Author’s Accepted Manuscript

Controllable synthesis and magnetic properties of

Xiaoyu Yang, Xiaojia Yu, Qun Yang, Dalei Zhao,

PII: S0272-8842(17)30493-5
DOI: http://dx.doi.org/10.1016/j.ceramint.2017.03.121
Reference: CERI14890
To appear in: Ceramics International
Received date: 9 March 2017
Revised date: 20 March 2017
Accepted date: 20 March 2017
Cite this article as: Xiaoyu Yang, Xiaojia Yu, Qun Yang, Dalei Zhao, Kang
Zhang, Jixin Yao, Guang Li, Haidong Zhou and Xueqin Zuo, Controllable
synthesis and magnetic properties of hydrothermally synthesised NiCo2O4 nano-
s p h e r e s , Ceramics International,
http://dx.doi.org/10.1016/j.ceramint.2017.03.121
This is a PDF file of an unedited manuscript that has been accepted for
publication. As a service to our customers we are providing this early version of
the manuscript. The manuscript will undergo copyediting, typesetting, and
review of the resulting galley proof before it is published in its final citable form.
Please note that during the production process errors may be discovered which
could affect the content, and all legal disclaimers that apply to the journal pertain.
Controllable synthesis and magnetic properties of

hydrothermally synthesised NiCo2O4 nano-spheres

Xiaoyu Yang1, Xiaojia Yu1, Qun Yang1, Dalei Zhao1, Kang Zhang1, Jixin

Yao1, Guang Li1, 2, , Haidong Zhou3,4, Xueqin Zuo1

1
School of Physics and Materials Science, Anhui University, Hefei 230601, China

2
Anhui Key Laboratory of Information Materials and Devices, Hefei 230601, China

3
Department of Physics and Astronomy, University of Tennessee, Knoxville, Tennessee 37996-1200,

USA
4
National High Magnetic Field Laboratory, Florida State University, Tallahassee, Florida 32310, USA

Abstract

In the work, we explored an efficient synthetic platform to purposefully fabricate different

morphologies of NiCo2O4 by controlling the hydrothermal temperature. All the obtained samples were

characterized by means of X-ray diffraction, scanning electron microscopy, high resolution

transmission electron microscopy. With the increase of hydrothermal temperature, the morphology of

obtained samples transformed from spongy nanosphere to ellipse-like, then to peanut-like structure and

an effective blue shifting of Raman spectroscopy occurred. The magnetic measurements indicated that

the materials transform from paramagnetic to weak ferromagnetic with the increase of hydrothermal

temperature.

Keyword: A. Powders: chemical preparation; NiCo2O4; Nanostructure; C. Magnetic

properties

1. Introductions

In the past decades, nanopowders and nanostructured materials have aroused

Corresponding author. Tel: (+86) 0551 63861867, Fax: (+86) 0551 63861992

e-mail address: liguang1971@ahu.edu.cn (G. Li), liguang64@163.com

1
extensive concern because of their special nature and wide applications. All of them

were applied in magnetic storage devices, microwave absorption devices, drug

delivery, electronic devices, sensors, catalysts, etc. [1-4]. These properties strongly

depend on size, morphology, structure, chemical composition of nanomaterials and

their synthesis methods [5-7]. In this respect, nanomaterials such as simple metal

oxides and transition metal oxides are currently the focal point for wide application.

Recent literatures suggest that the spinel NiCo2O4 was an excellent material and

widely applied, such as photocatalysis [8], electrical transport [9], sensors [10],

supercapacitors [11], H2O2 reduction reaction [12] and magnetic devices [13-15]. The

versatile applications of NiCo2O4 are due to its inspiring advantages, including low-

cost, abundant resources, stability, environmentally benign and exhibit variable

oxidation states. However, the synthesis of NiCo2O4 needs low temperature, which is

primarily owing to the instability of NiCo2O4 at a temperature over 673 K. Therefore,

a number of synthesis methods are achieved by utilizing different low temperature

routes, such as sol-gel [16], coprecipitation [17, 18], hydrazine carboxylate hydrates

[19] and hydroxide nitrates [16, 20]. The NiCo2O4 nano-particles with different

morphologies have different properties. Up to now, the diverse morphologies of

NiCo2O4 such as nanoflowers [21], nanorods [22], nanoplatelets [8, 9], nanoneedles

[23], and mesoporous [15] have been prepared. However, as far as we know, there are

only a few of these studies about the influences of the synthesis temperatures and

morphologies for magnetic properties of NiCo2O4.

In this paper, we explored a facile but efficient synthesis route to investigate the

synthesis of specific morphologies of NiCo2O4 by controlling the hydrothermal

temperatures without using any surfactant and template. It was found that the

hydrothermal temperature plays an important role in the synthesis of the spongy

2
nanospheres, ellipsoids, and peanut-like morphologies of NiCo2O4. Meanwhile, for

the different morphology of NiCo2O4 nanostructures, they show different magnetic

properties.

2. Experimental details

2.1 Preparation of NiCo2O4 magnetic nanoparticles

All the reagents were of analytical grade purity and used as received without

further purification before the synthesized process. To obtain the samples of NiCo2O4

nanostructures, a typical hydrothermal synthesis process was employed as followed: 1

mmol of Ni(CH3COO)2·4H2O and 2 mmol of Co(CH3COO)2·4H2O were firstly

dissolved into 80 mL of ethylene glycol with 40 mmol of NH4HCO3. The solution

was then transferred into a Teflon-lined stainless steel autoclave of 100 mL in volume,

which was kept at 120°C, 160°C and 200°C for 20 h, respectively. After natural

cooling to room temperature, the pink precipitates were washed with distilled water

and ethanol three times in turn, and then dried at 60°C overnight. These samples

annealed at 350°C for 2 h without any protective gas. The as-prepared samples were

labeled as NC-120, NC-160, and NC-200, respectively.

2.2 Characterizations

The powder X-ray diffraction (XRD) patterns of the samples were characterized by

X-ray diffraction (XRD, XD-3) using Cu Kα radiation (λ=0.154 nm) at 36kV and 20

mA and in the range of 2θ from 10° to 80° at scanning speed 4°/min. Morphologies

and sizes of synthesized samples were studied by scanning electron microscope (SEM,

S-4800, Japan) and transmission electron microscope (TEM, JEM-2100, Japan). The

Raman spectra were recorded by Raman spectrometer system (inVia-Reflex) using a

laser with 532 nm excitation. The magnetic properties of samples were recorded via a

vibrating sample magnetometer (VSM, MicroSense EZ9) at room temperature.

3
3. Results and discussion

3.1. XRD characterization

The crystal phases of NiCo2O4 samples were identified by XRD. Fig. 1 shows the

XRD patterns of the products obtained at 120°C, 160°C, and 200°C for 20 h,

respectively. The dominant peaks at about 18.9°, 31.2°, 36.7°, 38.4°, 44.6°, 55.4°,

59.2° and 65.1° correspond to the (hkl) planes of (111), (220), (311), (222), (400),

(422), (511) and (440) lattice planes, which coincide with the standard diffraction

pattern of PDF card of the spinel phase NiCo2O4 (JCPDS NO. 073-1702). There are

no other peaks detected except the peaks aforementioned, betokening high purity of

the products. All the diffraction peaks are sharp but broad, which indicate as-obtained

NiCo2O4 samples are composed of primary small crystal particles and possess a good

crystallinity.

3.2. Raman analysis

In order to further study the compositions and structures of as-obtained NiCo2O4

samples, Raman analysis was performed with typical spectra range of 100-1000 cm-1

(Fig. 2). The stretching vibration peaks observed at ~186, ~477, ~523 and ~671 cm-1

correspond to F2g, E2g, F2g and A1g models of NiCo2O4, respectively. Only the Co-O

and Ni-O vibrations of NiCo2O4 samples are detected, while no peak corresponding to

the OH group was observed, indicating that pure NiCo2O4 samples were formed after

calcinations. The results are in good agreement with the XRD results, which further

confirm the formation of NiCo2O4 nanocrystals [24-26]. However, comparing with

the NC-200 sample, the NC-120 sample shows blue shift of about 15 cm-1 for A1g

mode and 16 cm-1 for E2g mode but F2g modes (186 and 523 cm-1) are not impacted,

and the NC-160 sample shows blue shift of about 7 cm-1 for A1g mode and 9 cm-1 for

E2g mode but F2g modes (186 and 523 cm-1) are not affected. This result is attributed

4
to the nanosize effect of NiCo2O4 particles [27].

3.3. SEM and TEM characterization

The morphologies of NiCo2O4 samples from different hydrothermal temperatures

(120°C, 160°C, 200°C) are revealed in Fig. 3. Fig. 3a and Fig. 3b present different

magnification SEM images of NiCo2O4 sample with a hydrothermal reaction

temperature of 120°C. Obviously, the resulting products are composed of NiCo2O4

spongy nanospheres. It can be seen that the observed NiCo2O4 spongy nanospheres

have a uniform diameter of 600 nm. These nanospheres were further studied by TEM

(Fig. 4a). It can be found that the as-synthesized spongy nanospheres are constructed

by a large quantity of primary nanoparticles subunits of about 8 nm in size. The

HRTEM image (Fig. 4b) shows lattice fringes with a d-spacing of 0.47 nm, which

corresponds to the (111) lattice plane of NiCo2O4 [28, 29]. When the hydrothermal

reaction temperature is increased from 120°C to 160°C, a large amount of highly

unified ellipsoidal structures are exhibited in Fig. 3c and Fig. 3d, the SEM images

credibly reveal the feature for the ellipsoids of round 1 um in length and

approximately 850 nm in center width. A typical TEM image (Fig. 4c) unexpectedly

gives a solid evidence to reveal that the NiCo2O4 ellipsoids are constructed by lots of

nanoparticles with a diameter of about 11 nm. In addition, the HRTEM image (Fig. 4d)

shows the visual lattice fringes with spacing of ~0.47 nm can be legitimately ascribed

to (111) crystalline facet of the NiCo2O4. With the increase of hydrothermal reaction

temperature to 200°C, the peanut-like nanostructures are clearly displayed in the SEM

images, as shown in Fig. 3e and Fig. 3f. The TEM image (Fig. 4e) reflects the peanut-

like of NiCo2O4 nanostructures are constructed by a large quantity of nanoparticles

about 14 nm in size. The HRTEM image (Fig. 4f) exhibits a lattice spacing of 0.29

nm, corresponding to be (220) plane of NiCo2O4.

5
3.4 Magnetic properties

Fig. 5 represents the field dependent magnetic properties of the as-prepared

samples of NiCo2O4 from different hydrothermal temperatures (120°C, 160°C, 200°C)

measured at room temperature using a vibrating sample magnetometer, which are

typical magnetization hysteresis loops for NiCo2O4 samples at 300 K. Present

magnetization measurements show that the saturation magnetization (MS) and

coercivity (HC) increase with the increase of hydrothermal reaction temperature. The

magnetic parameters such as MS, HC and magnetic moment (nB) evaluated from M-H

loop are listed in Table 1. The nominal magnetic moment in B per formula unit is

computed using the following relation:

(1)

Mwt and MS represent the molecular weight of the ingredient and saturation

magnetization in g/mol and emu/g, respectively [30].

For the case of as-prepared NiCo2O4 sample with a hydrothermal reaction

temperature of 120°C, the magnetization does not saturate, even for the magnetic field

of 10000 Oe, and no hysteresis (or finite coercive field) is observed. The M-H curve is

typical of paramagnetic behavior associated with small magnetic particles for the as-

prepared NiCo2O4 sample (NC-120) [31, 32], as expected for NC-120 with small

magnetic particle size (10 nm). With increasing hydrothermal reaction temperature,

the material transforms from the paramagnetic to the weak ferromagnetic. The

obtained NiCo2O4 samples show higher HC and MS than the NiCo2O4 sample (NC-

120). Especially, the peanut-like NiCo2O4 structures (hydrothermal reaction

temperatures 200°C) exhibit superior coercivity and saturation magnetization, which

are 119.7 Oe and 1.8 emu g-1, respectively. Due to their different nanostructures,

higher HC is likely to have two main contributions apart from magnetocrystalline

coupling, where the ferromagnetic is origin from the defects of interfaces [33]. With

the material transforming from nanospheres to peanut-like, its shape anisotropy

increases significantly, resulting in an increase in coercivity.

4. Conclusions

In summary, we have synthesized NiCo2O4 nanostructured samples with three

different morphologies by a simple yet cost-effective synthetic methodology at 120°C,

160°C and 200°C autoclave temperatures. The as-prepared NiCo2O4 samples were

composed of many smaller nanoparticles and the size of these nanoparticles increases

with the increase of hydrothermal temperature. With the increase of hydrothermal

temperature, the morphology of obtained samples transforms from spongy nanosphere

to ellipse-like, then to peanut-like structure. Increasing hydrothermal temperature

results in an effective blue shifting of Raman spectroscopy, and the material

transforms from the paramagnetic to the magnetic. This phenomenon is widely

observed in magnetic materials at nanoscale due to the size effect.

Acknowledgements

This work was financially supported by National Natural Science Foundation of

China (11674001), Anhui Provincial Natural Science Foundation (1708085MA07),

the Opening Project of State Key Laboratory of High Performance Ceramics and

Superfine Microstructure (SKL201607SIC), and in part by the National Natural

Science Foundation of China (11174002), the Ph.D. Programs Foundation of Anhui

University (J01003206) and the Natural Science Foundation of Anhui Province

(1708085QE116).

References

[1] M. Muzaffari, S. Manouchehri, M.H. Yousefi, J. Amighian, The effect of solution temperature on

7
 crystallite size and magnetic properties of Zn substituted Co ferrite na-noparticles, J. Magn. Magn.

Mater. 322 (2010) 383–388.

[2] L.W. Yeary, J.W. Moon, C. Rawn, L.J. Lane, A. Rondinone, J.R. Tompson, B.C. Chakoumakis, T.J.

Phelps, Magnetic properties of bio-synthesized zinc ferrite nanop-articles, J. Magn. Magn. Mater.

323 (2011) 3043–3048.

[3] J. Slama, A. Gruskova, M. Usakova, E. Usak, J. Subrt, J. Lukac, Substituted Ni-Zn ferrites for

passive sensor applications, J. Electr. Eng. 57 (2006) 159–162.

[4] K. Chinnaraj, A. Manikandan, P. Ramu, S.A. Antony, P. Neeraja, Comparative studies of

microwave- and sol-gel-assisted combustion methods of Fe3O4 nanostructures: structural,

morphological, optical magnetic, and catalytic properties, J. Supercond. Novel Magn. 28 (1) (2014)

179–190.

[5] Yu.A. Koksharov, G.B. Khomutov, G.Yu. Yurkov, S.P. Gubin, Magnetic nanoparticles: preparation,

structure and properties, Russ. Chem. Rev. 74 (6) (2005) 489-520.

[6] M. Chand, S. Kumar, A. Shankar, R. Porwal, R. Pant, The size induced effect on

rheological properties of Co-ferrite based ferrofluid, J. Non-Cryst. Solids 361 (2013) 38–42.

[7] K. Ahalya, N. Suriyanarayanan, V. Ranjithkumar, Effect of cobalt substitution on structural and

magnetic properties and chromium adsorption of manganese ferrite nano particles, J. Magn. Magn.

Mater. 372 (2014) 208–213.

[8] B. Cui, H. Lin, Y.-Z. Liu, J.-B. Li, P. Sun, X.-C. Zhao, C.-J. Liu, Photophysical and Photocatalytic

Properties of Core-Ring Structured NiCo2O4 Nanoplatelets, J. Phys. Chem. C 113 (2009) 14083-

14087.

[9] L. Hu, L. Wu, M.Y. Liao, X. Hu, X.S. Fang, Electrical Transport Properties of Large, Individual

NiCo2O4 Nanoplates, Adv. Funct. Mater. 22 (2012) 998-1004.

[10] Y. Liu, Y. Zhang, T. Wang, P. Qin, Q. Guo, H. Pang, Mesoporous Ni0.3Co2.7O4 hierarchical

structures for effective non-enzymatic glucose detection, RSC Adv. 4 (2014) 33514-33519.

[11] N. Garg, M. Basu, A.K. Ganguli, Nickel Cobaltite Nanostructures with Enhanced

Supercapacitance Activity, J. Phys. Chem. C 118 (2014) 17332-17341.

[12] R. Ding, L. Qi, M.J. Jia, H.Y. Wang, Simple hydrothermal synthesis of mesoporous spinel

NiCo2O4 nanoparticles and their catalytic behavior in CH3OH electro-oxidation and H2O2 electro-

reduction, Catal. Sci. Technol. 3 (2013) 3207-3215.

8
[13] J.F. Marco, J.R. Gancedo, M. Gracia, J.L. Gautier, E.I. Ríos, H.M. Palmer, C. Greaves, F.J. Berry,

Cation distribution and magnetic structure of the ferrimagnetic spinel NiCo 2O4, J. Mater. Chem. 11

(2001) 3087-3093.

[14] S. Verma, H.M. Joshi, T. Jagadale, A. Chawla, R. Chandra, S. Ogale, Nearly Monodispersed

Multifunctional NiCo2O4 Spinel Nanoparticles: Magnetism, Infrared Transparency, and

Radiofrequency Absorption, J. Phys. Chem. C 112 (2008) 15106-15112.

[15] M. Cabo, E. Pellicer, E. Rossinyol, M. Estrader, A.L. Ortega, J. Nogues, O. Castell, S. Surinach,

M.D. Baro, Synthesis of compositionally graded nanocast NiO/NiCo 2O4/Co3O4 mesoporous

composites with tunable magnetic properties, J. Mater. Chem. 20 (2010) 7021-7028.

[16] J.F. Marco, J.R. Gancedo, M. Gracia, J.L. Gautier, E. Rios, F.J. Berry, Characterization of the

Nickel Cobaltite, NiCo2O4, Prepared by Several Methods: An XRD, XANES, EXAFS, and XPS

Study, J. Solid State Chem. 153 (2000) 74-81.

[17] P. Peshev, A. Toshev, G. Gyurov, Preparation of high-dispersity MCo2O4 (M = Mg, Ni, Zn)

spinels by thermal dissociation of coprecipitated oxalates, Mater. Res. Bull. 24 (1989) 33-40.

[18] D.P. Lapham, A.C.C. Tsenug, The effect of firing temperature, preparation technique and

composition on the electrical properties of the nickel cobalt oxide series Ni xCo1-xOy, J. Mater. Sci.

39 (2004) 251-264.

[19] P. Ravindranathan, G.V. Mahesh, K.C. Patil, Low-temperature preparation of fine-particle

cobaltites, J. Solid State Chem. 66 (1987) 20-25.

[20] L. Markov, K. Petrov, Nickel-cobalt oxide spinels prepared by thermal decomposition of

nickel(II)-cobalt(II) hydroxide nitrates, React. Solids 1 (1986) 319-327.

[21] L. Qian, L. Gu, L. Yang, H. Yuan, D. Xiao, Direct growth of NiCo2O4 nanostructures on

conductive substrates with enhanced electrocatalytic activity and stability for methanol oxidation,

Nanoscale 5 (2013) 7388-7396.

[22] M.U. Anu Prathap, B. Satpati, R. Srivastava, Facile preparation of β-Ni(OH)2-NiCo2O4 hybrid

nanostructure and its application in the electro-catalytic oxidation of methanol, Electrochim. Acta

130 (2014) 368-380.

[23] M. Yu, J.P. Chen, J.H. Liu, S.M. Li, Y. Ma, J. Zhang, J. An, Mesoporous NiCo2O4 nanoneedles

grown on 3D graphene-nickel foam for supercapacitor and methanol electro-oxidation, Electrochim.

Acta 151 (2015) 99-108.

9
[24] Z. Liu, K. Xiao, Q. Xu, N. Li, Y. Su, H. Wang, S. Chen, Fabrication of hierarchical flower-like

super-structures consisting of porous NiCo2O4 nanosheets and their electrochemical and magnetic

properties, RSC Adv., 3 (13) (2013) 4372-4380.

[25] J. Cheng, Y. Lu, K. Qiu, H. Yan, J. Xu, L. Han, X. Liu, J. Luo, J.-K. Kim, Y. Luo, Hierarchical

core/shell NiCo2O4@NiCo2O4 nanocactus arrays with dual-functionalities for high performance

supercapacitors and Li-ion batteries, Sci. Rep. 5 (2015) 12099.

[26] A.K. Das, R.K. Layek, N.H. Kim, D. Jung, J.H. Lee, Reduced graphene oxide (RGO)-supported

NiCo2O4 nanoparticles: an electrocatalyst for methanol oxidation Nanoscale, 6 (18) (2014) 10657-

10665.

[27] C.-W. Tang, C.-B. Wang, S.-H. Chien, Characterization of cobalt oxides studied by FT-IR, Raman,

TPR and TG-MS, Thermochim. Acta 473 (2008) 68-73.

[28] C.Z. Yuan, J.Y. Li, L.R. Hou, X.G. Zhang, L.F. Shen, X.W. Lou, Ultrathin Mesoporous NiCo 2O4

Nanosheets Supported on Ni Foam as Advanced Electrodes for Supercapacitors, Adv. Finct. Mater.

22 (2012) 4592-4597.

[29] G.Q. Zhang, X.W. Lou, General Solution Growth of Mesoporous NiCo2O4 Nanosheets on Various

Conductive Substrates as High-Performance Electrodes for Supercapacitors, Adv. Mater. 25 (2013)

976–979.

[30] U.B. Sontu, V. Yelasani, V.R.R. Musugu, Structural, electrical and magnetic characteristics of

nickel substituted cobalt ferrite nano particles, synthesized by self combustion method, J. Magn.

Magn. Mater. 374 (2015) 376-380.

[31] S. Rahmana, K. Nadeema, M. Anis-ur-Rehmanb, M. Mumtaza, S. Naeema, I. Letofsky-Papstc,

Structural and magnetic properties of ZnMg-ferrite nanoparticles prepared using the co-

precipitation method, Ceram. Int. 39 (2013) 5235-5239.

[32] Majid Niaz Akhtara, A. Rahman, A.B. Sulong, Muhammad Azhar Khan, Structural, spectral,

dielectric and magnetic properties of Ni0.5MgxZn0.5-xFe2O4 nanosized ferrites for microwave

absorption and high frequency applications, Ceram. Int. 43 (2017) 4357-4365.

[33] Y Z. Su, Q.Z. Xu, G.F. Chen, H. Cheng, N. Li, Z.Q. Liu, One dimensionally spinel NiCo 2O4

nanowire arrays: facile synthesis, water oxidation, and magnetic properties, Electrochimica. Acta 174

(2015) 1216-1224.

10
Figure Captions:

Fig.1. XRD patterns of the products obtained at 120°C, 160°C, and 200°C for 20 h.

Fig.2. Raman spectra of the NiCo2O4 nanostructures obtained at 120°C, 160°C, and 200°C for 20 h.

Fig.3. SEM images of the NiCo2O4 nanostructures synthesized at (a) and (b) 120°C, (c) and (d) 160°C,

(e) and (f) 200°C for 20 h.

Fig.4. TEM images of the NiCo2O4 nanostructures synthesized at (a) and (b) 120°C, (c) and (d) 160°C,

(e) and (f) 200°C for 20 h.

Fig.5. M-H curves of the NiCo2O4 nanostructures synthesized at 120°C, 160°C, and 200°C for 20 h.

Inset is the magnification of the curve to clearly show HC.

Table1. The parameters of Ms, B and Hc for the NiCo2O4 nanostructures synthesized at 120°C, 160°C,

and 200°C for 20 h.

Sample Ms (emu/g) nB (×10-3 B/f.u.) Hc (Oe)

120℃ 0.19 8.20 67.5

160℃ 0.54 23.30 -

200℃ 1.85 79.82 119.7

11
 Figures:

Intensity (a.u.)

(111)

20
(220)
(311)
(222)

40

12
(400)

Fig. 1
120oC

160oC

2Theta (deg.)
200oC
(422)
(511)

60
(440)

80
 A1g 120oC
F2g 160oC
F2g
E2g 200oC
Intensity (a.u.)

200 400 600 800 1000

13
Fig. 3

14
Fig. 4

15
 2 120oC
160oC
Magnetization (emu/g)

200oC

0
0.04
0.02
0.00
-0.02
-0.04
-2 -200-100 0 100 200
-10000 -5000 0 5000 10000
Magnetie field(Oe)

Fig. 5

16