Applied Surface Science 678 (2024) 161097

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Applied Surface Science

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Full Length Article

Influence of Ca2+ substitution on the surface hydration characteristics of

kaolinite: Combination of simulations and experiments
Qingdong Shu a , Fanfei Min a,b,* , Jun Chen a,b,*
a
Department of Materials Science and Engineering, Anhui University of Science and Technology, Huainan 232001, China
b
Anhui Engineering Research Center for Coal Clean Processing and Carbon Reduction

A R T I C L E I N F O A B S T R A C T

Keywords: To investigate the changes in kaolinite surface hydration characteristics after Ca2+ substitution, water molecule
Ca2+-substituted kaolinite adsorption onto the surface of Ca2+-substituted kaolinite was studied using density functional theory. Changes in
Density functional theory the hydration film on the surface of kaolinite (001) and the mineral surface hydrophilicity after Ca2+ substitution
Molecular dynamics
were studied using molecular dynamics methods. Several Ca2+-substituted kaolinite samples were hydrother­
Hydration characteristic
mally synthesized, and their hydration characteristics were analyzed using contact-angle and microcantilever
humidity-test methods. The energy of a water molecule adsorbed on a Ca2+-substituted kaolinite surface is > 5 %
lower than on pure kaolinite, and microscopic interactions between water molecules and the kaolinite surface are
enhanced. Further, water molecules are more likely to be adsorbed onto the (001) surface than the (001) surface
of kaolinite. After Ca2+ substitution, the hydration film on the kaolinite (001) surface becomes denser and the
hydrophilicity of the mineral surface is enhanced. Using X-ray diffraction, Fourier-transform infrared spectros­
copy, and X-ray photoelectron spectroscopy to characterize the synthesized samples, we confirmed successful
Ca2+ substitution within the kaolinite structure. Hydration-test results showed that the surface hydrophilicity of
kaolinite is enhanced after Ca2+ substitution and increases with increasing Ca2+ substitution. The experimental
results thus verified the simulations.

1. Introduction dynamics simulations to study the effects of metal cation solutions with
different valences on kaolinite hydration and concluded that the ability
Kaolinite is a common impurity mineral in coal slime [1,2]. It is of hydrated ions to disrupt the hydration film on a kaolinite surface
associated with other minerals [3,4] and exists widely in many types of increases with increasing metal cation valence. Yi et al [13] used mo­
mineral-processing wastewater [5,6]. Due to its surface/interface char­ lecular dynamics simulations to study the interfacial system between the
acteristics, kaolinite greatly impacts the separation and treatment of montmorillonite (001) surface and water and found that a hydration
sewage from mining tailings [7,8]. The hydration of kaolinite is an film of six ordered layers of water molecules formed on the montmo­
important characteristic of this mineral [9,10], which has a significant rillonite (001) surface.
impact on the separation, sedimentation, and dehydration of the clay in However, the phase structures of the clay minerals in these studies
mineral-processing wastewater. Investigators have conducted extensive are inconsistent with the state in which they exist in mining wastewater
research on these issues, utilizing both experiments and simulations. [14,15]. Due to the conditions in which the crystals are formed, the
Chen et al [11] studied the surface-hydration mechanism of kaolinite thermal movements of the atoms, radiation, stress, and other reasons,
using both density functional theory and molecular dynamics methods clay minerals are prone to lattice defects [16,17]. At present, however,
and found that surface-hydrated films on kaolinite consist of about three research on lattice defects in clay minerals is focused mainly on lattice
layers of water molecules that are mainly adsorbed on the surface by substitutions. Shi et al [18] studied Si4+/Al3+-substituted montmoril­
hydrogen bonding. Chang et al [12] used experiments and molecular lonite using density functional theory calculations and found that the

Abbreviations: Bn, bridge absorption site n; DD, density distribution; DFT, density functional theory; HI, Hinckley index; Hn, hollow adsorption site n; Hs,
hydrogen in a kaolinite surface; Hw, hydrogen in a water molecule; MD, Molecular dynamics; Os, oxygen in a kaolinite surface; Ow, oxygen in a water molecule; RDF,
radial distribution function; WL, water layer; XPS, X-ray photoelectron spectroscopy; XRD, X-ray diffraction.
* Corresponding authors at: Department of Materials Science and Engineering, Anhui University of Science and Technology, Huainan 232001, China.
E-mail addresses: ffmin@aust.edu.cn (F. Min), jchen412@126.com (J. Chen).

https://doi.org/10.1016/j.apsusc.2024.161097
Received 11 July 2024; Received in revised form 18 August 2024; Accepted 27 August 2024
Available online 28 August 2024
0169-4332/© 2024 Elsevier B.V. All rights are reserved, including those for text and data mining, AI training, and similar technologies.
Q. Shu et al. Applied Surface Science 678 (2024) 161097

substitution deformed the montmorillonite lattice structure, changing diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and
its cell parameters and bond angles significantly. Chen et al. [19] X-ray photoelectron spectroscopy (XPS).
explored the changes caused by the substitution of Fe2+/Fe3+ in The XRD data was obtained using a Labx-6000 X-ray powder
kaolinite, adopting the surfaces of Fe2+-substitute kaolinite to adsorb the diffractometer with a copper target plate. The scanning speed was
structural units of coal, and they analyzed the interaction force between 0.05◦ /s, and the scanning angles ranged from 10◦ to 65◦ . A Nicolet iS50
units and the surface. They found that after the Fe2+/Fe3+-substitution, spectrometer was used to record the FTIR spectra. The samples were
the force of interaction between the kaolinite and the structural units of made into KBr particles (with 1- wt% sample) and scanned from 4000 to
the coal was stronger and that the surface was also more reactive. Sun 400 cm− 1. Each sample was kept dry before being measured. The XPS
et al. [20] used density functional theory to study the surface-hydration spectra were obtained using an ESCALAB 250Xi instrument. A mono­
mechanism of Mg2+-substituted kaolinite and concluded that the hy­ chrome Al Kα Source (hν = 1486.6 eV) was utilized, and the vacuum in
dration activity on the (001) surface of kaolinite was considerably the analysis chamber was better than 1 × 10− 9 bar. High-resolution
improved after Mg2+-substituted. scans of Al 2p, Si 2p, and O 1 s were performed on each sample, and
Lattice substitutions cause changes in the lattice structure of high-resolution scans of substituted calcium were also performed. The
kaolinite, leading to changes in the properties of different cleavage sample’s surface composition and binding energy were analyzed using
planes of the crystal [21,22]. Particle interactions depend on their sur­ these high-resolution scans. The energy scales were calibrated using
face properties [23,24]. Because Ca2+ is a common impurity element in high-resolution scanned carbon. The C 1 s peak position was calibrated
kaolinite [25,26]—replacing Al3+ in the kaolinite lattice—it causes to a binding energy of 284.5 eV [28], and the peak positions in XPS
changes in the crystal structure, altering the distributions of orbital spectra were determined accordingly.
electrons, their orbital energies, charge densities, and ultimately
altering the reactivity of the kaolinite [27]. Replacing the atoms in
2.2. Hydration experiments
kaolinite crystals and changing their surface properties thus has a
notable impact on the aggregation and dispersion behavior of fine
The hydration characteristics of kaolinite samples into which
kaolinite particles in mining wastewater—such as coal slurry—as well as
different amounts of Ca2+ had been substituted were tested using the
on their processing and utilization characteristics. Accordingly, this
contact-angle and humidity test methods. An SL200C surface contact
article first uses density functional theory to calculate the adsorption of
angle tester was used to measure the contact angle. A 0.5 g sample was
water molecules onto the surface of Ca2+-substituted kaolinite and uti­
pressed for 3 min at a pressure of 10 MPa into the shape of a thin sheet.
lizes molecular-dynamics methods to study the mechanism through
Measurements were taken from three different areas of the sheet and the
which the substituted amount influences the interfacial hydration
average was calculated. The humidity method uses a microcantilever
characteristics. At the same time, contact angle simulation was con­
system [29]; it is based on the principle that different samples have
ducted to study the influence of Ca2+ substitution on the surface hy­
different hydration properties in an environment with the same hu­
drophilicity of kaolinite. In addition, samples of Ca2+-substituted
midity, which leads to different deflections of the microcantilever beam.
kaolinite were synthesized using hydrothermal synthesis, and hydration
As shown in Fig. 1, this principle is utilized to measure the hydration
tests were performed on these samples. Studying the surface-hydration
characteristics of the samples. Prepare a 2.5 mg/mL suspension by
process of Ca2+-substituted kaolinite through simulations and experi­
adding a small amount of sample to deionized water. This suspension is
ments gives us a theoretical basis for further research on the actual
coated onto the probe of the microcantilever and dried to form a film.
mechanisms of clay surface hydration, effective treatment of clay-
The proportion of dry and wet N2 introduced into the system chamber is
containing wastewater, and the utilization of coal-based clays as a
changed to maintain 70 % relative humidity in the chamber, and the
resource.
microcantilever deflection values are then obtained for the different
samples; see reference [29] for relevant testing parameters.
2. Material and methods

2.1. Preparation of samples 2.3. Simulation methodologies

2.1.1. Synthesis methodologies All calculations were performed using Material Studio (MS) 2017
This article adopts the sample-synthesis method described in the version software (BIOVIA Corporation). The simulations utilized the SPC
references [43,54]. All samples were prepared using a fixed aluminum/ water molecule model [30].
calcium ratio (Table 1), and the following synthesis steps were per­
formed: dissolve 0.0504 mol of kaolinite powder in 30 mL of deionized 2.3.1. Density functional theory
water and stir evenly. Add CaCl2⋅6H2O powder, and mix and stir for 30 Using the density functional theory (DFT) software in the Castep
min. Transfer the solution to a 100-mL Teflon container, place it in a module [31], the adsorption of individual water molecules onto the
steel autoclave, and heat it at 180 ◦ C for 10 h. After the reaction, allow (001) and (001) surfaces of Ca2+-substituted kaolinite was studied. The
the sample to cool to room temperature naturally. The solid particles are aluminum oxide surface of kaolinite was replaced during the simula­
washed six times with deionized water and then separated using tions: in each periodic 2 × 1 × 1 supercell model, Ca2+ was used to
centrifugation. The final product is obtained after drying the sample at replace Al3+ in the aluminum oxide octahedron, and the excess negative
40 ◦ C for 24 h. All chemicals are analytical grade. charge was neutralized with Na+. The surface model of Ca2+-substituted
kaolinite was obtained by cutting along the (001) and (001) planes of
2.1.2. Characterization methodologies the bulk crystal cells, and a vacuum layer of 20 Å was applied to the
The synthesized samples were characterized by powder X-ray surface. Optimization of the water molecules was performed by placing
them in crystal cells of 15 × 15 × 15 Å3. Each simulation used the
GGA–PBE function [32] as the exchange–correlation function, the plane-
Table 1
wave truncation energy was set at 500 eV, and Grimme’s dispersion-
Experimental parameters for synthesizing Ca2+-substituted kaolinite samples.
force correction was used. The Broyden–Fletcher–Goldfarb–Shanno
Sample Al:Ca Kaolinite (mol) CaCl2⋅6H2O (mol)
(BFGS) algorithm was used for model optimization, and the interaction
0% 32:0 0.0504 0 between atomic valence electrons was described using a super-soft
1.56 % 31:1 0.0016 pseudopotential [33]. The Monkhorst-Pack k-point set [34] was taken
3.13 % 15:1 0.0034
to be 3 × 2 × 3 during cell optimization, while the Gamma point was

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 Q. Shu et al. Applied Surface Science 678 (2024) 161097

Fig. 1. Schematic of humidity testing.

obtained during optimization of the surface and adsorption configura­ are in kJ/mol.
tions. The pseudopotential valence electrons of the atoms involved in
the calculations were Al 3s23p, Si 3s23p2, O 2s22p4, H 1 s, Na 3 s1, and Ca 2.3.2. Molecular dynamics
3s23p63d2. For other related parameter settings, please refer to citation Molecular dynamics (MD) was used to investigate the effect of Ca2+
[35]. The stable configurations of the water molecules and the (001) and substitution on the hydration properties of the kaolinite (001) surface
(001) surfaces of Ca2+-substituted kaolinite are shown in Fig. 2. and the hydrophilicity of the mineral surface. To investigate the hy­
Because multiple adsorption sites for water molecules on the surface dration mechanism of the kaolinite (001) surface after Ca2+ substitution,
of Ca2+-substituted kaolinite, we established bridge (B) and hollow (H) we first constructed the corresponding surface model. Kaolinite single-
adsorption sites for the (001) and (001) surfaces of Ca2+-substituted crystal cells [37] were imported using MS software and then expanded
kaolinite based on frontier-orbital theory [11,27] and on the symmetry into 8 × 4 × 2 supercells. A supercell was cleaved along the (001) plane,
of the optimized surface model (Fig. 3). The adsorption stability of water and an 80 Å vacuum layer was added to create the kaolinite (001) sur­
molecules on mineral surfaces can be expressed using the adsorption face. On this basis, Ca2+ substitution can be carried out in four ways:
energy; the lower the adsorption energy, the more stable the adsorption. once every 2 × 1 × 2 cycles, with a substitution ratio of 6.25 %; once
The adsorption energy is given by equation (1) [36]: every 2 × 2 × 2 cycles, with a substitution ratio of 3.13 %; once every 4
× 2 × 2 cycles, with a substitution ratio of 1.56 %; and without sub­
Eads = Etotal − (Esurface + EH2 O ) (1) stitution. The negative charge remaining following a substitution is
neutralized using Na+ (Fig. 4).
where Eads is the adsorption energy of a water molecule on the mineral To construct a model for the interfacial between the (001) surface of
surface, Etotal is the total energy of the stable adsorption system, and Ca2+-substituted kaolinite and water molecules, we first constructed a
Esurface and EH2 O represent the energy of the surface model before crystal box with dimensions a × b × c = 41 × 36 × c Å3 and randomly
adsorption and the energy of the water molecule, respectively. All values filled it with water molecules having a density of 1.0 g/cm3 using the
Amorphous Cell module. The thickness of the water layer is determined
by the size of the crystal box. There are five cases: c = 2, 5, 10, 20, and
30 Å. Using the Build Layer tool, we added water molecule layers of
different thicknesses to positions 2–3 Å away from the Ca2+-substituted
kaolinite surface. This results in a model of the structure of the Ca2+-
substituted kaolinite/water interface (Fig. 5). As an example, this figure
shows the initial configuration of the Ca2+-substituted kaolinite (001)
surface/20-Å water molecule layer at a substitution ratio of 6.25 %.
To directly demonstrate the effect of Ca2+ substitution on the surface
hydrophilicity of kaolinite, we simulated the contact angle. Firstly, A
water balloon with a diameter of 20 Å is constructed using an Amor­
phous Cell module and its density is 1.0 g/cm3. Then the kaolinite single
crystal cell was expanded to 12 × 6 × 2 supercells. The supercells are cut
along the (001) and (001) planes and a 100 Å vacuum layer is added to
form the surface. Using the Build Layer tool, water balloons are added
2–3 Å away from the surface where Ca2+ substituted kaolinite. This
results in a structural model of Ca2+ substituted kaolinite/water bal­
loons (Fig. 6). As an example, the figure shows the initial configuration
of the Ca2+ substituted kaolinite (001) surface/water balloon at a sub­
stitution ratio of 6.25 %. The change of surface hydrophilicity of
kaolinite after Ca2+ substitution can be expressed by surface free energy,
the higher the surface free energy, the stronger the hydrophilicity. The
surface free energy [38–40] is given by equation (2):
√̅̅̅̅̅̅
γ 2
cosθY = − 1 + 2 sv e− β(γlv − γsv ) (2)
γ lv

Fig. 2. Stable configurations of water molecules and of the (001) and (001) where θY is the contact angle of the water drop on the mineral surface,
surfaces of Ca2+-substituted kaolinite. γ sv is the surface free energy of the solid–gas interface (usually the sur

3
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Q. Shu et al. Applied Surface Science 678 (2024) 161097

Fig. 3. Adsorption sites for water molecules on Ca2+-substituted kaolinite surfaces. (a) The (001) surface, (b) The (001) surface.

Fig. 4. Molecular-dynamics models of the (001) surface of Ca2+-substituted kaolinite. (a) 0 %, (b) 1.56 %, (c) 3.13 %, and (d) 6.25 %.

× ×
Fig. 5. Initial model of a layer of water molecules adsorbed on the (001) surface of Ca2+-substituted kaolinite.

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Q. Shu et al. Applied Surface Science 678 (2024) 161097

× ×

Fig. 6. Initial model of a water droplet adsorbed on the (001) surface of Ca2+-substituted kaolinite.

face free energy of the solid surface), and γlv is the surface free energy of 3.1.1. Analysis of the optimal configuration
the liquid–gas interface (i.e. the surface free energy of the liquid). Beta is We optimized the adsorption configuration of a single water mole­
a constant [39] and has a value of 0.0001247. The unit of surface free cule at different sites on the surface of Ca2+-substituted kaolinite,
energy is mJ/m2. The surface free energy of water [38] at room tem­ calculated the stable adsorption energy of this configuration, and
perature is about 72.8 mJ/m2. compared the results to obtain the optimal adsorption configuration.
The Forcite plus module in MS is used for all MD simulations. The As shown in Fig. 7, the optimal adsorption sites for water molecules
calculation adopts the ClayFF [41] force field, which is suitable for clay on the (001) and (001) surfaces of Ca2+-substituted kaolinite are H12
mineral systems, and employs the NVT ensemble [42], with three- and B6, which have corresponding adsorption energies of approxi­
dimensional periodic boundary conditions. The Nose function is used mately − 78.25 and − 62.52 kJ/mol, respectively. For comparison, the
for temperature control, with a time step of 0.5 fs. Ewald and atom- minimum adsorption energies of a single water molecule on the (001)
based methods were used for long-range electrostatic and van der and (001) surfaces of pure kaolinite are approximately − 72.12 and −
Waals interactions, respectively, with a cutoff radius of 17.5 Å. To 19.23 kJ/mol [44], respectively. Therefore, the energy of the adsorption
reduce unreasonable contact between molecules, the model geometri­ system after Ca2+ substitution is lower than that of pure kaolinite. The
cally is optimized through the conjugate-gradient method. To ensure substitution of Ca2+ changes the adsorption sites for water molecules on
system equilibration, energy, and temperature convergence curves are the kaolinite surface, promoting water molecule adsorption. Comparing
monitored over time during the first 300 ps of system equilibration. The the adsorption system energies of the (001) surface and the (001) surface
resulting output of the balanced adsorption system continues to be also shows that regardless of whether or not Ca2+ was substituted into
calculated at intervals of 100 ps, with data output at intervals of 2.5 ps. the kaolinite, water molecules were more inclined to be adsorbed onto
For other specific parameter settings and simulation steps, please refer the (001) surface. The substitution of Ca2+ thus strengthens the surface
to reference [43]. hydration of fine kaolinite particles, making the dehydration of coal
slurry more difficult. This demonstrates that the effect of lattice sub­
3. Results and analysis stitutions must be considered to achieve efficient dehydration of fine
particles such as those in coal slurry.
3.1. Analysis of microscopic mechanisms
3.1.2. Analysis of microscopic interactions
Through DFT, we simulated the adsorption of water molecules on the Fig. 7 shows the optimal adsorption configurations of water mole­
(001) and (001) surfaces of Ca2+-substituted kaolinite and explored the cules on the (001) and (001) surfaces of Ca2+-substituted kaolinite. The
microscopic mechanism. blue dashed lines in the figure represent hydrogen bonding, while the
black dashed line represents non-hydrogen bonding between connected
atoms. As depicted in the figure, bonding interactions exist between the

Eads Eads

Fig. 7. Adsorption energies and optimal adsorption configurations of water molecules on Ca2+-substituted kaolinite surfaces. (a) The (001) surface, (b) The
(001) surface.

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water molecules and the surfaces of Ca2+-substituted kaolinite. Popu­

lation analysis was conducted to evaluate their role in the adsorption
process through existing bonds.
Table 2 shows the simulated bond parameters and corresponding
population values, where d(H…O) is the distance between the bonding
atoms H and O. According to the simulation results, there are three pairs
of hydrogen bonds between water molecules and the (001) surface of E E
Ca2+-substituted kaolinite, with an average length of 1.94 Å and bond
population values of 0.02–0.10. Conversely, there is no hydrogen bond
between water molecules and the (001) surface of Ca2+-substituted
kaolinite. However, other bonds—with a length of 2.57 Å and a popu­
lation value of 0.01—link the water molecules to the surface. Reference
[44] describes water molecules being adsorbed onto the pure kaolinite
(001) surface to form three pairs of hydrogen bonds, with an average
length of 1.97 Å and population values ranging from 0.03 to 0.10. They Fig. 8. Differential electron-density map for the optimal equilibrium configu­
also discuss two pairs of hydrogen bonds that are formed by adsorption rations. (a) The (001) surface, (b) The (001) surface. The isosurfaces are shown
onto the (001) surface, with an average length of 2.24 Å and a popula­ at 0.003 electrons/Å3.
tion value of 0.00–0.03. A comparative analysis revealed that the
bonding effect of water molecules on the (001) surface of kaolinite was adsorption of water molecules. Consequently, water molecules are more
enhanced after Ca2+ substitution. However, the bonding effect is weaker likely to be adsorbed onto the (001) surface than the (001) surface.
on the kaolinite (001) surface. Whether Ca2+ is substituted or not, the
bonding of water molecules on the (001) surface of kaolinite is stronger
3.2. Analysis of hydration mechanisms in different water layers
than that on the (001) surface. The conclusions obtained from this
bonding analysis do not fully correspond to the adsorption stability re­
The DFT simulations show that the adsorption of water molecules
sults, indicating there are other interactions besides bonding between
water molecules and Ca2+-substituted kaolinite surfaces. onto the (001) surface of kaolinite is stronger than onto the (001) sur­
Because Ca2+ substitution causes changes in the surface charge of face. To explore the hydration mechanism of a Ca2+-substituted
kaolinite, it generates electrostatic interactions with water molecules. kaolinite surface, we used the MD method to simulate the adsorption
The differential electron-density map shown in Fig. 8 (the blue repre­ kinetics of five different thicknesses of water layers on the kaolinite
sents electron aggregation, and the yellow represents electron con­ (001) surface after a Ca2+ substitution of 6.25 %.
sumption) and the Mulliken charge transfer amount were calculated for
the optimal adsorption configuration. As Fig. 8 shows, there is consid­ 3.2.1. Spatial-equilibrium configurations
erable charge transfer between water molecules and the surface in both The spatial-equilibrium configuration is the most intuitive manifes­
adsorption configurations, with electrons transferring from the mineral tation of water molecule adsorption on a surface, and it can be used to
surface to the water molecules. This results in electrostatic adsorption understand the microscopic characteristics of interfacial adsorption.
between the water molecules and the mineral surface. Fig. 9 shows the spatial-equilibrium configurations of water layers
The amounts of charge transferred to the water molecules from the with different thicknesses adsorption on the (001) surface of Ca2+-
substituted kaolinite. This figure shows that the water molecules are
(001) and (001) surfaces of Ca2+-substituted kaolinite are 0.05 and 0.06
strongly ordered when they are closer to the surface, while the farther
e; for comparison, the comparable amounts of charge transferred from
they are, the more diffuse they become. In addition, the balancing Na+
the (001) and (001) surfaces of pure kaolinite are 0.04 and 0.02 e [44].
tends to enter the water layer. Combined with the DFT analysis, this
As the amount of charge transfer increases, the electrostatic interaction
demonstrates that the water molecules closest to the (001) surface of
becomes stronger, and the adsorption configuration becomes more sta­
Ca2+-substituted kaolinite primarily form Os–Hw and Hs–Ow
ble. After Ca2+ substitution, the electrostatic interaction between the
hydrogen bonds with the surface. The water molecules also form a
kaolinite surface and the water molecule is enhanced, which makes the
spatial network structure [45–47] through hydrogen bonding, thereby
structure more stable. In addition, the electrostatic interaction between
forming a hydration film that covers the surface.
the water molecule and the (001) surface is stronger than that with the
(001) surface. 3.2.2. Dynamic analysis of water molecules
This analysis of the microscopic interactions thus shows that Ca2+ We have used concentration distributions, density distributions
substitution enhances the interaction between water molecules and the (DDs), and radial distribution functions (RDFs) to characterize the dy­
(001) surface of kaolinite. In comparison, although the bonding between namic characteristics of water molecules in the simulation results.
water molecules and the kaolinite (001) surface is weakened, the elec­ Fig. 10 (a) shows the normal concentration distributions of Ow atoms on
trostatic interaction is enhanced, which ultimately promotes the the (001) surface of Ca2+-substituted kaolinite for water layers (WLs) of
different thicknesses. These curves reflect the changes in the water
molecule concentrations. When the thickness of the WL is 2 Å, only one
Table 2
Mulliken bond population of water molecules adsorbed on Ca2+-substituted peak exists, located 1.961 Å from the surface. When the thickness of the
kaolinite surfaces. WL is increased to 5 Å, a second peak appears at a distance of 4.921 Å
from the surface. Further increasing the thickness of the WL to 10 Å
Configuration Position Eads (kJ/ Bonds d (H…O) Bond
mol) (Å) population results in a third peak appearing at a distance of 8.486 Å from the sur­
face. As the water layer thickness gradually increases, the concentra­
H2O/001 H12 − 78.25 Hs1… 2.10 0.02
tions of each peak in the distribution curve gradually decrease and shift
Ow
Hs2… 2.03 0.05 away from the surface. When the water layer is 2 Å thick, the water
Ow molecules are strongly bound to the (001) surface of the Ca2+-
Os… 1.70 0.10 substituted kaolinite. However, as the water layer thickens, the force
Hw
binding the water molecules to the surface gradually diminishes, form­
H2O/001 B6 − 62.52 Os–Hw 2.57 0.01
ing multiple layers of water molecules. When the thickness of the water

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Q. Shu et al. Applied Surface Science 678 (2024) 161097

Fig. 9. Spatial-equilibrium configurations of the (001) surface of Ca2+-substituted kaolinite with different thicknesses of adsorbed water layers. (a) 2, (b) 5, (c) 10,
(d) 20, and (e) 30 Å.

layer increases to 10 Å, there are three layers of water molecules (as differ. By increasing the thickness of the water layer, the force binding
shown by dashed lines labeled I, II, and III in the figure). the water molecules to the surface decreases, the interface effect
Fig. 10 (b) shows the DD [48,49] of H2O along the direction normal weakens, and the degree of order on the surface decreases. When the
to the (001) surface of Ca2+-substituted kaolinite. Based on the data in water layer thickness reaches 20 Å, the peak intensity changes tend to
the figure, the main distribution positions and density of water mole­ stabilize, indicating stabilization of the interfacial water layer structure.
cules at the interface under different thicknesses of WLs can be under­
stood. This figure illustrates that the peak position of the water molecule 3.2.3. Analysis of the influence of Na+ on the hydration mechanism
density remains essentially unchanged as the thickness of the water The formation of coordinated structures between the Na+ and the
layer gradually increases. However, the peak height first increases and surrounding water molecules in aqueous solutions—which affects the
then decreases, and the structure remains similar at 20 Å and 30 Å. This surface hydration of minerals—makes it necessary to analyze the dy­
indicates that the water molecules have transitioned from disorder to namic changes of the Na+-ion distribution during the hydration simu­
order, and the adsorbed layer’s structure tends to stabilize once it rea­ lations. Fig. 11 (a) shows the RDF of Na+ relative to the Ow atoms in
ches a thickness of 20 Å. water molecules on the (001) surface of Ca2+-substituted kaolinite,
Fig. 10 (c and d) show the RDFs [50,51] of the Os–Hw and Hs–Ow which reveals the degree of ordering of Ow atoms around Na+. This
atomic pairs, respectively, on the (001) surface of Ca2+-substituted figure shows that the position and shape of the peak of the RDF remain
kaolinite. By analyzing these figures, we can understand the degree of the same as the water layer thickness changes. This indicates that
ordering of water molecules on the Ca2+-substituted kaolinite (001) increasing the thickness of the water layer does not change the relative
surface. These figures show that the peak positions of the RDFs remain spatial positions of the Ow atoms around Na+; that is, the coordination
unchanged with increasing the thickness of the water layer. However, distance remains the same. As the water layer thickness increases, the
the intensities of the two RDF peaks decrease continuously with intensity of the first peak at 2.38 Å gradually decreases, indicating a
increasing the thickness of the water layer, but the shapes of the peaks reduced ordering of the Ow atoms around Na+.

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Q. Shu et al. Applied Surface Science 678 (2024) 161097

Fig. 10. Distribution characteristics of water molecule dynamics for water layers of different thicknesses. (a) CDP of Ow, (b) DD of H2O, (c) RDF for Os–Hw, and (d)
RDF for Hs–Ow.

Fig. 11. Characteristics of the dynamic distribution of Na+ in water layers of different thicknesses. (a) RDF of Na–Ow, (b) RDF of Na–Os.

Fig. 11 (b) shows the RDF of Na+ relative to the Os atoms on the In summary, the (001) surface of Ca2+-substituted kaolinite forms a
2+
Ca -substituted kaolinite (001) surface, which reveals the coordination three-layered hydration film in aqueous solution. As the water layer
between Na+ and Os atoms. This figure exhibits a tall and narrow peak at thickness increases, the force binding the water molecules to the surface
2.29 Å, and the position and shape of the peak remain the same for WLs decreases, and the interface effect weakens. The structure of the inter­
of different thicknesses. As the water layer thickness increases, the peak facial water layer tends to stabilize when its thickness reaches 20 Å. The
value tends to decrease. This indicates that changes in the water layer coordinated structure between Na+ and the oxygen atoms in the water
thickness do not alter the coordination distance between Na+ and Os molecules and on the surface enhances the surface-hydration
atoms. However, as the water layer thickens, Na+ is more likely to enter characteristics.
it.

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Q. Shu et al. Applied Surface Science 678 (2024) 161097

3.3. Analysis of the hydration mechanism with different amounts of Ca2+ different Ca2+ substitution amounts. The first peak is located at 2.856 Å
substitution from the surface, the second at 5.411 Å from the surface, and the third at
8.989 Å from the surface. As the amount of the Ca2+ substitution in­
The dynamic simulations of WLs of different thicknesses but with the creases, the heights of each peak in the distribution curve increase and
same amount of Ca2+ substitution showed that the structure of the shift toward the surface. This indicates that Ca2+ substitution increases
interfacial water layer becomes stable when it reaches a thickness of 20 the force binding water molecules to the kaolinite (001) surface, pro­
Å. To study how substituting varying amounts of Ca2+ affects the surface moting surface hydration. This effect is enhanced as the amount of Ca2+
hydration characteristics of kaolinite, we used the MD method to substitution increases.
simulate the effects of four different levels of Ca2+ substitutions on the Fig. 13 (b) shows the DDs of H2O on the kaolinite (001) surface for
hydration process of the kaolinite (001) surface. During the simulation, different amounts of Ca2+ substitutions. As shown in the figure, the peak
we consistently maintained a water layer thickness of 20 Å. of the H2O DD on the (001) surface of kaolinite remains unchanged for
different amounts of Ca2+ substitution, but as the substituted amount
3.3.1. Spatial-equilibrium configurations increases, the position of the peak gradually shifts inward toward the
Fig. 12 shows the spatial-equilibrium configurations of water mole­ kaolinite surface. Among the four amounts of Ca2+ substitutions, the
cules adsorbed onto the kaolinite (001) surface for different amounts of density of water molecules reaches its highest value when the
Ca2+ substitutions (0 %, 1.56 %, 3.13 %, and 6.25 %) covered by a 20 Å substituted amount is 3.13 %. This indicates that the force binding H2O
water layer. to the kaolinite (001) surface is enhanced by the Ca2+ substitution, with
This figure illustrates that water molecules exhibit strong order near the strongest binding force occurring at a substituted amount of 3.13 %.
the surface, and become more diffuse further away. When combined A larger Ca2+ substitution weakens the binding force.
with DFT analysis, it is evident that water molecules closest to the Fig. 13 (c and d) depict the RDFs for Os–Hw and Hs–Ow atomic
kaolinite (001) surface primarily interact with the surface via hydrogen pairs on the kaolinite (001) surface at various levels of Ca2+ substitution.
bonds. These water molecules also form connections with each other Fig. 13 (c) shows that the peak position of the RDF of Os–Hw atomic
through hydrogen bonds, resulting in the formation of a hydration film pairs on the kaolinite (001) surface remains unchanged for different
on the surface. amounts of Ca2+ substitution. Increasing the substituted amount leads to
an increase in the height of the peak. This indicates that the degree of
3.3.2. Dynamic analysis of water molecules order of water molecules arranged on the surface increases after Ca2+
Fig. 13 (a) shows the normal concentration distributions of Ow atoms substitution and that the extent of this increase increases with the
on the kaolinite (001) surface for different amounts of Ca2+ sub­ amount substituted. In contrast, Fig. 13 (d) shows that while the peak
stitutions. This figure shows that the concentration of Ow atoms on the position of the RDF of Hs–Ow atomic pairs on the kaolinite (001) sur­
kaolinite (001) surface reaches its peak at almost the same position for face remains unchanged with differing amounts of Ca2+ substitution, the

Fig. 12. Spatial-equilibrium configurations of water layer adsorption on the (001) surface of kaolinite different amounts of Ca2+ substitutions. (a) 0 %, (b) 1.56 %,
(c) 3.13 %, and (d) 6.25 %.

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Q. Shu et al. Applied Surface Science 678 (2024) 161097

Fig. 13. Characteristics of the dynamical distribution of water molecules with different amounts of Ca2+ substitutions. (a) CDP of Ow, (b) DD of H2O, (c) RDF for
Os–Hw, and (d) RDF for Hs–Ow.

Fig. 14. Characteristics of the dynamical distribution of Na+ for different amounts of Ca2+ substitution. (a) RDF of the Na–Ow atomic pairs, (b) RDF of the Na–Os
atomic pairs.

height of the peak decreases with increasing amounts of substitution. Å. However, the height of this peak gradually decreases as the
This indicates that the primary bonding interaction between water substituted amount increases. This indicates that the coordination dis­
molecules and the Ca2+-substituted kaolinite (001) surface is the tance between Na+ and the surface O atoms remains unchanged after
Os–Hw bond. Ca2+ substitution. However, as the substituted amount increases, Na+
tends to move away from the surface and into the water layer.
3.3.3. Analysis of the influence of Na+ on the hydration mechanism In summary, the interaction between the kaolinite (001) surface and
Fig. 14 shows the RDFs of the Na–Ow and Na–Os atomic pairs on water molecules is enhanced by Ca2+ substitution, and the interaction
the kaolinite (001) surface for different amounts of Ca2+ substitution. force tends to increase with an increase in the amount substituted. In
Fig. 14 (a) shows that the peak position of the RDF of the Na–Ow atomic addition, the simulation shows that the balancing Na+ also forms co­
pairs remains unchanged, reaching a peak at approximately 2.39 Å. As ordinated structures with the surrounding oxygen atoms, enhancing the
the substituted amount increases, the peak’s height gradually increases. surface-hydration characteristics of the kaolinite, but they tend to enter
Fig. 14 (b) shows that the peak position of the RDF of the Na–Os the water layer as the amount substituted increases.
atomic pairs remains unchanged, reaching a peak at approximately 2.29

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Q. Shu et al. Applied Surface Science 678 (2024) 161097

3.4. Simulations of contact angle Table 3

Surface free energy of kaolinite with different amounts of Ca2+ substitutions
The above simulation results show that Ca2+ substitution does pro­ (mJ/m2).
mote the surface hydration of kaolinite, but the current simulation Surface free energy 0% 1.56 % 3.13 % 6.25 %
cannot answer whether Ca2+ substitution changes the surface hydro­ γ001 67.67 69.40 69.51 71.82
philicity of kaolinite. For this purpose, the contact angle of water γ001 47.78 50.71 52.42 61.65
droplets on kaolinite surfaces with different Ca2+ substitution amounts
was measured by molecular simulation method, and the surface free
energy was calculated. synthesized samples are shown in Table 4; they show that the HI value
As shown in Fig. 15 and Table 3, contact angle simulation results and decreases and the proportion of high-defect kaolinite increases as the
corresponding surface free energy of kaolinite surfaces with different substituted amount increases.
Ca2+ substitution amounts are obtained. It can be seen that on the pure To investigate how the substituted metal content affects the lattice
kaolinite (001) surface, the contact angle is 22.8◦ , and the surface free parameters (a, b, and c) of kaolinite, the angular parameters (α, β, and γ)
energy is 67.67 mJ/m2. With the increase of Ca2+ substitution, the of the triclinic structures of the synthesized samples were inferred based
contact angle decreases and the surface free energy increases. On the on the XRD spectra of PDF # 79–1570 [54]; they correspond to α =
pure kaolinite (001) surface, the contact angle is 60.1◦ , and the surface 91.700◦ , β = 104.862◦ , and γ = 89.822◦ . By selecting the (020), (002),
free energy is 47.78 mJ/m2. With the increase of Ca2+ substitution, the and (110) planes, which have stronger diffraction peaks, to calculate the
change of contact angle and surface free energy is similar to that of the crystal-cell parameters [55], we obtained the results shown in Table 4.
(001) surface. This indicates that Ca2+ substitution promotes the surface Compared to pure kaolinite, the lattice parameters of the synthesized
wettability of kaolinite, and indeed changes the surface hydrophilicity of samples increase with increasing Ca2+ substitution. This leads to a
kaolinite, making its surface more hydrophilic, and water molecules can change in the kaolinite structure.
better spread on the surface of kaolinite, and finally form a water film. Changes in the lattice structure of a mineral result in corresponding
changes to its surface properties. Fig. 16 (c) shows the FTIR spectra of
the synthesized samples of Ca2+-substituted kaolinite. According to
3.5. Experimental verification reference [54], the infrared spectrum of kaolinite can be divided into
high-frequency (3500–3750 cm− 1) and low-frequency (400–1200 cm− 1)
The simulations above indicate that substituting Ca2+ enhances the sections. Four strong high-frequency bands near 3620, 3654, 3664, and
hydration of the kaolinite surface, leading to increased surface hydro­ 3695 cm− 1 were characteristic absorption peaks of pure kaolinite; they
philicity. Therefore, what exactly is this like in practice? To check the indicate changes in the O–H bonds in the mineral. Changes in the 1112
results of the simulations, we consequently synthesized samples using and 1038 cm− 1 bands at low frequencies indicate alterations in the
the hydrothermal method and performed hydration tests on them. Si–O–Si bonds. Changes in the 938 and 913 cm− 1 bands indicate
modifications in the Al–O–H bonds. Changes in the 540 cm− 1 band
3.5.1. Characterization of samples signify variations in the Al–O–Si bonds, while changes in the 429 cm− 1
First, we characterized the samples. Fig. 16 (a) shows the XRD band indicate alterations in the O–Al–O bond [56,57]. These results
spectra of the synthesized samples of Ca2+-substituted kaolinite, and show that the relative intensities of the 3620 and 3695, 1112 and 1038,
Fig. 16 (b) shows the three characteristic XRD peak spectra of the sample 938 and 913, and 540 and 429 cm− 1 bands decrease as the content of
on expanded angular scales. These figures show that the main diffraction substituted ions increases. The decreases in the relative intensities of
peak shifts after substitution, indicating that Ca2+ has entered the these bands indicate that the content of alumina groups in the synthe­
kaolinite structure. With increasing content of the substituted ion, the sized samples decreases as the substituted amount of Ca2+ increases.
reflection peak of the (060) plane shifts gradually to the left, indicating However, the main functional groups in the sample remain unchanged,
that the lattice parameter b of the kaolinite is gradually increased [52]; indicating that, while Ca2+ has entered the kaolinite lattice in the syn­
this is consistent with the gradual entry of Ca2+ into the structure. The thesized samples, their proportion remains small.
parameters shown in Table 4 summarize data from the XRD measure­ Fig. 16 (d) shows XPS scans of elemental Ca in the synthesized
ments of all three synthesized samples; kaolinite is considered the only samples of Ca2+-substituted kaolinite. We first evaluated the atomic
crystalline phase. However, metal substitution affects the lattice through environments in the synthesized samples and discovered that the bind­
isomorphic substitution, indicating the entry of metals into the lattice ing energies of the Al 2p, Si 2p, and O 1 s electronic states were
structure of kaolinite [43]. 74.5–74.7, 102.9–103.0, and 529.3–532.0 eV, respectively. These
In addition, the substitution of Ca2+ impacts the relative strength of values fall within the anticipated ranges for silicon and aluminum oxides
the XRD spectrum. The Hinckley index (HI) [53] can describe the ratio [58]. In addition, the binding energies of the Al 2p, Si 2p, and O 1 s
of low-defect kaolinite to high-defect kaolinite in samples by calculating electrons in the different samples are very similar, indicating that the
its relative strength from the spectra. The HI values of all three synthesized samples have similar binding environments. This figure

Fig. 15. Contact angle simulation results of kaolinite surface with different amounts of Ca2+ substitutions. (a) 0 %, (b) 1.56 %, (c) 3.13 %, and (d) 6.25 %.

11
Q. Shu et al. Applied Surface Science 678 (2024) 161097

Fig. 16. Characterization of synthesized samples. (a) Full XRD spectra, (b) XRD characteristic peaks, (c) Full FTIR spectra, (d) XPS scan of elemental Ca.

Table 4
Summary of data obtained from XRD spectra.
Sample a (Å) b (Å) c (Å) Hinckley index

0% 5.3486 9.2362 7.6647 1.373

1.56 % 5.3430 9.2455 7.6591 1.446
3.13 % 5.3526 9.2728 7.6776 1.230

Table 5
Surface composition of samples by XPS (atomic %).
Sample Si Al Ca O

0% 16.35 13.29 0.38 69.97

1.56 % 16.59 13.66 0.56 69.19
3.13 % 16.44 13.26 0.60 69.70

shows that the content of elemental Ca on the surface of the kaolinite is

substantially increased after Ca2+ substitution, and the surface content
increases with the amount substituted. The surface composition of the
Fig. 17. Hydration-test results for synthesized samples of Ca2+-
samples is shown in Table 5. This result is consistent with the previous
substituted kaolinite.
characterization.
In summary, after Ca2+ substitution, the main diffraction peak of the
XRD spectrum of kaolinite shifted, and the lattice parameters changed. requirements, the contact-angle and humidity test methods [43] were
According to the HI, the proportion of high-defect kaolinite increased as used to test the hydration characteristics of the synthesized samples of
the amount of Ca2+ substitution increased. The number and relative Ca2+-substituted kaolinite.
strengths of the functional groups on the kaolinite surface also changed, Fig. 17 shows that the pure kaolinite exhibits strong hydrophilicity
as shown by the FTIR spectra. In addition, the XPS test results confirmed and the contact angle decreases as Ca2+ substitution increases, which is
the increased content of elemental Ca in the synthesized samples. These the same as the contact angle simulation law of water droplets adsorbed
all indicate that Ca2+ has entered the structure of the kaolinite, meeting on the surface of kaolinite. The results of the microcantilever humidity
the requirements for further research. test show that the deflection of the microcantilever increases as the
amount of substitution increases. The larger the deflection of the
3.5.2. Hydration experiments microcantilever beam, the higher the humidity of the test sample. This
After confirming that the synthesized samples met the experimental demonstrates that the hydrophilicity of the kaolinite surface is enhanced

12
Q. Shu et al. Applied Surface Science 678 (2024) 161097

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