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Journal of Nanoscience and Nanotechnology Vol. 11, 16, 2011

Glycerol Mediated Low Temperature Synthesis of Nickel Nanoparticles by Solution Reduction Method
Kalpana Singh2 , Kunal H. Kate1 , V. V. Satayanarayana Chilukuri2 , and P. K. Khanna1
Nanoscience Laboratory, Centre for Materials for Electronics Technology (C-MET), Off Dr. Homi Bhabha Road, Panchawati, Pune 411008, India 2 Catalysis Division, National Chemical Laboratory, Dr. Homi Bhabha Road, Pune 411008, India Phase pure Nickel nano-particles were synthesized by in-situ generation of nickel hydrazine hydrate complex (Ni-HH) followed by its decomposition in an alkaline glycerol medium. The synthesis can be performed in an open beaker with or without the use of surface protective reagents. By using the present method, Ni nano-particles can be prepared in large scale. The black nano-powders soobtained were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), selected area electron diffraction (SAED), Scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), Fourier transform infra-red (FTIR) spectroscopy and thermal analysis (TGA). XRD and SAED analysis revealed that the synthesized particles were pure crystalline nickel with FCC structure.
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Keywords: Nano-Particles, Transition Metal, Chemical Reduction, Synthesis, XRD. 1. INTRODUCTION

In recent time there are several reports describing the use of nickel nano-particles in electronic and data storage devices1 as well as in catalysis, as magnetic materials, in conducting inks, and as ferrouids2 including applications as biosensors, as fuel-cell catalysts, composites and solar energy materials.3 Synthesis of nickel nano-particles have been reported by chemical methods by several researchers. Preparation in ethylene glycol2 in presence of various reducing agents such as sodium borohydride and hydrazine at elevated temperature has been described to be a very useful method. In addition, there are number of other reports on the synthesis of nickel nano-particles from aqueous solution.46 Sodium borohydride is one of the most effective reducing agent and in presence of trioctylphine oxide (TOPO) and amines high quality mono-disperse nickel nano-particles have been reported.7 Oleic acid capped nickel nano-particles have been reported but these seem to be too small and soft for harsh catalytic reactions however, such small particles are excellent candidates for magnetic devices.8 Hydrazine hydrate mediated Nickel complex [Ni (N2 H2 Cl2 i.e., Ni-HH] has often been used for the preparation of hard and bigger nano-particles. The formation and isolation of nickel hydrazine-hydrate complex is considered to be the key step. Thus, the complex can be rst

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isolated and then reduced to ne nickel powder9 or can be in-situ utilized for further reaction and reduction with excess hydrazine in highly basic reaction conditions and/or high boiling solvent like ethylene glycol.10 The problem however may arise out of the mixture of Ni-HH complex having various molecular weights which will have varied reactivity and their thermal decomposition may also therefore will vary from compound to compound. The longer reaction time, higher pH and higher temperature will thus allow the yield to increase at the cost of smaller particles. The reaction time for one type of Ni-HH complex will thus disturb the thermodynamics of the other complex due to intense competition during the reduction process. Ethylene glycol has been often described as one of the best medium for Ni-HH related experiments. Use of glycerol has been also reported for synthesis of Ni and NiO coreshell nano-particles but without involving nickel-hydrazine hydrate complex formation.11 We gathered that the large scale synthesis based on Ni-HH by using polymeric surfactants and glycerol has not appeared in the literature in plenty. Hydroxyethyl carboxymethyl cellulose has been used in one of the reports by Wang et al.12 to prepare nickel nano-particles at large scale using hydrazine hydrate. We have earlier shown that use of water soluble polymer such as polyvinyl alcohol (PVA) and polyvinylpyrrolidone (PVP) can be employed to stabilize the nano-particles. Successful use of sodium formaldehyde sulfoxylate (SFS) for preparation of nickel and copper nano-particles has been reported by us in
doi:10.1166/jnn.2011.4142

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Glycerol Mediated Low Temperature Synthesis of Nickel Nanoparticles by Solution Reduction Method

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the recent past.1314 To enhance the applicability of nanoparticles, it is desirable to make their surface hydrophilic or hydrophobic so that they can be easily redispersed and can be carried to the site of application. In the current methods of producing nickel nanoparticles in large scale (typically a few grammes) we made exclusive use of glycerol as a medium to obtain the particle size as small as 1520 nm. Present article, describes large scale synthesis of nickel nano-particles wherein reduction of nickel salt by hydrazine hydrate in alkaline pH has been carried out via formation of nickel hydrazinehydrate (Ni-HH) complex. Synthesis of nano -nickel by use of a coordinating hydrophilic polymers may reduce probability of surface oxidation.

3010 transmission electron microscope with an acceleration voltage of 300 kV. Randomly oriented particles on the TEM substrate were obtained by using diluted solution of the nano-particles. 2.2. Synthesis of Nickel Nano-Particles; A General Method Typically, to 200 ml Glycerol, 0.5 g PVA or PVP was added at 100 C with stirring. After the complete dissolution of polymer appropriate amount of NaOH was added to make the solution alkaline and bring the pH to 1214. Nickel chloride hexahydrate (5.0 gm) was then added to this polymeric solution and was allowed to dissolve completely. After 15 min, hydrazine hydrate was added drop wise over 10 min period at 180 C. During the addition blue colored precipitate of nickel hydrazinehydrate (NiHH) complex was formed. The resulting mixtures were stirred rapidly at the same temperature. As the reaction progressed, the blue solution turned black within an hour, indicating the decomposition of the Ni-HH complex and formation of metallic nickel. The reaction was continued for 2 more hours so as to make sure that reaction is complete. After cooling the reaction mixture to room temperature, it was ltered, washed with several portions of distilled water and nally with ethanol. The black residue in each case was dried overnight in an oven at 80 C to collect the free owing black powder in almost quantitative yield. For the neat reaction, the procedure was same except for the absence of PVA or PVP. The samples were named as Ni-Neat, Ni-PVA and Ni-PVP for clarity of discussion. Similar experiments were conducted at 120 C for preparation of smaller particles but with yield of about 2030%.

2. EXPERIMENTAL DETAILS
2.1. General All chemicals used were of analytical grade. Nickel chloride (NiCl2 2H2 O), hydrazine hydrate, PVP (chain consisting of (111)n , PVA (mW: 1,25,000) and glycerol were obtained commercially and were used as received. Powder XRD data was obtained using Philips Xpert instrument. Scanning electron microscopy (SEM) was carried out on a Quanta 200 3D machine. X-ray photoelectron spectra (XPS) were recorded with a 9 channeltron CLAM4 analyzer under a vacuum better than 1 108 Torr, using Mg-K radiation with a constant energy of 50 eV. FTIR spectra were recorded using KBr discs on Perkin Elmer FT-IR 2000 spectrophotometer in the range of 400 4000 cm1 . Low and high resolution transmission electron microscopy (TEM) images were taken on a FEI TECNAI

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PVA

PVP

Glycerol

PVP or PVA + NiCl2.xH2O + NaOH ----

= Ni ions trapped in polymeric matrix OH = basic pH due to NaOH Ni2+ PVA/PVP + NH2NH2.xH2O ---[Ni(N2H2)Cl2] (Intermediate Ni-HH complex)

[Ni (N2H2)Cl2] + NH2NH2.xH2O + NaOH ------

Ni(0)

Nickel nano-particles
Scheme 1. Schematic presentation of formation of nano-nickel via trapping of Ni-ions in polymeric surfactants, (via formation of Ni-HH intermediate and its subsequent dissociation) and their attraction towards the magnetic bar.

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Glycerol Mediated Low Temperature Synthesis of Nickel Nanoparticles by Solution Reduction Method
(A)

3. RESULTS AND DISCUSSION

The present work although not a repetition but can be categorized as the modication of the earlier methods that used ethylene glycol or glycerol but in different combinations of reducing agents and without these polymers.9 In the present work, the Ni-HH complex was thermally dissociated in basic medium between 120180 C, which generated two types of nano-particles. The lower temperature resulted in formation of zero-valent nickel with small particles size and the higher temperature yielded bigger nano-particles. The same pH and the ratio of surfactant at two different temperatures thus resulted in the crystallite size based on XRD, in the range of 1525 nm depending on the surfactant and temperature. However, the particle size estimated from the TEM was found to be always greater than XRD which is appropriate owing to possible agglomeration of the particles in polymeric surfactants. The low temperature experiments yielded the product in low yield due to the fact that the temperature was normally not enough with respect to time to dissociate the entire NiHH complex to zero valent nickel. This thus reduced the yield typically to 2030%. The product showed spherical morphology with size in the range of about 15 nm. The use of two polymeric surfactants e.g., PVP and PVA in glycerol medium was compared with the experiment that uses only glycerol. The effect of surfactant was mostly insignicant on the size of the particles. Similar observations and results were obtained for the reactions carried out at higher temperature of 180 C. The higher temperature although converted the Ni-HH complex completely to nickel metal but their size increased to about 2025 nm. Also, enhanced temperature resulted in particles which are highly crystalline and agglomerated. The choice of polymers along with pH and reducing agent concentration is believed to be crucial for such synthesis. It appears that the use of glycerol controls nucleation of particles, along with offering a thin coating and has impact on the rate of reduction of metal ions. Scheme 1 describes the unit chain of the PVA, PVP and glycerol. The nano-particles may bind with the functional group of the polymer and through OH of glycerol. Initially the metal ions are trapped in polymers in alkaline glycerol medium and are supposed to be homogeneously distributed. Subsequently, Ni-HH complex is formed uniformly throughout the matrix/medium which then dissociated to yield the nano-particles via nucleation and growth mechanism. XRD analysis of black powders, conrmed formation of phase pure nickel nano-particles. Figure 1 shows broadened XRD patterns of as-prepared nano-powders. XRD peaks are observed at 2 value of 44.5, 51.8 and 76.5 representing 111 , 200 and 220 planes of fcc crystal structures of nickel. An estimation of crystallite size by use of Scherrers equation and by averaging the values, revealed a crystallite size of about 2326 nm in case of the samples prepared at higher temperature i.e.,
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(B)

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Fig. 1. (A) XRD patterns of nano-Ni prepared at 180 C in glycerol. (a) Ni-Neat; (b) Ni-PVA and (c) Ni-PVP. (B) XRD patterns of nano-Ni prepared at 120 C in glycerol. (a) Ni-Neat; (b) Ni-PVA and (c) Ni-PVP.

180 C (Fig. 1) and 1420 nm in case of experiments conducted at 120 C (Fig. 1(a)). The low temperature experiments resulted in formation of smaller particles and the gure shows broader pattern than the high temperature experiments. The effect of temperature is therefore clearly dened in the present preparation in addition to the role of polymeric surfactants. It is also observed that the particles prepared without the surfactants at high temperature
Table I. Calculation of crystallite size of various Ni nano-particles prepared from Ni-HH complex using glycerol as a medium. Crystallite size (nm) Crystal planes S.No 1 2 3 4 5 6 sample Synthesis at 120 C Ni Neat Ni PVA Ni PVP Synthesis at 120 C Ni Neat Ni PVA Ni PVP 111 17 0 17 0 22 72 30 3 22 7 27 2 200 11.6 18.7 17.5 21.6 16.5 20.0 220 13.1 26.5 18.8 18.9 37.6 23.9 Average crystallite size (nm) 13.9 20.7 19.6 23.6 25.6 23.7

Glycerol Mediated Low Temperature Synthesis of Nickel Nanoparticles by Solution Reduction Method
(A) (B) (C)

Singh et al.

Fig. 2.

TEM (A) and HRTEM (ED inset) (B) and SEM (C) of nano-nickel prepared from Ni-HH complex in PVA glycerol at 180 C.

are almost similar in dimensions but they appear to be more crystalline. However, the low temperature experiments without the surfactants showed marked differences in crystallite size (14 nm). Amongst the polymers used, PVP is found to be less effective in controlling the particle nucleation and growth in 111 direction than in PVA. From Table I, it can be seen that the crystallite size in both the adopted experimental conditions at 111 plane, is bigger when PVP was employed and is smaller when PVA was used. TEM and HRTEM analysis of polymer capped nickel nano-particles prepared at 180 C, showed chained, clustered and elongated spherical agglomerates (Figs. 24) in the range of about 2050 nm which is bigger than the crystallite size calculated from the XRD pattern because many small crystallites come together to form particles. The particles prepared in presence of PVA (Fig. 2(A)) show ower like clusters due to high cross linking of the polymer chain. Similarly, PVP bound nickel nano-particles are like a clustered ower (Fig. 3(A)) but are much more agglomerated than PVA. The particles examined by TEM for the samples where no polymers (Fig. 4(A)) has been used can be seen to be much better in terms of aggregation and they show a chain like behavior indicating the interparticle attraction probably due to magnetism thus they might assemble themselves as a chain which was not possible for particles that are embedded in polymer leading to suppressed magnetism. The presence of well dened concentric ring in electron diffraction pattern indicates that the nano-particles are fairly crystalline (inset 2(b)4(b)).

SEM measurement of as-prepared nickel nano-particles in glycerol alone revealed formation of spherical agglomerates (Figs. 2(C)4(C)). The TEM of the nano-particles prepared at lower temperature (120 C) showed aggregates of smaller particles however these were more or less similar in appearance (Fig. 5). It is observed that the best spherical morphology of nickel nano-particles is obtained when the temperature is maintained at 180 C. The particles at 120 C show ill dened shapes and are highly agglomerated. In FTIR spectra shown in Figure 6, the broad absorption band centered around 1620 cm1 may correspond to HOH bending vibrational mode of water molecule. The presence of water might be due to that fact that glycerol is a highly dense liquid and is high boiling solvent. This therefore might retain the water molecules from the reaction mixture as well as due to the nal washing. Despite the fact that traces of water is present in the sample, it does not affect the nano-particles as there is no nickel oxide formation which is conrmed by absence of band around 460 cm1 .9 The absence of oxide is also revealed in XRD pattern. TGA studies were undertaken to see the total weight loss of the samples. The percentage weight loss due to the presence of PVA/PVP/Glycerol in the nal samples would reveal the extent of solid content. Figure 7 show that the curve for Ni-PVA indicates a total weight loss of about 10%. However the weight loss for the nanoparticles coated with PVP was about 5%, and the nickel nano-particles that were synthesized using only glycerol

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(A)

(B)

(C)

Fig. 3.

TEM (A) and HRTEM (ED inset) (B) and SEM (C) of nano-nickel prepared from Ni-HH complex in PVP glycerol at 180 C.

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Glycerol Mediated Low Temperature Synthesis of Nickel Nanoparticles by Solution Reduction Method
(B) (C)

Fig. 4.

TEM (A) and HRTEM (ED inset) (B) and SEM (C) of nano-nickel prepared from Ni-HH complex in glycerol alone at 180 C.

130

(A)

(B)
125 120

NiPVA NiNeat NiPVP

% Wt loss/gain
Fig. 5. TEM (of nano-nickel prepared from Ni-HH complex in glycerol PVA (A) and PVP (B) at 120 C.

115 110 105 100 95 90

showed less than 1% wt loss. When the polymeric capping agent is decomposed at temperature about 300 C, the Ni nano-particles get easily oxidized as shown in the gure by increase in the weight in all three cases. The binding energy value for metallic nickel is reported to be at 852.2 eV having a single peak corresponding to the Ni 2p3/2 level and it is characteristic of Ni 0 .1517 In the present case, the nanoparticles may get surface oxidized due to exposure to air during the pellatization for XPS measurement. In that case the pure Ni binding energy may be difcult to obtain as the samples have reasonable

85 30 130 230 330 430 530

Temperature (celcius)

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Fig. 7. TGA of nano-nickel prepared from Ni-HH complex in glycerol using various polymers.

amount of polymers in them (10% in case of Ni-PVA based on T GA). This then is likely to suppress the binding energy peak for nickel nano-particles. Indeed, the observation in the Figure 8 shows that the four peaks are due to formation of nickel oxide and presence of other Ni(II)

Fig. 6. FTIR of nano-nickel prepared from Ni-HH complex in glycerol using various polymers.

Fig. 8. Ni 2p core level XPS spectra showing binding energy for Ni in Ni-PVP, Ni-PVA and Ni-Neat.

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Glycerol Mediated Low Temperature Synthesis of Nickel Nanoparticles by Solution Reduction Method
Table II. XPS binding energies of various nickel samples. Samples prepared at 180 C Ni-Neat Ni-PVA Ni-PVP BE values observed (eV) 855, 860.9, 872.6, 879 855.6, 861.6, 873, 880 856, 862, 873.8, 880.1 Reported BE values [15, 16] (eV) 855, 855.9; 858.2, 873.8 852.9, 870.7

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Acknowledgments: We thank Director, C-MET for permission and Department of Information Technology (Govt. of India) for nancial support.

References and Notes

1. P. Calandra, Mater. Lett. 63, 2416 (2009). 2. F. B. Zhang, Y. T. Chen, J. Z. Zhao, and H. L. Li, Chem. Lett. 33, 146 (2004). 3. S. Gunter, Nanoparticles-from Theory to Application, 1st edn., Wiley-VCH Verlag GmbH, Germany (2004). 4. Y. D. Li, C. W. Li, H. R. Wang, L. Q. Li, and Y. T. Qian, Mater. Chem. Phys. 59, 88 (1999). 5. K. S. Chou and K. C. Huang, J. Nanoparticle Res. 3, 127 (2001). 6. K. S. Chou, S. C. Chang, and K. C. Huang, Azojomo-The AZo Journal of Materials Online; Advances in Technology of Material and Materials Processing 8, 172 (2006). 7. Y. Duan and J. Li, Mater. Chem. Phys. 87, 452 (2004). 8. D. S. Sidhaye, T. Bala, S. Srinath, H. Srikanth, P. Poddar, M. Sastry, and B. L. V. Prasad, J. Phys. Chem. C 113, 3426 (2009). 9. J. W. Park, E. H. Chane, S. H. Kim, J. H. Lee, J. W. Kim, S. M. Yoon, and J. Y. Choi, Mater. Chem. Phys. 97, 371 (2006). 10. S. H. Wu and D. H. Chen, J. Colloid and Interface Science 259, 282 (2003). 11. Y. Li, C. Mei, J. Rogers, Y. Xu, and W. Shen, Mater. Lett. 60, 750 (2006). 12. H. Wang, X. Kou, J. Zhang, and J. Li, Bull. Mater. Sci. 31, 97 (2008). 13. P. K. Khanna, P. V. More, J. P. Jawalkar, and B. G. Bharate, Mater. Lett. 63, 1384 (2009). 14. P. K. Khanna, T. S. Kale, M. Shaikh, N. K. Rao, and C. V. V. Satyanarayana, Mater. Chem. Phys. 110, 21 (2008). 15. X. J. Tao, Z. W. Li, H. J. Chen, P. Y. Zhang, Z. J. Zhang, Z. S. Wu, and H. X. Dang, Acta. Phys-Chem. Sin. 21, 560 (2005). 16. G. G. Couto, J. J. Klein W. H. R. Schreine, D. H. Mosca, A. J. A. de Oliveira, and A. L. G. Zarbin, J. Colloids and Interface Sciences 311, 461 (2007) 17. F. Alonso, P. Riente, J. A. T. Sirven, and M. Yus, Appl. Catal., A: General. 18. S. Lee, N. Lee, J. Park, B. H. Kim, Y. W. Yi, T. Kim, T. K. Kim, I. H. Lee, and S. R. Paik, Hyeon. Am. Chem. Soc. 10658, 128 (2006).

species. However, there is a clear shoulder at 852.2 eV (marked by an arrow in the Fig. 8) which is an indication of binding energy value of pure nickel in sample that has PVA. In the spectra of other samples, (Fig. 8) this might have overlapped with the peak in the region of 855 eV due to its broad nature. Thus it got merged with this peak. The other peaks have been reported for Ni(II) species in the samples and we also observe similar values (Table II). This indicates that the samples are prone to surface oxidation. The peak at about 855856 eV have been ascribed to the Ni 2p3/2 level of Ni(II) in NiO, due to the oxidation of nickel nanoparticles in air.18

4. CONCLUSIONS
The present study illustrates simple, convenient and technologically signicant methods for the synthesis of nickel nano particles in aqueous glycerol medium with or without the use of hydrophilic polymers which act as a matrix or the surfactant to protect the particle growth. XRD analysis indicated the presence of relevant crystal planes for fcc crystal structure of nickel. SEM and TEM analysis showed formation of spherical particles. Electron diffraction pattern showed characteristic concentric rings for nickel metal. The particles size was found to be about 1530 nm depending on the reaction temperature.

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Received: xx Xxxx xxxx. Accepted: xx Xxxx xxxx.

J. Nanosci. Nanotechnol. 11, 16, 2011