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Article

Adsorption of Y(III) on the Interface of Kaolinite-H2O: A DFT Study

by
Xiangrong Zeng
1,
Bin Zeng
1,
Lijinhong Huang
2,3,*,
Liang Zhong
4,
Xindong Li
4 and
Wanfu Huang
1,4,*
1
School of Resource and Environmental Engineering, Jiangxi University of Science and Technology, Ganzhou 341000, China
2
School of Architecture and Design, Jiangxi University of Science and Technology, Ganzhou 341000, China
3
Faculty of Science and Engineering, WA School of Mines, Minerals, Energy and Chemical Engineering, Curtin University, Perth, WA 6152, Australia
4
School of Civil and Surveying & Mapping Engineering, Jiangxi University of Science and Technology, Ganzhou 341000, China
*
Authors to whom correspondence should be addressed.
Minerals 2022, 12(9), 1128; https://doi.org/10.3390/min12091128
Submission received: 5 August 2022 / Revised: 31 August 2022 / Accepted: 1 September 2022 / Published: 5 September 2022
(This article belongs to the Section Clays and Engineered Mineral Materials)
Browse Figures
Versions Notes

Abstract

:
Ion-adsorbed rare earth minerals have rare earth ions adsorbed on the surfaces of clay minerals such as kaolinite and have high contents of medium and heavy rare earth elements. They are important resources supporting the development of high-tech industries. In this study, the CASTEP module in Materials Studio was used to study the adsorption of the rare earth ion Y(III) on the interface of (Al-OH)-H2O and (Si-O)-H2O with density functional theory. The monitoring and calculation of the chemical bond of the adsorption structure showed that Y(III) on the (Al-OH)-H2O interface has a bond with O32, O34, and water molecules in the interface. In the (Si-O)-H2O interface, Y(III) interacts with O3, O4, and O10 to form new chemical bonds. The Mulliken population and density of states analysis showed that Y(III) bonds with surface oxygen atoms and water molecules in the kaolinite-H2O interface, and finally adsorbs on the surface of kaolinite in the form of metal ion hydrate.

Graphical Abstract

1. Introduction

Rare earth elements can significantly improve the optical and electromagnetic properties of materials [1]. They are widely used in modern technology and have extremely high application value and strategic significance [2]. Rare earth ores are divided into mineral type rare earth ores and weathered type rare earth ores: mineral type rare earth ores are rich in light rare earth elements and are mainly represented by bastnaesite [3]; weathered rare earth minerals are mainly represented by adsorbed rare earth minerals [4], which are rich in medium and heavy rare earth elements with higher values [5]. Medium and heavy rare earths have higher values and are widely used in chemical sensing [6], superconducting materials [7], supercapacitors [8], permanent magnet materials [9], luminescent materials [10,11], biomedical nanocomposites [12,13], etc.
The rare earth elements in ion-adsorbed rare earth minerals are mainly adsorbed in clay minerals with an exchangeable adsorption state [14,15]. The clay minerals of ion-adsorbed rare earth minerals include kaolinite, montmorillonite, and illite [16]. Clay minerals [17] have been used in the treatment of rare earth element wastewater: the rich clay minerals in tailings are used as adsorbents to enrich rare earth elements, reduce the loss of rare earth elements, and improve environmental water quality.
With the development of science and technology, quantum chemistry (including ab initio, semiempirical methods, and density functional theory (DFT)) [18] has been greatly developed and widely used in mining [19,20,21], environmental [22], and material fields [23,24]. The DFT [25,26] method is more suitable for the calculation of macromolecular systems and solids [27]. Therefore, it is widely used to adsorb electrolyte cations on clay mineral surfaces [28,29]. For example, Qiu et al. [30] used the DFT method to study the coordination structure and properties of the dihydroxy hydrates of Y(III) ions, as well as their outer and inner adsorption mechanisms on the (001) surface of kaolinite. Chen et al. [31] used the theory of density functional theory to study the adsorption of Y(OH)3−nn+ ions on the surface of the kaolinite with different degrees of deprotonation. The results showed that Y(OH)3−nn+ ion interacts with the surface of kaolinite (001) through the combination of covalent bonds and electrostatic bonds and interacts with the surface of (00-1) mainly through electrostatic bonds. However, these studies focused on the adsorption of rare earth ions, hydrated rare earth ions, and single water molecules on the surface of kaolinite, and did not consider the influence of the presence of water molecular interfaces on the adsorption of rare earth ions. A small number of studies have involved the interaction of water molecules and rare earth ions on the surface of kaolinite in the presence of both. For example, Wang et al. [18] calculated the adsorption mechanism of Y(III), NH4+, and H2O on the periodic (001) surface and (00-1) surface of kaolinite by using DFT method. The results showed that Y3+ and NH4+ are more strongly adsorbed on the kaolinite (001) surface and the (00-1) surface, respectively. Both the hydrated NH4+ and Y3+ cations can be adsorbed on either the hydrated kaolinite (001) surface or the (00-1) surface, but the hydrated Y3+ can be more strongly adsorbed on the hydrated kaolinite surface than hydrated NH4+. Our work is based on the aforementioned studies. First, we added a water molecule layer when building kaolinite surface, which can better simulate the real solution situation. Then, we studied the adsorption mechanism of rare earth ions in the kaolinite-H2O interface to further deepen the research in this field. Finally, we revealed the role of rare earth ions in the clay mineral-H2O interface, which can promote the understanding of the existence of rare earth ions in clay minerals and provide a theoretical basis for the extraction of ion-adsorbed rare earth ores.
The proportion of yttrium in ion-adsorbed rare earth ore can reach 64.9% [30]. Yttrium is an important rare earth element and is widely used in TV screens, ray filters, laser materials [32], new magnetic materials [33], superconductors and superalloys [34], and special glasses [35]. Yttrium is also extremely resistant to high temperatures and corrosion and can be used as a cladding material for nuclear fuel. Therefore, it is of great significance to study the adsorption mechanism of Y(III) at the kaolinite-H2O interface on the atomic level, which will be beneficial to the development of yttrium. In this study, with Y(III) heavy rare earth as the representative, the kaolinite-H2O interface was established to study the adsorption mechanism of Y(III) in the interface. The DFT method was used to calculate the adsorption mechanism of Y(III) on the (Al-OH)-H2O interface and (Si-O)-H2O interface, and to propose and analyze the adsorption structure and energy, the Mulliken population, the partial density of states (PDOS), and the track analysis. Understanding the interaction of REE ions at the clay mineral-water interface is of great significance for understanding the process of REE mineralization, extraction, and recovery.

2. Calculation Method and Surface Model

2.1. Calculation Method and Parameter Setting

First-principles calculations were carried out in the framework of the DFT using the Cambridge Sequential Total Energy Package (CASTEP) [36,37]. The exchange-correlation function used was GGA-PBE [38], and the optimization algorithm used was BFGS and used DFT-D dispersion correction. The thickness of the vacuum slab used in calculations is 30 Å. The calculated energy cut-off value was 400 eV; the k-point was set to (2 × 1 × 2); and the self-consistent field SCF convergence accuracy was set to 2.0 × 10–6 eV/atom. The geometric optimization convergence criteria were as follows: the maximum atom displacement was 0.0002 nm, the interatomic force was 0.05 eV/Å, the interatomic internal stress was 0.1 GPa, and the total energy change of the system was 2.0 × 10−5 eV/atom [30,31].

2.2. Construction of Computational Model

In nature, the cleavage surfaces of kaolinite are divided into three types, the (001) surface, the (010) surface, and the (110) surface [39]. Quantum chemical analysis and broken bond analysis showed that the (001) surface was completely cleaved, and the (010) surface and the (110) surface were more difficult to cleave. After the surface of kaolinite (001) is completely cleaved, there are two kinds of surfaces: the Al-OH surface and the Si-O surface [14].
The CASTEP module was used to optimize the structure of kaolinite. After the optimized kaolinite unit cell was obtained, the Cleave Surface function of the MS software was used to cut the Al-OH surface and the Si-O surface of kaolinite. The model of the water molecule layer on the surface of kaolinite was built by the AC module in the MS software. The interaction between Y ions and the water molecule layer is due mainly to the participation of water molecules in the lower half. The use of 20 water molecules is suitable for the kaolinite surface system constructed in this paper. The water molecule layer on the kaolinite surface was added to establish the (Al-OH)-H2O and the (Si-O)-H2O adsorption interface models for the structure calculation and the property analysis of rare earth yttrium ion adsorption, as shown in Figure 1:

3. Results and Discussion

3.1. Frontier Orbit Analysis

Figure 2 shows the frontal orbital of the (Al-OH)-H2O and (Si-O)-H2O interface (HOMO orbital ((the highest occupied molecular orbital), LUMO orbital (the lowest unoccupied molecular orbital)) [40,41]. The calculation results show that the HOMO orbital value of the (Al-OH)-H2O interface is −0.27, and the LUMO orbital value is −0.07. The HOMO orbital value of the (Si-O)-H2O interface is −0.24, and the LUMO orbital value is −0.08. The electron cloud of the HOMO orbital is mainly concentrated on hydrogen atoms and some oxygen atoms; the electron cloud of the LUMO orbital is mainly distributed on the oxygen atoms on the surface of kaolinite and the oxygen atoms of water. It shows that the oxygen atoms on the surface of kaolinite and the oxygen atoms of water can easily obtain electrons and can interact with the rare earth ions that provide electrons. Therefore, rare earth ions are more likely to interact with these oxygen atoms.

3.2. Adsorption Geometries and Energies

3.2.1. Adsorption Geometries

According to the research of Peng et al. [31], the Y(III) is placed in kaolinite-H2O interface, and the initial configuration is geometrically optimized as shown in Figure 3. Figure 4 shows the serial numbers of oxygen atoms on the surface of kaolinite, and Table 1 shows the change in the distance between Y and O atoms on the surface of kaolinite. Figure 3 shows that the distance between the water molecular layer and kaolinite surface increases after relaxation. Table 1 shows that the vertical distance between Y(III) and kaolinite surface increases and moves to one side. In the (Al-OH)-H2O interface, Y(III) moves away from O16, O17, and O18, and move to the side of O32 and O34. After the adsorption is stable, the distance between Y(III) and O34 changes from 3.393 Å to 2.495 Å; the distance from O16 and O18 increases from 2.589 Å, 3.568 Å to 4.342 Å and 5.314 Å. In (Si-O)-H2O, Y(III) is far away from O5, O9, and O21, and approaches to the side of O3, O4, and O10. After the adsorption is stable, the distance between Y(III) and O4 changes from 2.901 Å to 2.685 Å; the distance from O9 and O21 increases from 2.956 Å, 2.976 Å to 3.772 Å and 3.27 Å. Figure 3 show that the monitoring and calculation of the chemical bond of the adsorption structure showed that Y(III) in the (Al-OH)-H2O interface has a bond with O32, O34, and water molecules in the interface. In the (Si-O)-H2O interface, Y(III) interacts with O3, O4, and O10 to form new chemical bonds. Y(III) bonds with surface oxygen atoms and water molecules in the kaolinite-H2O interface, and finally adsorbs on the surface of kaolinite in the form of metal ion hydrate.

3.2.2. Adsorption Energies

Based on the research described in this article, the energy released during the adsorption process is defined as the adsorption energy, and it is calculated as follows:
Eads = Eadsorbate/slab − Eadsorbate − Eslab
where Eads is the adsorption energy of the adsorbate on the surface, Eadsorbate/slab is the total energy of the system after the adsorbate is adsorbed on the surface, Eadsorbate is the total energy of the adsorbate before adsorption, and Eslab is the previous total energy for the surface of the layered crystals. The calculated adsorption energies are shown in Table 2.
The Eads values for Y on the (Al-OH)-H2O and (Si-O)-H2O planes were −246.05 kJ/mol and −482.46 kJ/mol, respectively, indicating that Y(III) underwent an adsorption reaction with the interface of kaolinite-H2O. The capacity for adsorption of Y(III) on the (Si-O)-H2O interface was stronger than that for the (Al-OH)-H2O interface. That may be due to the existence of an H atom layer at the (Si-O)-H2O surface of kaolinite.

3.3. Mulliken Population and Density of States Analysis

To further understand the interaction mechanism between the Y(III) and kaolinite-H2O interface, we analyzed the Mulliken population and density of states analysis in the most stable adsorption configuration. The Mulliken population analysis provides insight into the charge transfer of each element, the charge distribution between atoms, the state of valence electrons, and the form of bonding. The density of states can be used to analyze the contribution of different atomic orbitals to the valence band, the difference in the activity of atoms, and the hybridization of the orbitals between atoms. This can help foster understanding of the bonding information and electron transfer.

3.3.1. Adsorption of Y(III) on (Al-OH)-H2O Interface

To study the bonding mode and bonding strength of Y(III) at the (Al-OH)-H2O interface, bond population analysis was performed on the bonding atoms and the results are shown in Table 3. Figure 5 shows the partial-wave state density analysis of atoms participating in bonding.
Table 3 shows that after the adsorption reaction, Y(III) bonds with the two O atoms on the (Al-OH) surface of the kaolinite and the oxygen atoms in the four water molecules. The bond populations of Y-O32 and Y-O34 are 0.18 and 0.13, respectively, and the bond lengths are 2.50940 Å and 2.49713 Å. Y bonds with H2O(44), H2O(50), H2O(52), and H2O(56). The bond populations are 0.13, 0.13, 0.19, and 0.19, respectively, and the bond lengths are 2.66690 Å, 2.61842 Å, 2.43310 Å, 2.45606 Å. Y(III) has the strongest effect with O56, and the weakest with O34, O44 and O50.
Figure 5 shows that the 5s orbital of Y is mainly concentrated in the range of −9.5~−7 eV, 2~10 eV, the 4p orbital is concentrated in the range of −10~−5 eV, −1~13 eV, and the 4d orbital is concentrated in the range of −9~−4 eV, −1~10 eV. In the range of −10~−4 eV, the 4d orbital of Y overlaps the s and p orbitals of O32 and O34 atoms, but the overlap of the 4d orbital of Y with the s orbital of O32 is significantly higher than that of the s orbital of O34. It shows that the intensity of the interaction between Y and O32 is higher than that of O34, which is consistent with the results in Table 2. In the range of −10~−8 eV, the 4d orbital of Y overlaps with the 2s orbitals of O52 and O56 atoms and slightly overlaps with the 2s orbitals of O44 and O50 atoms. It shows that the bonding effect of Y with O52 and O56 is higher on the surface of kaolinite, which is consistent with the conclusion of the Mulliken population analysis.

3.3.2. Adsorption of Y(III) on (Si-O)-H2O Interface

To study the bonding mode and bonding strength of Y(III) at the (Si-O)-H2O interface, bond population analysis was performed on the bonding atoms and the results are shown in Table 4. Figure 6 shows the partial-wave state density analysis of the atoms participating in the bonding.
Table 4 show that after the adsorption reaction, Y(III) bonds with the three O atoms on the (Al-OH) surface of kaolinite and the oxygen atoms in the three water molecules. The bond populations of Y-O10, Y-O3 and Y-O4 are 0.1,0.07 and 0.00, respectively, and the bond lengths are 2.58615 Å, 2.68984 Å and 2.68546 Å. Y bonds with H2O(38), H2O(39), and H2O(52). The bond populations are 0.21, 0.19, and 0.18, respectively, and the bond lengths are 2.41467 Å, 2.42406 Å, 2.61860 Å.
Figure 6 shows that in the range of −9~−4 eV, the Y 4d orbital overlaps the O 2s and 2p orbitals significantly, and the overlap of the 2s orbital with O38, O39, and O52 is higher than that of O10, O3, O4, indicating that Y has stronger bonding with O38, O39, O52. O10, O3, and O4 come from the oxygen atoms on the surface of kaolinite, while O38, O39, and O52 come from the water molecules in the interface. That indicates that the bond between Y and the (Si-O) interface is stronger than that of H2O, which is consistent with the Mulliken bond population results. In the range of 5~8 eV, the 4d orbital of Y obviously overlaps with the 2s orbitals of O10 and O3 atoms, and slightly overlaps with the 2s orbitals of O4 atoms. It shows that the bonding effect of Y and O4 on the surface of kaolinite is relatively lower, which is consistent with the conclusion in Table 4. Comprehensive analysis infers that: Y preferentially bonds with water molecules in the kaolinite-H2O interface, and then hybridizes with the 2s and 2p orbitals of O on the surface of kaolinite through its 4d orbital.

4. Conclusions

In this paper, the adsorption behaviours of rare earth ions during extraction processes of ion-adsorbed rare earth ores are studied, and the adsorption behaviours of Y(III) adsorbed on the (Al-OH)-H2O interface and (Si-O)-H2O interface are studied using quantum chemistry calculation methods. The unit cell structure, adsorption energy, density of states distribution and other properties of the surface adsorption model are analysed. In this study, we reveal the role of rare earth ions in the clay mineral-H2O interface, which can promote the understanding of the existence of rare earth ions in clay minerals and provide a theoretical basis for the extraction of ion-adsorbed rare earth ores.
The Eads values for Y on the (Al-OH)-H2O and (Si-O)-H2O planes were −246.05 kJ/mol and −482.46 kJ/mol, respectively, indicating that Y(III) underwent an adsorption reaction with the interface of kaolinite-H2O. The capacity for adsorption of Y(III) on the (Si-O)-H2O interface was stronger than that for the (Al-OH)-H2O interface. The monitoring and calculation of the chemical bond of the adsorption structure showed that Y(III) in the (Al-OH)-H2O interface has a bond with O32, O34, and water molecules in the interface. In the (Si-O)-H2O interface, Y(III) interacts with O3, O4, and O10 to form new chemical bonds. The Mulliken population and density of states analysis showed that Y(III) bonds with surface oxygen atoms and water molecules in the kaolinite-H2O interface, and finally adsorbs on the surface of kaolinite in the form of metal ion hydrate.

Author Contributions

X.Z.: Conceptualization, methodology, investigation, data curation, writing—original draft. B.Z.: Investigation, data curation. L.H.: Investigation, data curation. L.Z.: Investigation, data curation. X.L.: Data curation. W.H.: Conceptualization, supervision, writing—review and editing, funding acquisition. All authors have read and agreed to the published version of the manuscript.

Funding

This research was supported by the National Natural Science Foundation of China (Number: 41362003).

Acknowledgments

We would like to thank the Jiangxi Key Laboratory of Mining Engineering. Special thanks also go to the editors and anonymous reviewers for their input.

Conflicts of Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

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Minerals 12 01128 g001 550
Figure 1. Construction of interface adsorption model of kaolinite-H2O.
Figure 1. Construction of interface adsorption model of kaolinite-H2O.
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Minerals 12 01128 g002 550
Figure 2. Front orbital of (Al-OH)-H2O and (Si-O)-H2O interface.
Figure 2. Front orbital of (Al-OH)-H2O and (Si-O)-H2O interface.
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Minerals 12 01128 g003 550
Figure 3. Geometry optimization of Y(III) on kaolinite-H2O interface.
Figure 3. Geometry optimization of Y(III) on kaolinite-H2O interface.
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Minerals 12 01128 g004 550
Figure 4. The serial numbers of oxygen atoms on the surface of kaolinite. (Note that the atomic number is automatically generated by the MS software system.).
Figure 4. The serial numbers of oxygen atoms on the surface of kaolinite. (Note that the atomic number is automatically generated by the MS software system.).
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Minerals 12 01128 g005 550
Figure 5. Partial density of states of Y and O in (Al-OH)-H2O interface.
Figure 5. Partial density of states of Y and O in (Al-OH)-H2O interface.
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Figure 6. Partial density of states of Y and O in (Si-O)-H2O interface.
Figure 6. Partial density of states of Y and O in (Si-O)-H2O interface.
Minerals 12 01128 g006
Table
Table 1. Change of distance between Y(III) and O atoms on the kaolinite surface.
Table 1. Change of distance between Y(III) and O atoms on the kaolinite surface.
InterfaceBondBefore AdsorptionAfter Adsorption
(Al-OH)-H2OY-O162.5894.342
Y-O173.8124.619
Y-O183.5685.314
Y-O312.2403.130
Y-O322.4172.509
Y-O343.3932.493
(Si-O)-H2OY-O32.2422.690
Y-O42.9012.685
Y-O53.3043.968
Y-O92.9563.782
Y-O102.4412.586
Y-O212.9763.527
Table
Table 2. Adsorption energies of rare earth Y(III) on the (Al-OH)-H2O and (Si-O)-H2O interface (units: kJ/mol).
Table 2. Adsorption energies of rare earth Y(III) on the (Al-OH)-H2O and (Si-O)-H2O interface (units: kJ/mol).
InterfaceEads
(Al-OH)-H2O−246.05
(Si-O)-H2O−482.46
Table
Table 3. Distribution of the Mulliken bonds of Y(III) on the (Al-OH)-H2O interface.
Table 3. Distribution of the Mulliken bonds of Y(III) on the (Al-OH)-H2O interface.
InterfaceBondPopulationLength(A)
(Al-OH)-H2OO32-Y0.182.50940
O34-Y0.132.49713
O44-Y0.132.66690
O50-Y0.132.61842
O52-Y0.182.43310
O56-Y0.192.45606
Table
Table 4. Distribution of the Mulliken bonds of Y(III) on the (Si-O)-H2O interface.
Table 4. Distribution of the Mulliken bonds of Y(III) on the (Si-O)-H2O interface.
InterfaceBondPopulationLength(A)
(Si-O)-H2OO10-Y0.102.58615
O3-Y0.072.68984
O4-Y0.002.68546
O38-Y0.212.41467
O39-Y0.192.42406
O52-Y0.182.61860
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Zeng, X.; Zeng, B.; Huang, L.; Zhong, L.; Li, X.; Huang, W. Adsorption of Y(III) on the Interface of Kaolinite-H2O: A DFT Study. Minerals 2022, 12, 1128. https://doi.org/10.3390/min12091128

AMA Style

Zeng X, Zeng B, Huang L, Zhong L, Li X, Huang W. Adsorption of Y(III) on the Interface of Kaolinite-H2O: A DFT Study. Minerals. 2022; 12(9):1128. https://doi.org/10.3390/min12091128

Chicago/Turabian Style

Zeng, Xiangrong, Bin Zeng, Lijinhong Huang, Liang Zhong, Xindong Li, and Wanfu Huang. 2022. "Adsorption of Y(III) on the Interface of Kaolinite-H2O: A DFT Study" Minerals 12, no. 9: 1128. https://doi.org/10.3390/min12091128

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