Large-scale synthesis of nickel sulfide micro/nanorods via a hydrothermal process

Abstract

Rhombohedral-phase NiS micro/nanorods were synthesized on a large scale through a hydrothermal method using NiCl₂·6H₂O and thiourea crystals as starting precursors. Recrystallized thiourea was observed to play an important role in the formation of micro/nanosized rods and flower-like structures. The molar ratio and reaction temperature of the precursors influenced the morphology and phase of NiS products. Pure rhombohedral NiS micro/nanorods were obtained on a large scale when the molar ratio between NiCl₂·6H₂O and thiourea crystals was fixed at 2:1, and the mixture was heated at 250°C for 5 h. Flower-like NiS nanostructures were formed when the molar ratio between NiCl₂·6H₂O and thiourea crystals was maintained at 1:1. The Raman and Fourier-transform infrared (FTIR) spectra of the as-prepared rhombohedral NiS micro/nanorods were collected, and their magnetic properties were investigated. The results showed that the FTIR absorption peaks of the as-prepared product are located at 634 cm⁻¹ and their Raman peaks are located at 216 and 289 cm⁻¹; the as-prepared NiS micro/nanorods exhibited weak ferromagnetic behavior due to the size effect.

Keywords

nickel sulfide / nanorods / hydrothermal synthesis / optical properties / magnetic measurement

References

[1] Ryu HS, Ha CW, Ji SY, Ahn IS, Ahn JH, Ahn HJ, Kim KW. Electrochemical properties of the NiS powder prepared by co-precipitation method for lithium secondary battery. J. Nanosci. Nanotechnol., 2014, 14(10): 7943.

[2] Yang JQ, Duan XC, Guo W, Li D, Zhang HL, Zheng WJ. Electrochemical performances investigation of NiS/rGO composite as electrode material for supercapacitors. Nano Energy, 2014, 5, 74.

[3] Yan XY, Tong XL, Ma L, Tian YM, Cai YS, Gong CW, Zhang MG, Liang LP. Synthesis of porous NiS nanoflake arrays by ion exchange reaction from NiO and their high performance supercapacitor properties. Mater. Lett., 2014, 124, 133.

[4] Yan SC, Shi Y, Sun LT, Xiao ZD, Sun B, Xu X. Controlled synthesis of NiS nanoparticle/CdS nanowire heterostructures via solution route and their optical properties. Mater. Sci. Eng. B, 2013, 178(1): 109.

[5] Li YB, Wang HF, Zhang HM, Liu PR, Wang Y, Fang WQ, Yang HQ, Li Y, Zhao HJ. A {0001} faceted single crystal NiS nanosheet electrocatalyst for dye-sensitised solar cells: sulfur-vacancy induced electrocatalytic activity. Chem. Commun., 2014, 50, 5569.

[6] Tang CJ, Zang CH, Su JF, Zhang DM, Li GH, Zhang YS, Yu K. Structure and magnetic properties of flower-like a-NiS nanostructures. Appl. Surf. Sci., 2011, 257(8): 3388.

[7] Ruan HC, Li YF, Qiu HY, Wei MD. Synthesis of porous NiS thin films on Ni foam substrate via an electrodeposition route and its application in lithium-ion batteries. J. Alloys Compd., 2014, 588, 357.

[8] Wang ZQ, Li X, Yang Y, Cui YJ, Pan HG, Wang ZY, Chen BL, Qian GD. Highly dispersed ß-NiS nanoparticles in porous carbon matrices by a template metal–organic framework method for lithium-ion cathode. J. Mater. Chem. A, 2014, 2, 7912.

[9] Ni SB, Yang XL, Li T. Fabrication of a porous NiS/Ni nanostructured electrode via a dry thermal sulfuration method and its application in a lithium ion battery. J. Mater. Chem., 2012, 22, 2395.

[10] Wang Y, Zhu QS, Tao L, Su XW. Controlled-synthesis of NiS hierarchical hollow microspheres with different building blocks and their application in lithium batteries. J. Mater. Chem., 2011, 21, 9248.

[11] Aso K, Hayashi A, Tatsumisago M. Preparation conditions of NiS active material in high-boiling solvents for all-solid-state lithium secondary batteries. New J. Chem., 2014, 38, 1731.

[12] H.M. Chuang, C.T. Li, M.H. Yeh, C.P. Lee, R. Vittal, and K.C. Ho, A coral-like film of Ni@NiS with core–shell particles for the counter electrode of an efficient dye-sensitized solar cell, J. Mater. Chem. A, 2(2014), p. 5816.

[13] Sun HC, Qin D, Huang SQ, Guo XZ, Li DM, Luo YH, Meng QB. Dye-sensitized solar cells with NiS counter electrodes electrodeposited by a potential reversal technique. Energy Environ. Sci., 2011, 4, 2630.

[14] Meng JL, Yu ZM, Li Y, Li YD. PdS-modified CdS/NiS composite as an efficient photocatalyst for H2 evolution in visible light. Catal. Today, 2014, 225, 136.

[15] Chen ZH, Sun P, Fan B, Zhang ZG, Fang XM. In situ template-free ion-exchange process to prepare visible-light-active g-C³N⁴/NiS hybrid photocatalysts with enhanced hydrogen evolution activity. J. Phys. Chem. C, 2014, 118(15): 7801.

[16] Pan Q, Xie J, Liu SY, Cao GS, Zhu TJ, Zhao XB. Facile one-pot synthesis of ultrathin NiS nanosheets anchored on graphene and the improved electrochemical Li-storage properties. RSC Adv., 2013, 3, 3899.

[17] Pan Q, Xie J, Zhu T, Cao G, Zhao X, Zhang S. Reduced graphene oxide-induced recrystallization of NiS nanorods to nanosheets and the improved Na-storage properties. Inorg. Chem., 2014, 53(7): 3511.

[18] Zhang YH, Guo L, He L, Liu K, Chen CP, Zhang Q, Wu ZY. Controlled synthesis of high-quality nickel sulfide chain-like tubes and echinus-like nanostructures by a solution chemical route. Nanotechnology, 2007, 18(48): 485609.

[19] Jiang XC, Xie Y, Lu J, Zhu LY, He W, Qian YT. A hydrogen bond-template route to nickel sulfide submicrotubes. Adv. Mater., 2001, 13, 1278.

[20] Zhang WQ, Xu LQ, Tang KB, Li FQ, Qian YT. Solvothermal synthesis of NiS 3D nanostructures. Eur. J. Inorg. Chem., 2005, 2005(4): 653.

[21] Mi LW, Chen YF, Wei WT, Chen WH, Hou HW, Zheng Z. Large-scale urchin-like micro/nano-structured NiS: controlled synthesis, cation exchange and lithium-ion battery applications. RSC Adv., 2013, 3, 17431.

[22] Li HB, Chai LL, Wang XQ, Wu XY, Xi GC, Liu YK, Qian YT. Hydrothermal growth and morphology modification of ß-NiS three-dimensional flowerlike architectures. Cryst. Growth Des., 2007, 7(9): 1918.

[23] Zhou H, Lv BL, Wu D, Sun YH. Hydrothermal synthesis and characterization of NiS flower-like architectures. Particuology, 2012, 10(6): 783.

[24] Wu ZC, Pan C, Li TW, Yang GJ, Xie Y. Formation of uniform flowerlike patterns of NiS by macrocycle polyamine assisted solution-phase route. Cryst. Growth Des., 2007, 7(12): 2454.

[25] Zhan FM, Geng BY, Guo YJ, Wang L. One-step synthesis of hierarchical carnation-like NiS superstructures via a surfactant-free aqueous solution route. J. Alloys Compd., 2009, 482(1-2): L1.

[26] Yang PF, Song B, Wu R, Zheng YF, Sun YF, Jian JK. Solvothermal growth of NiS single-crystalline nanorods. J. Alloys Compd., 2009, 481(1-2): 450.

[27] Ghezelbash A, Sigman MB, Korgel BA. Solventless synthesis of nickel sulfide nanorods and triangular nanoprisms. Nano Lett., 2004, 4(4): 537.

[28] Yang J, Duan X, Qin Q, Zheng W. Solvothermal synthesis of hierarchical flower-like ß-NiS with excellent electrochemical performance for supercapacitors. J. Mater. Chem. A, 2013, 1, 7880.

[29] Salavati-Niasari M, Banaiean-Monfared G, Emadi H, Enhessari M. Synthesis and characterization of nickel sulfide nanoparticles via cyclic microwave radiation. C. R. Chim., 2013, 16(10): 929.

[30] Nithima K, Areeporn O, Jinda K, Makoto O. Formation of MnS- and NiS-montmorillonites by solid-solid reactions. Appl. Clay Sci., 2009, 43, 238.

[31] Jiang JH, Yu R, Yi R, Qin WQ, Qiu GZ, Liu XH. Biomolecule-assisted synthesis of flower-like NiS microcrystals via a hydrothermal process. J. Alloys Compd., 2010, 493(1-2): 529.

[32] Wang LL, Zhu YC, Li HB, Li QW, Qian YT. Hydrothermal synthesis of NiS nanobelts and NiS2 microspheres constructed of cuboids architectures. J. Solid State Chem., 2010, 183(1): 223.

[33] Zhao PT, Zeng QM, Huang KX. Fabrication of ß-NiS hollow sphere consisting of nanoflakes via a hydrothermal process. Mater. Lett., 2009, 63(2): 313.

[34] Meng ZY, Peng YY, Yu WC, Qian YT. Solvothermal synthesis and phase control of nickel sulfides with different morphologies. Mater. Chem. Phys., 2002, 74(2): 230.

[35] Yu SH, Yoshimura M. Fabrication of powders and thin films of various nickel sulfides by soft solution-processing routes. Adv. Funct. Mater., 2002, 12(4): 277.

[36] Shen XP, Sun JQ, Wang GX, Park JS, Chen KM. A facile single-source approach to urchin-like NiS nanostructures. Mater. Res. Bull., 2010, 45(7): 766.

[37] Pan QT, Huang K, Ni SB, Yang F, He DY. Synthesis of flower- and rod-like nickel sulfide nanostructures by an organic-free hydrothermal process. Mater. Res. Bull., 2008, 43(6): 1440.

[38] Wang JH, Cheng Z, Brédas JL, Liu ML. Electronic and vibrational properties of nickel sulfides from first principles. J. Chem. Phys., 2007, 127, 214705.

[39] Bishop DW, Thomas PS, Ray AS. Micro Raman characterization of nickel sulfide inclusions in toughened glass. Mater. Res. Bull., 2000, 35(7): 1123.

[40] Zhang HT, Wu G, Chen XH. Synthesis and magnetic properties of NiS1+x nanocrystallines. Mater. Lett., 2005, 59(28): 3728.

[41] Sparks JT, Komoto T. Metal-to-Semiconductor Transition in Hexagonal NiS. Rev. Mod. Phys., 1968, 40, 752.

[42] Dewitt C, Dreyfus B, de Gennes PD. Low Temperature Physics, 1962, New York, Gordon and Beach, 413.

[43] Salavati-Niasari M, Davar F, Mazaheri M. Synthesis, characterization and magnetic properties of NiS1+x nanocrystals from [bis(salicylidene)nickel(II)] as new precursor. Mater. Res. Bull., 2009, 44(12): 2246.

[44] Cao F, Liu RX, Zhou L, Song SY, Lei YQ, Shi WD, Zhao FY, Zhang HJ. One-pot synthesis of flowerlike Ni7S6 and its application in selective hydrogenation of chloronitrobenzene. J. Mater. Chem., 2010, 20, 1078.

[45] Kodama RH, Makhlouf SA, Berkowitz AE. Finite size effects in antiferromagnetic NiO nanoparticles. Phys. Rev. Lett., 1997, 79, 1393.

[46] Sobhani A, Salavati-Niasari M. Synthesis, characterization, optical and magnetic properties of a nickel sulfide series by three different methods. Superlattices Microstruct., 2013, 59, 1.