Study of the Effect of Absorbed Cu Species on the Surface of Specularite (0 0 1) by the DFT Calculations
Abstract
:1. Introduction
2. Computational Details
3. Results and Discussion
3.1. The Effect of Cu Species Adsorbed on the Structure of the Specularite (0 0 1) Surface
3.2. The Effect of Cu Species Adsorption on the Electronic Properties of Specularite
3.3. Adsorption of Cu Species on the Surface of Specularite
3.3.1. The Role of Cu Species Absorbed on the Surface of Specularite
3.3.2. Density of States Analysis of Interaction between Cu Species and Specularite (0 0 1) Surface
3.3.3. Interatomic Charge Transfer Analysis of Interaction between Cu Species and Specularite (0 0 1) Surface
3.3.4. Analysis of Bond Properties of Cu Species Adsorbed on the Specularite Surface
4. Conclusions
- (1)
- The results of crystalline structure and electronic properties of a specularite (0 0 1) suface show that the geometric structure and electronic properties of the surface of specularite (0 0 1) are significantly changed after absorbing the Cu species, and the structure of O3–Fe1–O1 near the absorbate is more easily affected.
- (2)
- The results of adsorption energy analysis show that Cu2+, Cu(OH)+, and Cu(OH)2 can be spontaneously adsorbed on the surface of specularite (0 0 1), and the adsorption stability of Cu components that are on the surface of specularite increase in the order of Cu2+ < Cu(OH)+ < Cu(OH)2.
- (3)
- The results of the adsorption module and PDOS analysis show that the adsorptions of Cu species on the surface of specularite are different. Cu2+ may be adsorbed on the surface of specularite through a Cu atom directly interacting with O atoms to form Cu–O complexes, while Cu(OH)+ and Cu(OH)2 may be adsorbed on the surface of specularite through the interaction between OI (OII) atoms in –OH and Fe atoms on the surface of specularite to form Cu–O–Fe complexes.
- (4)
- The results of charge transfer analysis show that the charges in the Cu–O bond formed after the adsorption of absorbates were mainly transferred from the Cu 4s orbital to the O 2p orbital and that the charges in the Fe–O bond formed were mainly transferred from the 4s and 2p orbitals of the Fe atom to the 2p orbital of the O atom.
- (5)
- By comparing Cu–O and Fe–O of the three Cu components on the surface of specularite (0 0 1), it can be seen that the bond populations of Cu–O are smaller than those of Fe–O, indicating that Cu–O is more ionic and Fe–O is more covalent.
Author Contributions
Funding
Acknowledgments
Conflicts of Interest
References
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Adsorbates | Bond Length (Å) | |||
---|---|---|---|---|
Fe1–O1 | O1–Fe2 | Fe2–O2 | O3–Fe1 | |
Original | 1.749 | 1.918 | 1.910 | 1.749 |
Cu2+ | 1.809 | 1.943 | 1.925 | 1.764 |
Cu(OH)+ | 1.887 | 1.912 | 1.926 | 1.775 |
Cu(OH)2 | 1.844 | 1.908 | 1.930 | 1.722 |
Adsorbates | Bond Angles (°) | ||||
---|---|---|---|---|---|
Fe1–O1–Fe2 | O1–Fe2–O2 | O3–Fe1–O1 | O1–Fe2–O4 | O4–Fe2–O2 | |
Original | 118.461 | 101.402 | 115.903 | 86.237 | 82.717 |
Cu2+ | 119.474 | 100.695 | 108.848 | 87.559 | 83.609 |
Cu(OH)+ | 119.829 | 99.038 | 111.672 | 86.879 | 83.956 |
Cu(OH)2 | 118.235 | 100.270 | 112.594 | 87.574 | 83.873 |
Adsorbates | DCu–Fe1 (Å) | DCu–O1 (Å) | DFe1–OI (Å) | DFe2–OII (Å) | Energy (eV) | |
---|---|---|---|---|---|---|
Cu2+ | Before | 1.614 | 1.613 | – | – | – |
After | 2.387 | 1.987 | – | – | −0.76 | |
CuOH+ | Before | 1.665 | 1.661 | 1.538 | – | – |
After | 2.808 | 1.985 | 1.854 | – | −0.85 | |
Cu(OH)2 | Before | 1.708 | 1.713 | 1.721 | 2.296 | – |
After | 2.750 | 2.146 | 1.887 | 1.909 | −1.78 |
Adsorbates | Atom | s | p | d | f | Total | Charge/e | |
---|---|---|---|---|---|---|---|---|
Cu2+ | Cu | Before | 1.00 | 0.00 | 10.00 | 0.00 | 11.00 | 0.00 |
After | 0.78 | 0.12 | 9.81 | 0.00 | 10.71 | 0.29 | ||
Fe1 | Before | 0.40 | 0.24 | 6.49 | 0.00 | 7.14 | 0.86 | |
After | 0.41 | 0.38 | 6.54 | 0.00 | 7.32 | 0.68 | ||
O1 | Before | 1.88 | 4.71 | 0.00 | 0.00 | 6.59 | −0.59 | |
After | 1.86 | 4.76 | 0.00 | 0.00 | 6.62 | −0.62 | ||
CuOH+ | Cu | Before | 0.65 | 0.11 | 9.76 | 0.00 | 10.52 | 0.48 |
After | 0.53 | 0.17 | 9.79 | 0.00 | 10.50 | 0.50 | ||
OI | Before | 1.90 | 5.03 | 0.00 | 0.00 | 6.93 | −0.93 | |
After | 1.87 | 4.96 | 0.00 | 0.00 | 6.83 | −0.83 | ||
Fe1 | Before | 0.40 | 0.24 | 6.49 | 0.00 | 7.14 | 0.86 | |
After | 0.27 | 0.32 | 6.45 | 0.00 | 7.05 | 0.95 | ||
O1 | Before | 1.88 | 4.71 | 0.00 | 0.00 | 6.59 | −0.59 | |
After | 1.86 | 4.78 | 0.00 | 0.00 | 6.64 | −0.64 | ||
Cu(OH)2 | Cu | Before | 0.62 | 0.09 | 9.44 | 0.00 | 10.16 | 0.84 |
After | 0.58 | 0.08 | 9.67 | 0.00 | 10.33 | 0.67 | ||
OI | Before | 1.90 | 4.98 | 0.00 | 0.00 | 6.87 | −0.87 | |
After | 1.87 | 4.94 | 0.00 | 0.00 | 6.81 | −0.81 | ||
OII | Before | 1.90 | 4.99 | 0.00 | 0.00 | 6.88 | −0.88 | |
After | 1.86 | 4.96 | 0.00 | 0.00 | 6.83 | −0.83 | ||
Fe1 | Before | 0.40 | 0.24 | 6.49 | 0.00 | 7.14 | 0.86 | |
After | 0.27 | 0.35 | 6.43 | 0.00 | 7.05 | 0.95 | ||
O1 | Before | 1.88 | 4.71 | 0.00 | 0.00 | 6.59 | −0.59 | |
After | 1.87 | 4.76 | 0.00 | 0.00 | 6.62 | −0.62 |
Adsorbates | Bond | Population |
---|---|---|
Cu2+ | O1–Cu | 0.14 |
Cu(OH)+ | O1–Cu | 0.17 |
OI–Fe1 | 0.33 | |
Cu(OH)2 | OI–Fe1 | 0.30 |
OII –Fe5 | 0.30 |
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Huangfu, M.; Li, J.; Zhang, X.; Hu, Y.; Deng, J.; Wang, Y.; Wei, P. Study of the Effect of Absorbed Cu Species on the Surface of Specularite (0 0 1) by the DFT Calculations. Minerals 2021, 11, 930. https://doi.org/10.3390/min11090930
Huangfu M, Li J, Zhang X, Hu Y, Deng J, Wang Y, Wei P. Study of the Effect of Absorbed Cu Species on the Surface of Specularite (0 0 1) by the DFT Calculations. Minerals. 2021; 11(9):930. https://doi.org/10.3390/min11090930
Chicago/Turabian StyleHuangfu, Mingzhu, Jiaxin Li, Xi Zhang, Yiming Hu, Jiushuai Deng, Yu Wang, and Pingping Wei. 2021. "Study of the Effect of Absorbed Cu Species on the Surface of Specularite (0 0 1) by the DFT Calculations" Minerals 11, no. 9: 930. https://doi.org/10.3390/min11090930