020) 145876

Fig. 2. Structures of Hg0 adsorption on pure and Mn doped Fe3O4(1 1 1) surfaces: 1A, 1A′ and 1B′ for pure surfaces; 1B-1G and 1C′-1E′ for Mn doped surfaces; 1A-1G
for p(1 × 1) surfaces; 1A′-1E′ for p(2 × 1) surfaces.

Table 1 adsorbates such as mercury. Moreover, all units of adsorption energy in

The specific parameters of stable configurations for Hg0 adsorption on this paper are converted from eV to kJ/mol.
Fe3O4(1 1 1) surfaces. Linear synchronous transit/quadratic synchronous (LST/QST)
p(1 × 1) surface cell p(2 × 1) surface cell method was employed to search the transition states during the process
of Hg0 oxidation to HgCl2 [56] and the energy barriers E(barrier) were
Ebind RHg-X MHg-X QHg Ebind RHg-X MHg-X QHg calculated from the next formula:
1A −32.089 2.856 0.36 0.05 1A′ −31.913 2.853 0.36 0.06 Ebarrier = ETS − EIM
1B −32.526 2.839 0.35 0.05 1B′ −14.118 2.896 0.31 −0.02
1C −11.660 3.290 – −0.06 1C′ −39.865 2.808 0.37 0.06 where E(Transition) and E(Intermediate) represent the total energies of the
1D −29.235 2.886 0.31 0.03 1D′ −40.393 2.918 0.22 0.03 transition states and the intermediate states respectively.
1E −37.150 2.710 0.42 0.02 1E′ −31.086 2.826 0.37 0.04 Moreover, the energy pathway shown in Fig. 1S in supporting in-
1F −26.819 2.850 0.30 0.00
1G −42.420 2.770 0.39 0.03
formation was obtained to describe the process of Hg0 oxidation from
the adsorbed elemental state to oxidation one.
Notes: Ebind represents adsorption energy (kJ/mol), RHg-Mn and RHg-Fe represent
the length of adsorbed Hg and Mn/Fe, respectively (Å), MHg-Mn and MHg-Fe 3. Calculation results and discussion
represent the corresponding bond population between Hg and Mn/Fe, QHg re-
presents Mulliken charges of Hg atom (e). 3.1. Hg0 interaction with pure and Mn doped Fe3O4(1 1 1) surfaces

Ebind = E(sub + ad) − E(sub) − E(ad) The p (1 × 1) and p (2 × 1) surface cells were used to investigate
In the formula, E(sub + ad) represents the total energy of the substrate the interactions between Hg0 and pure surfaces, Mn doped Fe3O4(1 1 1)
with adsorbates, and E(sub) represents the total energy of the substrate surfaces, respectively. A single adatom was allowed to approach Fe3O4
before calculation. Additionally, E(ad) is the ground state energy of and Mn/Fe3O4 from different sites, including Feoct top, Fetet top, Mnoct

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J. Chen, et al. Applied Surface Science 514 (2020) 145876

Fig. 3. Structures of HgCl adsorption on pure Fe3O4(1 1 1) surfaces: 2A-2D on Mn doped surfaces.

Table 2
The specific parameters of stable configurations for HgCl adsorption on pure Fe3O4(1 1 1) surfaces.
Ebind RHg-X RCl-X MHg-X MCl-X QHg QCl

2 × 1 surface cell 2A −314.199 2.887 2.202 0.34 0.59 0.07 −0.41

2B −271.182 – 2.210 – 0.54 −0.01 −0.43
2C −197.558 2.887/2.711 2.424 0.23/0.37 0.46 0.06 −0.42
2D −107.893 2.265 2.418 0.23 0.45 0.34 −0.34

Notes: Ebind represents adsorption energies (kJ/mol), RHg-X represents the length of adsorbed Hg and Fetet/Feoct/O, respectively (Å), RCl-X represents distances
between the Cl atom and Fetet/Feoct/Hg, respectively (Å), MHg-X and MCl-X represent the corresponding bond population between Hg and Fetet/Feoct/O and Cl and
Fetet/Feoct/Hg, respectively, QHg and QCl represent Mulliken charge of Hg atoms and Cl atoms, respectively (e).

top, Mntet top, O sites, and hollow sites. After calculation, all stable supporting information, two energy barriers (262.4 kJ/mol and
configurations are shown in Fig. 2 when the systems are in equilibrium; 306.8 kJ/mol) were found during Hg0 oxidation from the adsorbed
the optimized parameters of the configurations are given in Table 1. elemental state to oxidation one. However, these energy barriers were
According to the configurations, Hg prefers to interact with Mn and relatively high, and the energy of the final state was 328.286 kJ/mol
Fe atoms on the surface. The adsorption energies suggest that Mnoct top higher than that of the reactant state. It can be suggested that the
is the most attractive sites to mercury, then Mntet top, and at last, Fetet oxidation process of Hg0 on the Mn-doped Fe3O4 surface was en-
top. Among the obtained structures of p(1 × 1) cells, configuration 1G dothermic and hardly spontaneous due to the high energy barriers.
is most stable and its binding energy is −42.420 kJ/mol. The bond Therefore, the removal mechanism of Hg0 by the Mn-doped Fe3O4 is
length of Hg-Mn is 2.770 Å. 0.03 e charges transferring from Hg0 to the mainly physical and weak chemical adsorption.
substrate surface is shown by the bond population. In addition, with the
increase of Mn atoms content, the binding energies are increasing, and
3.2. HgCl adsorption on pure and Mn doped Fe3O4(1 1 1) surfaces
the result corresponds with the experimental conclusion [27]. To re-
duce the computational complexity, the model of the substituted Mntet
3.2.1. HgCl binding on Fe3O4(1 1 1) surface
and Mnoct on the surface was used to clarify Hg0 adsorption mechanism
HgCl was geometrically optimized before calculation. The bond
on the doped p(2 × 1) surface. The binding energies of Hg0 adsorption
length of HgCl is 2.471 Å. The number of Hg Mulliken charge is 0.37 e
are arranged in the following order: 1D′ > 1C′ > 1E′. Meanwhile,
and that of Cl atom is −0.37 e, respectively. Three different config-
0.03 e, 0.06 e, and 0.04 e charges transform to the Mn-doped surfaces
urations of the relative location between HgCl and Fe3O4 (1 1 1) sites
and the bond populations are 0.22, 0.37, and 0.37, respectively.
were considered before calculation on the p(2 × 1) supercell surfaces.
However, the adsorption energy ranges from −11.660 kJ/mol to
(1) Hg-Cl bond was set parallelly over the surface, and the HgCl was
−42.420 kJ/mol, suggesting that Hg0 adsorption on both pure surfaces
placed on the hollow site, Fetet, Feoct and O top sites; (2) Hg-Cl bond
and Mn-doped surfaces is physical and weak chemical behaviors. The
was placed perpendicularly over the surface, and the Hg atom of HgCl
possible catalytic oxidation process of Hg0 by the adsorbed Cl atoms on
was placed down toward the same adsorption sites as above; (3) Hg-Cl
the Mn-doped Fe3O4 surface was also considered. As shown in Fig. 1S in
bond was placed perpendicularly over the surface, and the Cl atom of

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J. Chen, et al. Applied Surface Science 514 (2020) 145876

Table 3 HgCl binding to Feoct termination of the pure Fe3O4(1 1 1) through a

The specific parameters of stable configurations for HgCl adsorption on Mn/ dissociation adsorption reaction. In addition, it can be inferred that the
Fe3O4(1 1 1) surface. decomposition reaction is an exothermic process according to the ne-
Ebind RHg-X RCl-X MHg-X MCl-X QHg QCl gative values of adsorption energy.

3A −321.511 2.789 2.354 0.42 0.44 0.13 −0.46

3B −301.121 2.876 2.276 0.34 0.53 0.09 −0.45
3.2.2. HgCl binding on Mn doped Fe3O4(1 1 1) surface
3C −359.973 2.853 2.184 0.35 0.59 0.10 −0.44
3D −363.086 2.835 2.419/ 0.38 0.34/0.31 0.09 −0.41 P(2 × 1) supercells were employed to investigate interactions be-
2.443 tween HgCl and Mn doped Fe3O4(1 1 1) surface. The adsorption site
3E −351.182 2.820 2.286 0.39 0.52 0.10 −0.45 referred to in this calculation is similar to that of HgCl adsorption on
3F −350.526 – 2.366/ – 0.33/0.32 0.06 −0.39
pure Fe3O4(1 1 1) surface.
2.451
3G −319.777 2.835 2.262 0.38 0.49 0.11 −0.44
As shown in Table 3 and Fig. 4, configuration 3A to 3H are obtained
3H −319.153 2.829 2.262 0.34 0.52 0.06 −0.46 after geometric optimization when HgCl is placed horizontality. The
3A′ −198.876 2.692 2.444 0.51 0.44 0.01 −0.44 order of the stability is 3D > 3C > 3E > 3F > 3A > 3G > 3H >
3B′ −216.403 2.628 2.430 0.61 0.43 0.10 −0.47 3B. The bond of HgCl in these configurations is lengthened and breaks
3C′ −216.707 2.571 2.417 0.61 0.43 0.11 −0.45
to Hg atom and Cl atom. In configuration 3D and 3F, Cl atoms are
3D′ −339.075 – 2.400/ – 0.34/0.32 0.02 −0.40
2.406 bound to Mnoct and Fetet on the surface with their respective bond
3E′ −300.843 – 2.232 – 0.59 −0.01 −0.45 length of 2.419/2.443 Å and 2.366/2.451 Å. 0.32 e and 0.33 e charges
3F′ −278.887 – 2.301 – 0.48 0.00 −0.47 transfer from the basement to Hg and Cl, respectively. In configuration
3G′ −213.421 2.982/ 2.464 0.16/0.41 0.41 0.00 −0.45 3D, Hg is attached to the Feoct on the surface while Hg frees from the
2.723
3H′ −124.000 2.328 2.452 0.18 0.42 0.24 −0.37
surface in configuration 3F. Cl atom strongly interacts with Mnoct-Fetet
3I′ −214.623 2.652 2.472 0.59 0.39 0.12 −0.49 bridge site by forming two new bonds: Cl-Mnoct bond and Cl-Fetet bond.
Cl, Mnoct and Fetet atoms are connected by the three bonds and the
Notes: Ebind represents adsorption energies (kJ/mol); RHg-X represents the structure is in the shape of a triangle. The binding mechanism can be
length of adsorbed Hg and Fetet/Feoct/Mntet/Mnoct/O, respectively (Å); RCl-X demonstrated by analyzing the PDOS of related atoms after adsorption.
represents distance between the Cl atom and Fetet/Feoct/Mntet/Mnoct/Hg, re- In Fig. 5, s, p, and d orbitals for Cl adsorbed on Mn doped Fe3O4(1 1 1)
spectively (Å); MHg-X and MCl-X represent the corresponding bond population surface are analyzed to investigate the interaction between Cl and
between Hg and Fetet/Feoct/Mntet/Mnoct/O and Cl and Fetet/Feoct/Mntet/Mnoct/
Mnoct/Fetet. Fig. 5 (b) shows different superposition states of the p or-
Hg, respectively; QHg and QCl represent Mulliken charge of Hg atoms and Cl
bital of Cl and the d orbital of Mn at −4.9 and −1.3 eV. Meanwhile, a
atoms, respectively (e).
multiple overlapping is shown, the p orbital of the Cl and the p, d or-
bitals of Fe overlap at −6.4 and −0.4 eV. Strong orbital hybridization
HgCl was placed down toward the same adsorption sites as above. After
of Cl and Mnoct/Fetet result in enhancing the interaction between the
calculation, eight stable structures of HgCl binding on pure Fe3O4(1 1 1)
HgCl and the substrates. The energy favorable for HgCl adsorption on
surfaces are obtained. Fig. 3 shows the stable structures. The adsorption
the surface is −363.086 kJ/mol, which confirms the strong interaction.
energy, Mulliken charge, bond population, and bond length are ex-
HgCl is adsorbed on Mn doped surfaces with a higher energy than that
hibited in Table 2.
on clean surfaces. In configuration 3A and 3B, Hg atoms and Cl atoms
As shown in Table 2, the binding energy values ranging from
can be adsorbed by interacting with both Mntet and Mnoct. However, the
−107.893 kJ/mol to −314.199 kJ/mol clarify that HgCl is chemi-
interaction occurred on both Mnoct and Feoct surface in configuration 3C
sorbed on Fe3O4(1 1 1) surface with an exothermic process. Config-
and 3E. Combined with the Mulliken charge analysis, a certain amount
uration 2A is the most stable model among the calculated results and its
of electrons transfers to the substrate in configuration 3A, 3B, 3C and
binding energy is −314.199 kJ/mol. The distance between Hg and Cl is
extended to 3.665 Å. Mulliken charge population shows that 0.34 e 3E. 0.33 e and 0.40 e charges transfer from the substrate to Hg and Cl,
charges transfer from the substrate to Hg and Cl. The bond population is respectively. All parameters indicate that HgCl has a definite chemical
0.59. In Fig. 5(a), s, p, and d orbitals for Cl adsorbed on pure interaction with Mn-doped surface.
Fe3O4(1 1 1) surface are analyzed to investigate the interaction between By placing HgCl on the doped surface perpendicularly, nine stable
Cl and Feoct. Fig. 5 (a) shows different superposition states of the p configurations (Configuration 3A′ to 3I′) are obtained after calculation.
orbital of Cl and the d orbital of Feoct at −4.1, −1.9 and 0.5 eV. Thus, There is dissociation adsorption reaction in configuration 3D′, 3E′ and
Hg and Cl have a strong interaction with Fetet and Feoct. The length of 3F′. The binding energy is among −278.887 ~ −339.075 kJ/mol; all
Hg-Cl bond in configuration 2B is elongated to 4.167 Å, which is much of them are strong chemical adsorption. Cl is bound to Mntet or Mnoct of
longer than that in original HgCl, and it contributes to the dissociation the surface by strong chemical absorption in 3E′ and 3F′. The bond
of HgCl. After the dissociation, Cl is strongly bound to the surface with population of Cl and Mntet or Mnoct are 0.59 and 0.48 while the bond
Hg far from the surface. Meanwhile, 0.44 e charges transfer from the lengths of Cl and Hg are elongated by 1.213 and 1.907 Å, respectively.
basement to the Cl atom. Contrary to 2A and 2B, the Hg atoms were put Therefore, Cl, in such configurations, interacts strongly with Mn atoms,
down toward the surface in configuration 2C and 2D. HgCl was ad- weakening the interaction between Cl and Hg. Similar to configuration
sorbed on the surface without dissociation. Configuration 2C shows that 3D and 3F, Cl is bound to the Fetet-Mnoct bridge site in configuration
Hg interacts with Feoct and Fetet. 0.36 e charges transfer from the 3D′, but Hg frees from the surface. The binding energy of configuration
substrate to Hg and Cl. Different from 2A and 2B, initially, the Hg atom 3D′ is a little lower than that of configuration 3D. When the structural
of HgCl was placed on O top in configuration 2D. After calculation, system maintains its equilibrium, the structure of molecular HgCl does
HgCl is adsorbed by Otet top yielding the energy of −107.893 kJ/mol. not change significantly in 3A′, 3B′, 3C′, 3G′, 3H′ and 3I′ with their
A new Hg-O bond is formed with a length of 2.265 Å in this structure. bond length ranging from 2.417 to 2.472 Å. Therefore, Hg atom of HgCl
Simultaneously, the length of Hg-Cl bond is reduced to 2.418 Å, which prefers to attach to Mn top compared with other considered sites.
is close to the original length of 2.471 Å. Thus, 2D is chemically ad- In general, horizontally placed HgCl can be better adsorbed on the
sorbed but not stable. surface through comparative analysis. Once the dissociation of HgCl
When the HgCl is adsorbed on the surface through breaking into two happens, the HgCl will be chemically adsorbed. Moreover, HgCl is most
atoms, the adsorption energies are higher than the structures without likely to dissociate and to be adsorbed on Mn doped Fe3O4(1 1 1)
HgCl dissociation. The result can be interpreted as chemisorption of surface.

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J. Chen, et al. Applied Surface Science 514 (2020) 145876

Fig. 4. Structures of HgCl adsorption on Mn doped Fe3O4(1 1 1) surfaces.

3.3. HgCl2 adsorption on pure and Mn doped Fe3O4(1 1 1) surfaces supercell was employed for calculation. The initial placement of HgCl2
on the surface corresponds with the initial structures of HgCl adsorption
Taking the large size of HgCl2 molecule and the mutual exclusion on the above discussion. The specific parameters of these configurations
between the periodic adsorbates into account, only the p(2 × 1) are listed in Table 4. The optimized configurations after calculations are

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J. Chen, et al. Applied Surface Science 514 (2020) 145876

Fig. 5. PDOS of Cl adsorbed on pure and Mn doped Fe3O4(1 1 1) surface in configuration 2A′, 3D, 4A and 4C′ (a) 2A′, (b) 3D, (c) 4A and (d) 4C′; the values of Fe and
Mn were set to negative for analysis; red, s orbital; blue, p orbital; magenta, d orbital).

shown in Fig. 6. HgCl2 was optimized geometrically before calculation. HgCl2 changes a lot with Cl1 and Cl2 adsorbed on two Fetet sites.
Each Hg-Cl distance is 2.299 Å. The bond angle of Cl1-Hg-Cl2 is 180°. Meanwhile, 0.18 e, 0.28 e and 0.18 e charges transfer from the sub-
The Mulliken charge of Hg atom, Cl1, and Cl2 atom are 0.44 e, −0.23 e strate to the Cl1, Hg and Cl2 atoms, respectively. In Fig. 5 (d), s, p, and d
and −0.23 e, respectively. orbitals for Cl atoms adsorbed on Mn doped Fe3O4(1 1 1) surface are
Configurations 4A and 4B depicted in Fig. 6 are stable structures of analyzed to investigate the interaction between Cl and Fetet/Mnoct/
HgCl2 adsorbed on pure Fe3O4(1 1 1) with Feoct2- termination surface. Mntet. Different superposition states of the p orbital of Cl2 and the d
The binding energy of configuration 4B is −74.100 kJ/mol, suggesting orbital of Mnoct at −4.4, −3.4 and −2.1 eV were shown in the first
a weak relationship between HgCl2 and the basement. The Cl2 is ad- figure. In the second figure, a multiple overlapping is shown, the p
sorbed on the Feoct with a distance of 2.235 Å. However, the bond orbital of the Cl2 and the d orbital of Fetet overlap at −6.0, −3.6, −1.8
length of Cl2 and Hg is elongated to 0.452 Å. Thus, the HgCl2 in parallel and 0.6 eV and the s orbital of Cl2 and the p orbital of Fetet overlap at
position was weak chemisorption. The binding energy of configuration −15.4 eV. As for Cl1, its p orbital and d orbital of Mntet overlap at
4A is −306.720 kJ/mol, which is much higher than 4B. The molecular

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J. Chen, et al. Applied Surface Science 514 (2020) 145876

Fig. 5. (continued)

Table 4
The specific parameters of stable configurations for HgCl2 adsorption on Fe3O4(1 1 1) surfaces.
Ebind RHg-X RCl1-X/RCl2-X MHg-X MCl1-X/MCl2-X QHg QCl1/Cl2

4A −306.720 2.828 2.226/2.228 0.43 0.50/0.50 0.16 −0.41/−0.41

4B −74.100 2.440 2.440/2.235 0.26 0.26/0.48 0.37 −0.39/−0.37
4A′ −342.890 – 2.231/2.437/2.443 – 0.50/0.33/0.31 0.07 −0.41/−0.39
4B′ −357.878 2.850 2.259/2.160 0.38 0.56/0.62 0.14 −0.43/−0.38
4C′ −371.185 2.834 2.481/2.488/2.543/2.338 0.40 0.31/0.31/0.27/0.38 0.15 −0.44/−0.40
4D′ −86.171 2.448 2.448/2.207 0.25 0.25/0.51 0.32 −0.39/−0.38
4E′ −107.799 2.504 2.504/2.384/2.397 0.23 0.23/0.33/0.34 0.21 −0.40/−0.38
4F′ −77.034 2.462 2.462/2.270 0.24 0.24/0.50 0.34 −0.39/−0.42
4G′ −54.916 2.475 2.335 0.24 0.24/0.43 0.28 −0.39/−0.43
4H′ −97.691 2.493 −/2.516/2.408 0.24 −/0.27/0.35 0.24 −0.38/−0.39
4I′ −72.695 2.492 2.492/2.425/2.428 0.24 0.24/0.29/0.33 0.20 −0.39/−0.36

Notes: Ebind represents adsorption energy (kJ/mol); RHg-X represents the length of adsorbed Hg and Feoct/Mntet, respectively (Å); RCl1-X represents distance between
the Cl1 atom and Fetet/Mntet/Mnoct/Hg, respectively (Å); RCl2-X represents distance between the Cl2 atom and Fetet/Feoct/Mntet/Mnoct/Hg, respectively (Å); MHg-X and
MCl-X represent the corresponding bond population between Hg and Fetet/Feoct/Mntet/Mnoct/O and Cl and Fetet/Feoct/Mntet/Mnoct/Hg, respectively; QHg and QCl
represent Mulliken charge of Hg and Cl, respectively (e).

−3.0 eV and its s orbital and p orbital of Mntet overlap at −15.1 eV. obtained stable configurations are also demonstrated in Fig. 6. From the
The last figure shows that the p orbital of Cl1 and d orbital of Mnoct adsorption energy, it can be concluded that 4C′ is the most stable ad-
overlap at −2.1 eV and the s orbital of Cl1 and the p orbital of Mnoct at sorption configuration. The structure of HgCl2 molecule greatly changes
−15.1 eV. Considered the bond lengths of Cl1-Fetet and Cl2-Fetet and after adsorption in configurations 4A′-4C′. The two Hg-Cl bonds are
PDOS of Cl and Fe atoms, the results clarify that HgCl2 is adsorbed broken with binding energies ranging from −342.890 to −371.185 kJ/
chemically on the substrate in configuration 4A. mol. In configuration 4A′, Cl1 and Cl2 are adsorbed on the Mn and Fetet
Simultaneously, the interaction between HgCl2 and Mn doped top sites, respectively. The angle of Cl1-Hg-Cl2 decreases to 98.5°.
Fe3O4(1 1 1) with Feoct2- termination surface was investigated. All the Meanwhile, 0.21 e, 0.29 e and 0.17 e charges transfer from the

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J. Chen, et al. Applied Surface Science 514 (2020) 145876

Fig. 6. Structures of HgCl2 adsorption on clean surfaces and Mn doped surfaces: 4A and 4B for clean surfaces; 4A′-4I′ for Mn doped surfaces.

substrate to the Cl1, Hg and Cl2 atoms, respectively. The difference through binding Cl atoms to Mn or Fe on the surface. In configurations
between configuration 4A′ and 4C′ is the free state of Hg in 4A′. Fur- 4E′, 4H′, and 4I′, Cl2 atom is adsorbed on the Mnoct-Fetet bridge site, the
thermore, the binding energy of 4C′ is a little higher than that of 4A′, Mnoct-Mntet bridge site and the Feoct-Fetet bridge site, respectively. In
which is predicted as the former state of 4C′. In Fig. 5 (d), s, p, and d configuration 4D′, 4F′, and 4G, HgCl2 breaks Hg–Cl2 bond with Cl1
orbitals for Cl atoms adsorbed on pure Fe3O4(1 1 1) surface are ana- atom adsorbed on the Mn top. The binding energy ranges from
lyzed to investigate the interaction between Cl atoms and Fe atoms. The −54.916 to −86.171 kJ/mol, implying that HgCl2 is chemically bound
left one shows different superposition states of the p orbital of Cl2 and to the substrate [57,58].
the d orbital of Fetet at −6.0, −5.0, −3.5, −1.9 and 0.5 eV. In the right The interaction between entirely dissociative HgCl2 molecule is
figure, a multiple overlapping is shown, the p orbital of the Cl1 and the stronger than the interaction between partially dissociative HgCl2 mo-
d orbital of Fe′tet overlap at −5.0, −1.8 and 0.5 eV. The Hg, Cl1, and lecule after doping Mn on Fe3O4(1 1 1) surface. Simultaneously, the
Cl2 atoms are all adsorbed on the 4A′ basement. However, adsorption overall adsorption effect of vertical placement is far less than that of
sites are different from that in configuration 4C′. horizontal placement. Thus, completely dissociation adsorption of
The structures of 4D′, 4E′, 4F′, 4G′, 4H′, and 4I′ are optimized when HgCl2 is most likely to occur on the surface and configurations 4A′-4C′
HgCl2 molecule is perpendicular to the surface. HgCl2 adsorption is are more likely to be obtained.

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J. Chen, et al. Applied Surface Science 514 (2020) 145876

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