Citation: NARAYANAM Nagaraju, CHINTAKRINDA Kalpana, FANG Weihui, ZHANG Lei, ZHANG Jian. Atomically Precise Zr-Oxo and Zr/Ti-Oxo Nanoclusters by Deep Eutectic-Solvothermal Synthesis[J]. Acta Physico-Chimica Sinica, ;2018, 34(7): 781-785. doi: 10.3866/PKU.WHXB201711131 shu

Atomically Precise Zr-Oxo and Zr/Ti-Oxo Nanoclusters by Deep Eutectic-Solvothermal Synthesis

1.
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, P. R. China
2.
International College, University of Chinese Academy of Sciences, 100049 Beijing, P. R. China

Corresponding author: ZHANG Lei, LZhang@fjirsm.ac.cn
Received Date: 17 October 2017
Revised Date: 6 November 2017
Accepted Date: 7 November 2017
Available Online: 13 July 2017
Fund Project: The project was supported by the National Natural Science Foundation of China (21473202, 21673238) and Natural Science Foundation of Fujian Province, China (2017J06009)the National Natural Science Foundation of China 21673238Natural Science Foundation of Fujian Province, China 2017J06009the National Natural Science Foundation of China 21473202

Atomically precise nanoclusters form an important class of functional materials that have recently attracted research interest for their unique properties and easily tunable surface functionalities. Core-shell nanomaterials with precise structural information can be produced to better understand the structure–property relationships for different applications. Polyoxo-titanium clusters (PTCs) are such a kind of nanomaterial for different functional applications in catalysis, photovoltaics, ceramics, etc. However, the high bandgap of semiconductive PTCs is the limiting factor in their practical solar application in the visible region of sunlight. The development of PTCs with different surface-bound ligands is an emerging area of research in the design and synthesis of core-shell nanoclusters with reduced bandgaps. It has been extensively reported that the polynuclear growth of PTCs requires molecular-level water supply in reactions. Moreover, it is important to identify more environment-friendly synthetic methods. Deep eutectic-solvothermal (DES) synthesis is an emerging green method for the synthesis of different crystalline materials. The hygroscopic nature of DES should enhance the provision of water during polynuclear growth of nanoclusters. Hence, we chose to synthesize different kinds of PTCs using DES as solvent. Two nanoclusters, Zr-oxo (PTC-65) and Zr/Ti-oxo (PTC-66) clusters having surface-bound 1, 10-phenanthroline (1, 10-phn) and phenol ligands, were successfully synthesized using this approach; 1, 10-phn was employed as the precursor in the synthetic reaction, and phenol was not employed directly in the chemical reaction, but was supplied from the DES solvent used in the reaction. In the presence of chromophoric ligands, 1, 10-phn and phenol are believed to enhance the light absorption properties of the resulting functional nanomaterials. Their crystal structure revealed that they form core-shell mimics with Zr-oxo and Ti/Zr-oxo core units having surface-bound shell ligands. Based on their different structural characteristics, photocatalytic hydrogen evolution studies were performed on these two functional materials using an aqueous solution of H₂O (50 mL)/triethanol amine (10 mL). Interestingly, PTC-65 formed a turbid solution, whereas PTC-66 formed a clear solution. The possible reasons for their different dispersion behaviors are widely discussed, with emphasis on their structure–property relationships. This study provides a potential tool for the homogenization of Ti-O materials to improve their photocatalytic activities. Moreover, the success of our work confirms that deep eutectic-solvothermal synthesis can be an effective method for cluster preparation. Many other interesting polynuclear complexes like polyoxometalates, chalcogenides, and noble-metal clusters could be obtained by this synthetic methodology.
- Nanocluster,
- Titanium,
- Zirconium,
- Deep-eutectic solvothermal,
- H₂ evolution
1. [1]
  Indranath, C.; Thalappil, P. Chem. Rev. 2017, 117, 8208. doi: 10.1021/acs.chemrev.6b00769 doi: 10.1021/acs.chemrev.6b00769
2. [2]
  Goswami, N.; Zheng, K.; Xie, J. Nanoscale 2014, 6, 13328. doi: 10.1039/C4NR04561K doi: 10.1039/C4NR04561K
3. [3]
  Yuan, X.; Luo, Z.; Yu, Y.; Yao, Q.; Xie, J. Chem. Asian J. 2013, 8, 858. doi: 10.1002/asia.201201236 doi: 10.1002/asia.201201236
4. [4]
  Zhou, Y.; Li, Z. M.; Zheng, K.; Li, G. Acta Phys. -Chim. Sin. 2018, 34(7), 786. doi: 10.3866/PKU.WHXB201709292
5. [5]
  Fang, J.; Zhang, B.; Yao, Q.; Yang, Y.; Xie, J.; Yan, N. Coord. Chem. Rev. 2016, 322, 1. doi: 10.1016/j.ccr.2016.05.003 doi: 10.1016/j.ccr.2016.05.003
6. [6]
  Zhu, M.; Li, M. B.; Yao, C. H.; Xia, N.; Zhao, Y.; Yan, N.; Liao, L. W.; Wu, Z. K. Acta Phys. -Chim. Sin. 2018, 34(7), 792. doi: 10.3866/PKU.WHXB201710091
7. [7]
  Sun, G. D.; Kang, X.; Jin, S.; Li, X. W.; Hu, D. Q.; Wang, S. X.; Zhu, M. Z. Acta Phys. -Chim. Sin. 2018, 34(7), 799. doi: 10.3866/PKU.WHXB201710124
8. [8]
  Chaudhuri, R. G.; Paria, S. Chem. Rev. 2012, 112, 2373. doi: 10.1021/cr100449n doi: 10.1021/cr100449n
9. [9]
  Xiao, P. W.; Zhao, L, Sui, Z. Y.; Han, B. H. Langmuir 2017, 33, 6038. doi: 10.1021/acs.langmuir.7b00331 doi: 10.1021/acs.langmuir.7b00331
10. [10]
  Tominaga, C.; Hikosou, D.; Osaka, I.; Kawasak, H. Acta Phys. -Chim. Sin. 2018, 34(7), 805. doi: 10.3866/PKU.WHXB201710271 doi: 10.3866/PKU.WHXB201710271
11. [11]
  Li, N.; Matthews, P. D.; Luob, H. K.; Wright, D. S. Chem. Commun. 2016, 52, 11180. doi: 10.1039/C6CC03788G doi: 10.1039/C6CC03788G
12. [12]
  Snoeberger, R. C., Ⅲ; Young, K. J.; Tang, J.; Allen, L. J.; Crabtree, R. H.; Brudvig, G. W.; Coppens, P.; Batista, V. S.; Benedict, J. B. J. Am. Chem. Soc. 2012, 134, 8911. doi: 10.1021/ja301238t doi: 10.1021/ja301238t
13. [13]
  Fang, W. H.; Wang, J. F.; Zhang, L.; Zhang, J. Chem. Mater. 2017, 29, 2681. doi: 10.1021/acs.chemmater.7b00324 doi: 10.1021/acs.chemmater.7b00324
14. [14]
  Zhao, Z.; Zhang, X. Y.; Zhang, G. Q.; Liu, Z. Y.; Qu, D.; Miao, X.; Feng, P. Y.; Sun, Z. C. Nano Res. 2015, 8, 4061. doi: 10.1007/s12274-015-0917-5 doi: 10.1007/s12274-015-0917-5
15. [15]
  Coppens, P.; Chen, Y.; Trzop, E. Chem. Rev. 2014, 114, 9645. doi: 10.1021/cr400724e doi: 10.1021/cr400724e
16. [16]
  Liu, J. X.; Gao, M. Y.; Fang, W. H.; Zhang, L.; Zhang, J. Angew. Chem. Int. Ed. 2016, 55, 5160. doi: 10.1002/anie.201510455 doi: 10.1002/anie.201510455
17. [17]
  Lv, Y.; Cheng, J.; Steiner, A.; Gan, L.; Wright, D. S. Angew. Chem. Int. Ed. 2014, 53, 1934. doi: 10.1002/anie.201307721 doi: 10.1002/anie.201307721
18. [18]
  Sokolow, J. D.; Trzop, E.; Chen, Y.; Tang, J.; Allen, L. J.; Crabtree, R. H.; Benedict, J. B.; Coppens. P. J. Am. Chem. Soc. 2012, 134, 11695. doi: 10.1021/ja303692r doi: 10.1021/ja303692r
19. [19]
  Wagle, D. V.; Zhao, H.; Baker, G. A. Acc. Chem. Res. 2014, 7, 2299. doi: 10.1021/ar5000488 doi: 10.1021/ar5000488
20. [20]
  Cooper, E. R.; Andrews, C. D.; Wheatley, P. S.; Webb, P. B.; Wormald, P.; Morris, R. E. Nature 2004, 430, 1012. doi: 10.1038/nature02860 doi: 10.1038/nature02860
21. [21]
  Zhang, Q.; Vigier, K. D. O.; Royer, S.; Jerome, F. Chem. Soc. Rev. 2012, 41, 7108. doi: 10.1039/C2CS35178A doi: 10.1039/C2CS35178A
22. [22]
  Smith, E. L.; Abbott, A. P.; Ryder, K. S. Chem. Rev. 2014, 114, 11060. doi: 10.1021/cr300162p doi: 10.1021/cr300162p
23. [23]
  Zhang, J.; Wu, T.; Chen, S.; Feng, P.; Bu, X. Angew. Chem. Int. Ed. 2009, 48, 3486. doi: 10.1002/anie.200900134 doi: 10.1002/anie.200900134
24. [24]
  Wragg, D. S.; Slawin, A. M. Z.; Morris, R. E. Solid State Sci. 2009, 11, 411. doi: 10.1016/j.solidstatesciences.2008.09.008 doi: 10.1016/j.solidstatesciences.2008.09.008
25. [25]
  Nagaraju, N.; Fang, W. H.; Kalpana, C.; Zhang, L.; Zhang, J. Chem. Commun. 2017, 53, 8078. doi: 10.1039/c7cc04388k doi: 10.1039/c7cc04388k
26. [26]
  Sheldrick, G. M. Acta Crystallogr. Sect. A 2008, 64, 112. doi: 10.1107/S0108767307043930 doi: 10.1107/S0108767307043930
27. [27]
  Sheldrick, G. M. SHELXL-2014, University of Gottingen, Germany, 2014.
28. [28]
  Kickelbick, G.; Wiede, P.; Schubert, U. Inorg. Chim. Acta 1999, 284, 1. doi: 10.1016/S0020-1693(98)00251-5 doi: 10.1016/S0020-1693(98)00251-5
29. [29]
  Gao, M. Y.; Wang, F.; Gu, Z. G.; Zhang, D. X.; Zhang, L.; Zhang, Z. J. Am. Chem. Soc. 2016, 138, 2556. doi: 10.1021/jacs.6b00613 doi: 10.1021/jacs.6b00613
30. [30]
  Zhang, G.; Liu, C.; Long, D. L.; Cronin, L.; Tung, C. H.; Wang, Y. J. Am. Chem. Soc. 2016, 138, 11097. doi: 10.1021/ jacs.6b06290 doi: 10.1021/jacs.6b06290
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