Citation: Yu-Hua GUO, You-Zhu YU, Yong-Sheng NIU, Zhen WANG, Wei-Yun SHI, Xian-Li WU. Solvothermal Synthesis, Crystal Structure and Photocurrent Property of a Ti₆-Core-based Titanium Oxo Cluster[J]. Chinese Journal of Structural Chemistry, ;2021, 40(3): 357-362. doi: 10.14102/j.cnki.0254–5861.2011–2921 shu

Solvothermal Synthesis, Crystal Structure and Photocurrent Property of a Ti₆-Core-based Titanium Oxo Cluster

a.
Henan Joint International Research Laboratory of Nanocomposite Sensing Materials, School of Chemical and Environmental Engineering, Anyang Institute of Technology, Anyang 455000, China
b.
College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450001, China

Corresponding author: You-Zhu YU, 119yyz@163.com
Received Date: 28 June 2020
Accepted Date: 11 August 2020

Fund Project: the National Natural Science Foundation of China 21702005the Foundation of the Henan Joint International Research Laboratory of Nanocomposite Sensing Materials and the Foundation of Anyang Institute of Technology YPY2019003

Figures(7)

A Ti₆-core-based titanium oxo cluster (TOC) [Ti₆(μ₂-O)₂(μ₃-O)₂(Bpo)₂(PhCOO)₈(OiPr)₄] assembled by 2, 2΄-biphenol (H₂Bpo) and benzoic acid has been synthesized and characterized by IR, elemental analyses, thermogravimetric analysis and X-ray diffraction technique. Single-crystal X-ray diffraction analysis revealed that the complex crystallizes in monoclinic system, space group P2₁/n. The structure contains two Ti₃(μ₃-O) units featuring a flat mode as building blocks. Solid-state UV/Vis absorption spectrum reveals that complex 1 shows a wide range from 240 to 650 nm. Moreover, the optical band gap of 1 is estimated to be 2.35 eV. Additionally, the Ti₆-TOC exhibits good photocurrent response.
- titanium oxo cluster,
- crystal structure,
- band gap,
- photocurrent response
1. [1]
  Wadia, C.; Alivisatos, A. P.; Kammen, D. M. Materials availability expands the opportunity for large-scale photovoltaics deployment. Energy Environ. Sci. 2009, 43, 2072–2077.
2. [2]
  Liu, S.; Tang, Z. R.; Sun, Y.; Colmenares, J. C.; Xu, Y. J. One-dimension-based spatially ordered architectures for solar energy conversion. Chem. Soc. Rev. 2015, 44, 5053–5075. doi: 10.1039/C4CS00408F
3. [3]
  Singh, A. K.; Montoya, J. H.; Gregoire, J. M.; Persson, K. A. Robust and synthesizable photocatalysts for CO₂ reduction: a data-driven materials discovery. Nat. Commun. 2019, 10, 1–9. doi: 10.1038/s41467-018-07882-8
4. [4]
  Kuehnel, M. F.; Orchard, K. L.; Dalle, K. E.; Reisner, E. Selective photocatalytic CO₂ reduction in water through anchoring of a molecular Ni catalyst on CdS nanocrystals. J. Am. Chem. Soc. 2017, 139, 7217–7223. doi: 10.1021/jacs.7b00369
5. [5]
  Kongkanand, A.; Tvrdy, K.; Takechi, K.; Kuno, M.; Kamat, P. V. Quantum dot solar cells. Tuning photoresponse through size and shape control of CdSe-TiO₂ architecture. J. Am. Chem. Soc. 2008, 130, 4007–4015. doi: 10.1021/ja0782706
6. [6]
  Yu, J.; Low, J.; Xiao, W.; Zhou, P.; Jaroniec, M. Enhanced photocatalytic CO₂-reduction activity of anatase TiO₂ by coexposed {001} and {101} facets. J. Am. Chem. Soc. 2014, 136, 8839–8842. doi: 10.1021/ja5044787
7. [7]
  Guan, G. Q.; Zou, M. Z.; Lin, J. P.; Yan, G. Y. Annealing temperature effects of TiO₂ nanofiber anodes for the rechargeable lithium ion batteries. Chin. J. Struct. Chem. 2017, 36, 729–737.
8. [8]
  Shen, S. F.; Qian, K. T.; Chen, J. P.; Wen, M. Y. One-step growth of hierarchical nanotreelike TiO₂ on ITO without template and its application in gas sensor. Chin. J. Struct. Chem. 2019, 38, 1743–1751.
9. [9]
  Xu, X.; Randorn, C.; Efstathiou, P.; Irvine, J. T. A red metallic oxide photocatalyst. Nat. Mater. 2012, 11, 595. doi: 10.1038/nmat3312
10. [10]
  Wang, C.; Liu, C.; Tian, H. R.; Li, L. J.; Sun, Z. M. Designed cluster assembly of multidimensional titanium coordination polymers: syntheses, crystal structure and properties. Chem. -Eur. J. 2018, 24, 2952–2961. doi: 10.1002/chem.201705013
11. [11]
  Yu, Y. Z.; Guo, Y.; Zhang, Y. R.; Liu, M. M.; Feng, Y. R.; Geng, C. H.; Zhang, X. M. A series of silver doped butterfly-like Ti₈Ag₂ clusters with two Ag ions panelled on a Ti₈ surface. Dalton Trans. 2019, 48, 13423–13429. doi: 10.1039/C9DT02508A
12. [12]
  Pelaez, M.; Nolan, N. T.; Pillai, S. C.; Seery, M. K.; Falaras, P.; Kontos, A. G.; Dunlop, P. S.; Hamilton, J. W.; Byrne, J. A.; O'shea, K. A review on the visible light active titanium dioxide photocatalysts for environmental applications. Appl. Catal., B 2012, 125, 331–349. doi: 10.1016/j.apcatb.2012.05.036
13. [13]
  Benkstein, K. D.; Kopidakis, N.; Van de Lagemaat, J.; Frank, A. Influence of the percolation network geometry on electron transport in dye-sensitized titanium dioxide solar cells. J. Phys. Chem. B 2003, 107, 7759–7767. doi: 10.1021/jp022681l
14. [14]
  Labat, F.; Le Bahers, T.; Ciofini, I.; Adamo, C. First-principles modeling of dye-sensitized solar cells: challenges and perspectives. Acc. Chem. Res. 2012, 45, 1268–1277. doi: 10.1021/ar200327w
15. [15]
  Duncan, W. R.; Prezhdo, O. V. Temperature independence of the photoinduced electron injection in dye-sensitized TiO₂ rationalized by ab initio time-domain density functional theory. J. Am. Chem. Soc. 2008, 130, 9756–9762. doi: 10.1021/ja800268x
16. [16]
  Yu, Y. Z.; Zhang, Y. R.; Geng, C. H.; Sun, L.; Guo, Y.; Feng, Y. R.; Wang, Y. X.; Zhang, X. M. Precise and wide-ranged band-gap tuning of Ti₆-core-based titanium oxo clusters by the type and number of chromophore ligands. Inorg. Chem. 2019, 58, 16785–16791. doi: 10.1021/acs.inorgchem.9b02951
17. [17]
  Fang, W. H.; Zhang, L.; Zhang, J. Synthetic strategies, diverse structures and tuneable properties of polyoxo-titanium clusters. Chem. Soc. Rev. 2018, 47, 404–421. doi: 10.1039/C7CS00511C
18. [18]
  Fang, W. H.; Zhang, L.; Zhang, J. A 3.6 nm Ti₅₂-oxo nanocluster with precise atomic structure. J. Am. Chem. Soc. 2016, 138, 7480–7483. doi: 10.1021/jacs.6b03489
19. [19]
  Liu, J. X.; Gao, M. Y.; Fang, W. H.; Zhang, L.; Zhang, J. Bandgap engineering of titanium-oxo clusters: labile surface sites used for ligand substitution and metal incorporation. Angew. Chem., Int. Ed. 2016, 55, 5160–5165. doi: 10.1002/anie.201510455
20. [20]
  Benedict, J. B.; Coppens, P. The crystalline nanocluster phase as a medium for structural and spectroscopic studies of light absorption of photosensitizer dyes on semiconductor surfaces. J. Am. Chem. Soc. 2010, 132, 2938–2944. doi: 10.1021/ja909600w
21. [21]
  Narayanam, N.; Fang, W. H.; Chintakrinda, K.; Zhang, L.; Zhang, J. Deep eutectic-solvothermal synthesis of titanium-oxo clusters protected by pi-conjugated chromophores. Chem. Commun. 2017, 53, 8078–8080. doi: 10.1039/C7CC04388K
22. [22]
  Lv, H. T.; Li, H. M.; Zou, G. D.; Cui, Y.; Huang, Y.; Fan, Y. Titanium-oxo clusters functionalized with catecholate-type ligands: modulating the optical properties through charge-transfer transitions. Dalton Trans. 2018, 47, 8158–8163. doi: 10.1039/C8DT01844H
23. [23]
  Sheldrick, G. M. SHELXS-97, Program for X-ray Crystal Structure Solution. University of Göttingen, Germany 1997.
24. [24]
  Sheldrick, G. M. Crystal structure refinement with SHELXL. Acta Crystallogr., Sect. C: Struct. Chem. 2015, 71, 3−8. doi: 10.1107/S2053229614024218
25. [25]
  Soler-Illia, G. J. D. A.; Rozes, L.; Boggiano, M. K.; Sanchez, C.; Majoral, J. I. New mesotextured hybrid materials made from assemblies of dendrimers and titanium(IV)-oxo-organo clusters. Angew. Chem., Int. Ed. 2000, 39, 4419–4424.
26. [26]
  Wendlandt, W. W.; Hecht, H. G. Reflectance Spectroscopy, Interscience, New York 1966.
1. [1]
  Ruikui YAN , Xiaoli CHEN , Miao CAI , Jing REN , Huali CUI , Hua YANG , Jijiang WANG . Design, synthesis, and fluorescence sensing performance of highly sensitive and multi-response lanthanide metal-organic frameworks. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 834-848. doi: 10.11862/CJIC.20230301
2. [2]
  Yao HUANG , Yingshu WU , Zhichun BAO , Yue HUANG , Shangfeng TANG , Ruixue LIU , Yancheng LIU , Hong LIANG . Copper complexes of anthrahydrazone bearing pyridyl side chain: Synthesis, crystal structure, anticancer activity, and DNA binding. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 213-224. doi: 10.11862/CJIC.20240359
3. [3]
  Jia JI , Zhaoyang GUO , Wenni LEI , Jiawei ZHENG , Haorong QIN , Jiahong YAN , Yinling HOU , Xiaoyan XIN , Wenmin WANG . Two dinuclear Gd(Ⅲ)-based complexes constructed by a multidentate diacylhydrazone ligand: Crystal structure, magnetocaloric effect, and biological activity. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 761-772. doi: 10.11862/CJIC.20240344
4. [4]
  Lu LIU , Huijie WANG , Haitong WANG , Ying LI . Crystal structure of a two-dimensional Cd(Ⅱ) complex and its fluorescence recognition of p-nitrophenol, tetracycline, 2, 6-dichloro-4-nitroaniline. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1180-1188. doi: 10.11862/CJIC.20230489
5. [5]
  Lulu DONG , Jie LIU , Hua YANG , Yupei FU , Hongli LIU , Xiaoli CHEN , Huali CUI , Lin LIU , Jijiang WANG . Synthesis, crystal structure, and fluorescence properties of Cd-based complex with pcu topology. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 809-820. doi: 10.11862/CJIC.20240171
6. [6]
  Xiumei LI , Yanju HUANG , Bo LIU , Yaru PAN . Syntheses, crystal structures, and quantum chemistry calculation of two Ni(Ⅱ) coordination polymers. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 2031-2039. doi: 10.11862/CJIC.20240109
7. [7]
  Xiumei LI , Linlin LI , Bo LIU , Yaru PAN . Syntheses, crystal structures, and characterizations of two cadmium(Ⅱ) coordination polymers. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 613-623. doi: 10.11862/CJIC.20240273
8. [8]
  Chao LIU , Jiang WU , Zhaolei JIN . Synthesis, crystal structures, and antibacterial activities of two zinc(Ⅱ) complexes bearing 5-phenyl-1H-pyrazole group. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1986-1994. doi: 10.11862/CJIC.20240153
9. [9]
  Xiaoxia WANG , Ya'nan GUO , Feng SU , Chun HAN , Long SUN . Synthesis, structure, and electrocatalytic oxygen reduction reaction properties of metal antimony-based chalcogenide clusters. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1201-1208. doi: 10.11862/CJIC.20230478
10. [10]
  Xiaoling WANG , Hongwu ZHANG , Daofu LIU . Synthesis, structure, and magnetic property of a cobalt(Ⅱ) complex based on pyridyl-substituted imino nitroxide radical. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 407-412. doi: 10.11862/CJIC.20240214
11. [11]
  Yan XU , Suzhi LI , Yan LI , Lushun FENG , Wentao SUN , Xinxing LI . Structure variation of cadmium naphthalene-diphosphonates with the changing rigidity of N-donor auxiliary ligands. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 395-406. doi: 10.11862/CJIC.20240226
12. [12]
  Kaimin WANG , Xiong GU , Na DENG , Hongmei YU , Yanqin YE , Yulu MA . Synthesis, structure, fluorescence properties, and Hirshfeld surface analysis of three Zn(Ⅱ)/Cu(Ⅱ) complexes based on 5-(dimethylamino) isophthalic acid. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1397-1408. doi: 10.11862/CJIC.20240009
13. [13]
  Huan ZHANG , Jijiang WANG , Guang FAN , Long TANG , Erlin YUE , Chao BAI , Xiao WANG , Yuqi ZHANG . A highly stable cadmium(Ⅱ) metal-organic framework for detecting tetracycline and p-nitrophenol. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 646-654. doi: 10.11862/CJIC.20230291
14. [14]
  Meirong HAN , Xiaoyang WEI , Sisi FENG , Yuting BAI . A zinc-based metal-organic framework for fluorescence detection of trace Cu²⁺. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1603-1614. doi: 10.11862/CJIC.20240150
15. [15]
  Shuyan ZHAO . Field-induced Co^Ⅱ single-ion magnet with pentagonal bipyramidal configuration. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1583-1591. doi: 10.11862/CJIC.20240231
16. [16]
  Yinling HOU , Jia JI , Hong YU , Xiaoyun BIAN , Xiaofen GUAN , Jing QIU , Shuyi REN , Ming FANG . A rhombic Dy₄-based complex showing remarkable single-molecule magnet behavior. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 605-612. doi: 10.11862/CJIC.20240251
17. [17]
  Mohamed Saber Lassoued , Faizan Ahmad , Yanzhen Zheng . Film thickness effect on 2D lead-free hybrid double perovskite properties: Band gap, photocurrent and stability. Chinese Chemical Letters, 2025, 36(4): 110477-. doi: 10.1016/j.cclet.2024.110477
18. [18]
  Wen LUO , Lin JIN , Palanisamy Kannan , Jinle HOU , Peng HUO , Jinzhong YAO , Peng WANG . Preparation of high-performance supercapacitor based on bimetallic high nuclearity titanium-oxo-cluster based electrodes. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 782-790. doi: 10.11862/CJIC.20230418
19. [19]
  Xiaowei TANG , Shiquan XIAO , Jingwen SUN , Yu ZHU , Xiaoting CHEN , Haiyan ZHANG . A zinc complex for the detection of anthrax biomarker. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1850-1860. doi: 10.11862/CJIC.20240173
20. [20]
  Hai-Ling Wang , Zhong-Hong Zhu , Hua-Hong Zou . Structure and assembly mechanism of high-nuclear lanthanide-oxo clusters. Chinese Journal of Structural Chemistry, 2024, 43(9): 100372-100372. doi: 10.1016/j.cjsc.2024.100372

Get Citation

PDF

XML

Metrics

PDF Downloads(2)
Abstract views(336)
HTML views(16)

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

Solvothermal Synthesis, Crystal Structure and Photocurrent Property of a Ti6-Core-based Titanium Oxo Cluster

Metrics

通讯作者: 陈斌, bchen63@163.com

Solvothermal Synthesis, Crystal Structure and Photocurrent Property of a Ti₆-Core-based Titanium Oxo Cluster