Citation: ZHENG Ming, ZHANG Hong-Xing, YUAN Fu-Long, PAN Qing-Jiang. Relativistic DFT Calculations of Interaction between Rutile TiO₂ Nanoparticle Clusters and Uranyl Species[J]. Chinese Journal of Inorganic Chemistry, ;2018, 34(5): 874-882. doi: 10.11862/CJIC.2018.120 shu

Relativistic DFT Calculations of Interaction between Rutile TiO₂ Nanoparticle Clusters and Uranyl Species

1.
Key Laboratory of Functional Inorganic Material Chemistry of Education Ministry, School of Chemistry and Materials Science, Heilongjiang University, Harbin 150080, China
2.
Institute of Theoretical Chemistry, Jilin University, Changchun 130023, China

Corresponding author: YUAN Fu-Long, panqjitc@163.com PAN Qing-Jiang, yuanfulong@hlju.edu.cn
Received Date: 28 October 2017
Revised Date: 7 February 2018

Figures(6)

The interaction between rutile TiO₂ nanoparticle clusters (NPCs) and aquouranyl species have been examined using a relativistic functional theory (DFT). Effects of NPCs with various layers (1~4) and different surface areas on structural parameters of uranium adsorption complexes as well as adsorption interaction energies were investigated. It is found that the two-layered (2L) NPC (labeled as 2L-Ti15) with a surface area of 1.1 nm×0.6 nm and containing 63 atoms can reasonably stand for experimentally real TiO₂ nanocrystallite. Moreover, the model is able to save computational resources. Calculations reveal a covalent bonding interaction in the 2L-Ti15-[(UO₂)(H₂O)₃]²⁺ complex. The direct evidences include that the bond lengths of U-O_surf were optimized to be 0.233~0.238 nm, which fall well within the range of U-O distances of reported uranyl complexes. The process that the NPC adsorbs aquouranyl species is exothermic in the gas phase, releasing energy of -3.02 eV; the consideration of environment media of solution results in a slightly uphill process, requiring 0.16 eV energy. The energetic decomposition indicates that U-O_surf bonds are dominated by orbital interactions, accounting for 94%; other factors show a little effect, although electrostatic attraction is a little larger than Pauli repulsion. Electron density-based QTAIM (quantum theory of atoms in molecule) analyses unravel that the U-O_surf interaction is a dative bond per se, whose strength is stronger than that of U-OH₂, but much weaker than that of U=O_yl. Inspection of wavefunction demonstrates that HOMO is contributed by O(2p) of NPC TiO₂ mixed with a small amount of σ(U=O) bonding character, while LUMO is U(5f)-based character modified by Ti(3d). The HOMO-LUMO gap was calculated to be 2.40 eV, which much narrower than the one of NPC semiconductor (3.35 eV). From a point of view of absorption spectra, the complex system would present a visible light-harvesting capability.
- rutile TiO₂ nanoparticle clusters,
- uranium contaminant,
- adsorption interaction nature,
- electronic structures,
- relativistic DFT
1. [1]
  Hashke J M, Stakebake J L. The Chemistry of the Actinide and Transactinide Elements. Dordrecht:Springer, 2006:3199-3272
2. [2]
  Chen Z, Zhuang Z Y, Cao Q, et al. ACS Appl. Mater. Interfaces, 2014, 6(2):1301-1305 doi: 10.1021/am405306j
3. [3]
  GU Jia-Fang, XU Ke, CHEN Wen-Kai. Chinese J. Inorg. Chem., 2017, 33(9):1579-1586 doi: 10.11862/CJIC.2017.179
4. [4]
  Natrajan L S, Swinburne A N, Andrews M B, et al. Coord. Chem. Rev., 2014, 266:171-193
5. [5]
  Sandhu S S, Kohli K B, Brar A S. Inorg. Chem., 1984, 23(22):3609-3612 doi: 10.1021/ic00190a036
6. [6]
  Nieweg J A, Lemma K, Trewyn B G, et al. Inorg. Chem., 2005, 44(16):5641-5648 doi: 10.1021/ic050130e
7. [7]
  Krishna V, Kamble V S, Gupta N M, et al. J. Phys. Chem. C, 2008, 112(40):15832-15843 doi: 10.1021/jp802779e
8. [8]
  Vandenborre J, Drot R, Simoni E. Inorg. Chem., 2007, 46(4):1291-1296 doi: 10.1021/ic061783d
9. [9]
  Zhao S, Zhong Y, Guo Y, et al. Acta Chim. Sinica, 2016, 74(8):683-688 doi: 10.6023/A16060294
10. [10]
  GU Jia-Fang, MAN Mei-Ling, LU Chun-Hai, et al. Chinese. J. Inorg. Chem., 2012, 28(7):1324-1332
11. [11]
  Perron H, Domain C, Roques J, et al. Inorg. Chem., 2006, 45(17):6568-6570 doi: 10.1021/ic0603914
12. [12]
  Pan Q J, Odoh S O, Schreckenbach G, et al. Dalton Trans., 2012, 41(29):8878-8885 doi: 10.1039/c2dt31055d
13. [13]
  Zhao H B, Zheng M, Schreckenbach G, et al. Inorg. Chem., 2017, 56(5):2763-2776 doi: 10.1021/acs.inorgchem.6b02927
14. [14]
  Dossot M, Cremel S, Vandenborre J, et al. Langmuir, 2006, 22(1):140-147 doi: 10.1021/la0519913
15. [15]
  Laikov D N. Chem. Phys. Lett., 1997, 281(1/2/3):151-156
16. [16]
  Fonseca Guerra C, Snijders J G, te Velde G, et al. Theor. Chem. Acc., 1998, 99(6):391-403
17. [17]
  Bader R F W. J. Phys. Chem. A, 1998, 102:7314-7323 doi: 10.1021/jp981794v
18. [18]
  Pye C C, Ziegler T. Theor. Chem. Acc., 1999, 101(6):396-408 doi: 10.1007/s002140050457
19. [19]
  van Lenthe E, Baerends E J, Snijders J G. J. Chem. Phys., 1993, 99(6):4597-4610 doi: 10.1063/1.466059
20. [20]
  Frisch M J, Trucks G W, Schlegel H B, et al. Gaussian09, Gaussian, Inc., Wallingford CT, 2009.
21. [21]
  Lu T, Chen F. J. Comput. Chem., 2012, 33(5):580-592 doi: 10.1002/jcc.v33.5
22. [22]
  Pan Q J, Schreckenbach G. Inorg. Chem., 2010, 49(14):6509-6517 doi: 10.1021/ic100245a
23. [23]
  Arnold P L, Jones G M, Odoh S O, et al. Nat. Chem., 2012, 4(3):221-227 doi: 10.1038/nchem.1270
24. [24]
  Den Auwer C, Drot R, Simoni E, et al. New J. Chem., 2003, 27(3):648-655 doi: 10.1039/b209961f
25. [25]
  Sebbari K, Roques J, Simoni E, et al. Surf. Sci., 2012, 606(15/16):1135-1141
1. [1]
  Peng ZHOU , Xiao CAI , Qingxiang MA , Xu LIU . Effects of Cu doping on the structure and optical properties of Au₁₁(dppf)₄Cl₂ nanocluster. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1254-1260. doi: 10.11862/CJIC.20240047
2. [2]
  Xinyu Yin , Haiyang Shi , Yu Wang , Xuefei Wang , Ping Wang , Huogen Yu . Spontaneously Improved Adsorption of H₂O and Its Intermediates on Electron-Deficient Mn^(3+δ)+ for Efficient Photocatalytic H₂O₂ Production. Acta Physico-Chimica Sinica, 2024, 40(10): 2312007-. doi: 10.3866/PKU.WHXB202312007
3. [3]
  Yingchun ZHANG , Yiwei SHI , Ruijie YANG , Xin WANG , Zhiguo SONG , Min WANG . Dual ligands manganese complexes based on benzene sulfonic acid and 2, 2′-bipyridine: Structure and catalytic properties and mechanism in Mannich reaction. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1501-1510. doi: 10.11862/CJIC.20240078
4. [4]
  Xin MA , Ya SUN , Na SUN , Qian KANG , Jiajia ZHANG , Ruitao ZHU , Xiaoli GAO . A Tb₂ complex based on polydentate Schiff base: Crystal structure, fluorescence properties, and biological activity. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1347-1356. doi: 10.11862/CJIC.20230357
5. [5]
  Zhaoyang WANG , Chun YANG , Yaoyao Song , Na HAN , Xiaomeng LIU , Qinglun WANG . Lanthanide(Ⅲ) complexes derived from 4′-(2-pyridyl)-2, 2′∶6′, 2″-terpyridine: Crystal structures, fluorescent and magnetic properties. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1442-1451. doi: 10.11862/CJIC.20240114
6. [6]
  Jie ZHAO , Sen LIU , Qikang YIN , Xiaoqing LU , Zhaojie WANG . Theoretical calculation of selective adsorption and separation of CO₂ by alkali metal modified naphthalene/naphthalenediyne. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 515-522. doi: 10.11862/CJIC.20230385
7. [7]
  Yonghui ZHOU , Rujun HUANG , Dongchao YAO , Aiwei ZHANG , Yuhang SUN , Zhujun CHEN , Baisong ZHU , Youxuan ZHENG . Synthesis and photoelectric properties of fluorescence materials with electron donor-acceptor structures based on quinoxaline and pyridinopyrazine, carbazole, and diphenylamine derivatives. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 701-712. doi: 10.11862/CJIC.20230373
8. [8]
  Haitang WANG , Yanni LING , Xiaqing MA , Yuxin CHEN , Rui ZHANG , Keyi WANG , Ying ZHANG , Wenmin WANG . Construction, crystal structures, and biological activities of two Ln^Ⅲ₃ complexes. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1474-1482. doi: 10.11862/CJIC.20240188
9. [9]
  Jingjing QING , Fan HE , Zhihui LIU , Shuaipeng HOU , Ya LIU , Yifan JIANG , Mengting TAN , Lifang HE , Fuxing ZHANG , Xiaoming ZHU . Synthesis, structure, and anticancer activity of two complexes of dimethylglyoxime organotin. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1301-1308. doi: 10.11862/CJIC.20240003
10. [10]
  Xinting XIONG , Zhiqiang XIONG , Panlei XIAO , Xuliang NIE , Xiuying SONG , Xiuguang YI . Synthesis, crystal structures, Hirshfeld surface analysis, and antifungal activity of two complexes Na(Ⅰ)/Cd(Ⅱ) assembled by 5-bromo-2-hydroxybenzoic acid ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1661-1670. doi: 10.11862/CJIC.20240145
11. [11]
  Jingke LIU , Jia CHEN , Yingchao HAN . Nano hydroxyapatite stable suspension system: Preparation and cobalt adsorption performance. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1763-1774. doi: 10.11862/CJIC.20240060
12. [12]
  Zongfei YANG , Xiaosen ZHAO , Jing LI , Wenchang ZHUANG . Research advances in heteropolyoxoniobates. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 465-480. doi: 10.11862/CJIC.20230306
13. [13]
  Kun WANG , Wenrui LIU , Peng JIANG , Yuhang SONG , Lihua CHEN , Zhao DENG . Hierarchical hollow structured BiOBr-Pt catalysts for photocatalytic CO₂ reduction. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1270-1278. doi: 10.11862/CJIC.20240037
14. [14]
  Qi Li , Pingan Li , Zetong Liu , Jiahui Zhang , Hao Zhang , Weilai Yu , Xianluo Hu . Fabricating Micro/Nanostructured Separators and Electrode Materials by Coaxial Electrospinning for Lithium-Ion Batteries: From Fundamentals to Applications. Acta Physico-Chimica Sinica, 2024, 40(10): 2311030-. doi: 10.3866/PKU.WHXB202311030
15. [15]
  Fanxin Kong , Hongzhi Wang , Huimei Duan . Inhibition effect of sulfation on Pt/TiO2 catalysts in methane combustion. Chinese Journal of Structural Chemistry, 2024, 43(5): 100287-100287. doi: 10.1016/j.cjsc.2024.100287
16. [16]
  Liang MA , Honghua ZHANG , Weilu ZHENG , Aoqi YOU , Zhiyong OUYANG , Junjiang CAO . Construction of highly ordered ZIF-8/Au nanocomposite structure arrays and application of surface-enhanced Raman spectroscopy. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1743-1754. doi: 10.11862/CJIC.20240075
17. [17]
  Lihua HUANG , Jian HUA . Denitration performance of HoCeMn/TiO₂ catalysts prepared by co-precipitation and impregnation methods. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 629-645. doi: 10.11862/CJIC.20230315
18. [18]
  Hongye Bai , Lihao Yu , Jinfu Xu , Xuliang Pang , Yajie Bai , Jianguo Cui , Weiqiang Fan . Controllable Decoration of Ni-MOF on TiO2: Understanding the Role of Coordination State on Photoelectrochemical Performance. Chinese Journal of Structural Chemistry, 2023, 42(10): 100096-100096. doi: 10.1016/j.cjsc.2023.100096
19. [19]
  Wenhao Wang , Guangpu Zhang , Qiufeng Wang , Fancang Meng , Hongbin Jia , Wei Jiang , Qingmin Ji . Hybrid nanoarchitectonics of TiO₂/aramid nanofiber membranes with softness and durability for photocatalytic dye degradation. Chinese Chemical Letters, 2024, 35(7): 109193-. doi: 10.1016/j.cclet.2023.109193
20. [20]
  Mengli Xu , Zhenmin Xu , Zhenfeng Bian . Achieving Ullmann coupling reaction via photothermal synergy with ultrafine Pd nanoclusters supported on mesoporous TiO2. Chinese Journal of Structural Chemistry, 2024, 43(7): 100305-100305. doi: 10.1016/j.cjsc.2024.100305

Get Citation

PDF

XML

Metrics

PDF Downloads(3)
Abstract views(659)
HTML views(140)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Relativistic DFT Calculations of Interaction between Rutile TiO2 Nanoparticle Clusters and Uranyl Species

Metrics

通讯作者: 陈斌, bchen63@163.com

Relativistic DFT Calculations of Interaction between Rutile TiO₂ Nanoparticle Clusters and Uranyl Species