Sandile H. KHOZA, Siphamandla C. MASIKANE, Sixberth MLOWE, Neerish REVAPRASADU, Itegbeyogene P. EZEKIEL, Thomas MOYO

Thermolytic synthesis of cobalt and cobalt sulfide nanoparticles using Cobalt(II) N∧O Schiff base complexes as single molecular precursors

Two novel N∧O-type Schiff base ligands and the corresponding Co(II) complexes are reported. Thermogravimetric analysis indicated that the complexes are potential molecular precursors for the fabrication of cobalt andcobalt-containing nanomaterials. The significant difference in the thermal decomposition profiles is recognized as aninfluence of structural differences on the complexes. Thus, the complexes were thermally decomposed using the melt andhot injection methods to examine the properties of the obtained cobalt and cobalt sulfide nanoparticles, respectively.The reaction parameters employed during the fabrication processes, in addition to structural differences, influencedthe morphological and crystallographic phases and magnetic properties of the synthesized nanoparticles. We have investigated the morphological properties and the crystallographic phase compositions of the nanoparticles by variouselectron microscopy and diffraction techniques, as well as energy-dispersive X-ray spectroscopy. The melt reactionsproduced phase-pure cobalt nanoparticles, which exhibit ferromagnetic behavior. The hot injection method utilized 1-dodecanethiol (DDT) as both sulfur source and capping agent. We indexed the DDT-capped cobalt sulfide nanoparticlesto cubic $Co_9S_8$ and $Co_3S_4$ phases using powder X-ray diffraction, high-resolution transmission electron microscopyimaging, and selected area electron diffraction. The crystallite sizes for $Co_9S_8$ and $Co_3S_4$ nanoparticles, based on theScherrer equation, were 12.4 nm and 14.1 nm, respectively. We find significant differences in the magnetic properties,attributed to nonmagnetic inclusions and vacancies due to the presence of S atoms.

PDF

___

1. Trindade, T.; O’Brien, P.; Pickett, N. L. Chem. Mater. 2001, 13, 3843-3858.
2. Connolly, J.; St. Pierre, T. G.; Rutnakornpituk, M.; Riffle, J. S. J. Phys. D. Appl. Phys. 2004, 37, 2475-2482.
3. Puntes, F. V.; Krishnann, M. K.; Alivisatos, P. A. Science 2001, 291, 2115-2117.
4. Murray, C. B.; Sun, S.; Gaschler, W. IBMJ. Res. Dev. 2001, 45, 47-56.
5. Dong, X. L.; Choi, C. J.; Kim, B. K. Scripta Mater. 2002, 47, 857-861.
6. Wang, Z. H.; Choi, C. J.; Kim, B. K.; Zhang, Z. D. J. Alloys Compd. 2003, 351, 319-323.
7. Sun, S.; Murray, C. B. J. Appl. Phys. 1999, 85, 4325-4330.
8. Luna, C.; Morales, M. P.; Serna, C. J.; Vazquez, M. Mater. Sci. Eng. C 2003, 23, 1129-1132.
9. Ichiyanagi, Y.; Yamada, S. Polyhedron 2005, 24, 2813-2816.
10. Shukla, N.; Svedberg, E. B.; Ell, J.; Roy, A. J. Mater. Lett. 2006, 60, 1950-1955.
11. Salavati-Niasari, M.; Davar, F.; Mazaheri, M.; Shaterian, M. J. Magn. Magn. Mater. 2008, 320, 575-578.
12. Maneeprakorn, W.; Malik, A. M.; O’Brien, P. J. Mater. Chem. 2010, 20, 2329-2335.
13. Ramasamy, K.; Malik, M. A.; Revaprasadu, N.; O’Brien, P. Chem. Mater. 2013, 25, 3551-3569.
14. Lai, C. H.; Lu, M. Y.; Chen, L. J. J. Mater. Chem. 2012, 22, 19-30.
15. Wu, Y.; Wadia, C.; Ma, W. L.; Sadtler, B.; Alivisatos, A. P. Nano Lett. 2008, 8, 2551-2555.
16. Li, T. L.; Lee, Y. L.; Teng, H. S. J. Mater. Chem. 2011, 21, 5089-5098.
17. Bierman, M. J.; Jin, S. Energy Environ. Sci. 2009, 2, 1050-1059.
18. Chen, X. Y.; Zhang, Z. J.; Qiu, Z. G., Shi, C. W., Li, X. L. J. Colloid Interface Sci. 2007, 308, 271-275.
19. Wold, A.; Dwight, K. Solid State Chemistry; Chapman and Hall: New York, NY, USA, 1993.
20. Rao, C. N. R.; Pisharody, K. P. R. Prog. Solid State Chem. 1976, 10, 207-270.
21. Bao, S.; Li, Y.; Li, C. M.; Bao, Q.; Lu, Q.; Guo, J. Cryst. Growth Des. 2008, 8, 3745-3749.
22. Smith, G. B.; Ignatiev, A.; Zajac, G. J. Appl. Phys. 1980, 51, 4186-4196.
23. Whitney, T. M.; Jiang, J. S.; Searson, P.; Chien, C. Science 1993, 261, 1316-1319.
24. Wang, G.; Zhuo, S. Phys. Chem. Chem. Phys. 2013, 15, 13801-13804.
25. Tai, S. Y.; Chang, C. F.; Liu, W. C.; Liao, J. H.; Lin, J. Y. Electrochim. Acta 2013, 107, 66-70.
26. Faber, M. S.; Park, K.; Cabán-Acevedo, M.; Santra, P. K.; Jin, S. J. Phys. Chem. Lett. 2013, 4, 1843-1849.
27. Kung, C. W.; Chen, H. W.; Lin, C. Y.; Huang, K. C.; Vittal, R.; Ho, K. C. ACS Nano. 2012, 6, 7016-7025.
28. Chen, H. W.; Kung, C. W.; Tseng, C. M.; Wei, T. C.; Sakai, N.; Morita, S.; Ikegami, M.; Miyasaka, T.; Ho, K. C. J. Mater. Chem. A 2013, 1, 13759-13768.
29. Yue, G. H.; Yan, P. X.; Fan, X. Y.; Wang, M. X.; Qu, D. M.; Wu, Z. G.; Li C.; Yan, D. Electrochem. Solid State Lett. 2007, 10, D29-D31.
30. Wang, Q.; Jiao, L.; Han, Y.; Du, H.; Peng, W.; Huan, Q.; Song, D.; Si, Y.; Wang, Y.; Yuan, H. J. Phys. Chem. C 2011, 115, 8300-8304.
31. Zhou, Y. X.; Yao, H. B.; Wang, Y.; Liu, H. L.; Gao, M. R.; Shen, P. K.; Yu, S. H. Chem. Eur. J. 2010, 16, 12000-12007.
32. Maneeprakorn, W.; Malik, M. A.; O’Brien, P. J. Mater. Chem. 2010, 20, 2329-2335.
33. Ramasamy, K.; Maneerprakorn, W.; Malik, M. A.; O’Brien, P. Phil. Trans. R. Soc. A 2010, 368, 4249-4260.
34. Kumar, N.; Raman, N.; Sundaresan, A. Anorg. Allg. Chem. 2014, 640, 1069-1074.
35. Pawar, A. S.; Garje, S. S. Bull, Mater. Sci. 2015, 38, 1843-1850.
36. Bornside, D. E.; Macosko, C. W.; Scriven, L. E. J. Imaging Technol. 1987, 13, 122-130.
37. Pengfei, Y.; Lili, S.; Xiangyu, H.; Chuanhui, X.; Haiying, W.; Feng, W. Rare Metal Mater. Eng. 2016, 45, 1700- 1704.
38. Wirtz, M.; Martin, C. R. Adv. Mater. 2003, 15, 455-458.
39. Johnson, C. P.; Atwood, J. L.; Steed, J. W.; Bauer, C. B.; Rogers, R. D. Inorg. Chem. 1996, 35, 2602-2610.
40. Alizadeh, N.; Ershad, S.; Naeimi, H.; Sharghi, H.; Shamsipur, M. Pol. J. Chem. 1999, 73, 915-925.
41. Thangadurai, T. D.; Gowri, M.; Natarajan, K. Synth. React. Inorg. Met. Org. Chem. 2002, 32, 329-343.
42. Pui, A. Croatica Chem. Acta 2002, 75, 165-173.
43. Casella, L.; Gullotti, M. Inorg. Chem. 1986, 25, 1293-1303.
44. Aazam, E. S.; El-Said, W. A. Bioorganic Chem. 2014, 57, 5-12.
45. Parsaee, Z.; Mohammadi, K.; Ghahramaninezhad, M.; Hosseinzadeh, B. New J. Chem. 2016, 40, 10569-10583.
46. Bu, X. R.; Jackson, C. R.; Derveer, D. V.; You, X. Z.; Meng, Q. J.; Wang, R. X. Polyhedron 1997, 16, 2991-3001.
47. Kolawole, G. A.; Patel, K. S. J. Chem. Soc., Dalton Trans. 1981, 1241-1245.
48. Patel, K. S.; Kolawole, G. A.; Earnshaw, A. J. Inorg. Nucl. Chem. 1981, 43, 3107-3112.
49. Osowole, A. A.; Kolawole, G. A.; Fagade, O. E. Synth. React. Inorg. Met. Org. Chem. 2005, 35, 829-836.
50. Nejo, A. A.; Kolawole, G. A.; Nejo, A. O. J. Coord. Chem. 2010, 63, 4398-4410.
51. Abd-Elza, M. M.; J. Chin. Chem. Soc. 2001, 48, 153-158.
52. Lee, C. H.; Hsu, C. K.; Chan, C. L. Thermochim. Acta 2002, 392, 173-176.
53. Scherrer, P. Nachr. Ges. Wiss. Göttingen Math. Phys. Kl. 1918, 26, 98-100.
54. Abdallah, H. M. I.; Moyo, T.; Ezekiel, I. P.; Osman, N. S. E. J. Magn. Magn. Mater. 2014, 365, 83-87.
55. Waseda, Y.; Matsubara, E.; Shinoda, K. In: X-Ray Diffraction Crystallography; Waseda, Y.; Matsubara, E.; Shinoda, K., Eds. Springer-Verlag: Berlin, Germany, 2011, pp. 107-167.
56. Bao, S. J.; Li, C. M.; Guo, C. X.; Qiao, Y. J. Power Sources 2008, 180, 676-681.
57. Andreev, S. V.; Bartashevich, M. I.; Pushkarsky, V. I.; Maltsev, V. N.; Pamyatnykh, L. A.; Tarasov, E. N.; Kudrevatykh, N. V.; Goto, T. J. Alloys Compd. 1997, 260, 196-200.
58. Khan, M. H. R.; Hossain, A. K. M. A. J. Magn. Magn. Mater. 2012, 324, 550-558.
59. Nyamen, L. D.; Rajasekhar Pullabhotla, V. S.; Nejo, A. A.; Ndifon, P.; Revaprasadu, N. New J. Chem. 2011, 35, 1133-1139.