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Materials Letters 65 (2011) 1871–1874

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Materials Letters
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / m a t l e t

Repeatable synthesis of Cu2O nanorods by a simple and novel reduction route


Zhipeng Cheng, Jiming Xu ⁎, Hui Zhong, XiaoZhong Chu, Juan Song
Jiangsu Key Laboratory for Chemistry of Low-Dimensional Materials, Huaiyin Normal University, Huaian 223300, China

a r t i c l e i n f o a b s t r a c t

Article history: Cu2O nanorods were synthesized by reducing bamboo leaf-shaped Cu(OH)2 with sodium hypophosphite
Received 15 February 2011 (NaH2PO2) in an H2O/ethylene glycol (EG) mixing solution. The Cu(OH)2 was prepared by adding an alkaline
Accepted 24 March 2011 solution to an aqueous solution containing CuSO4 and NaH2PO2 at room temperature. The optimum
Available online 31 March 2011
temperature range for the reduction of the Cu(OH)2 to Cu2O nanorods was 55–70 °C. The products were
characterized by X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, and
Keywords:
Nanoparticles
high-resolution transmission electron microscopy. The result showed the prepared Cu2O nanorods were
X-ray techniques uniform and had diameters of 10–20 nm and lengths of 150–200 nm. The synthesis is simple, inexpensive,
Cu2O nanorods and highly repeatable.
Cu(OH)2 © 2011 Elsevier B.V. All rights reserved.

1. Introduction 2. Experimental procedure

Over the past few years, controlling the size and shape of metal All reagents were of analytical grade purity and used directly
oxides has attracted significant interest because the shape and size of without further purification. In the typical synthetic process, copper
these materials have significant influence on their chemical and sulfate pentahydrate (0.125 g) and sodium hypophosphite (0.12 g)
physical properties [1–5]. Among the numerous metal oxides were dissolved in 10 mL water. The solution was stirred with a magnetic
available, Cu2O, a p-type semiconductor with unique optical and stirrer for 10 min to ensure that the CuSO4 and NaH2PO2 completely
magnetic properties, has received much attention for its potential dissolved. Under constant stirring, 10 mL of 0.15 M NaOH was added to
applications in gas sensing [6], CO oxidation [7], photocatalysis [8], the CuSO4 and NaH2PO2 solution at room temperature. A blue Cu(OH)2
photochemical evolution of H2 from water [9], photocurrent gener- precipitate was soon produced. After stirring for 15 min, 20 mL ethylene
ation [10], and organic synthesis [11]. Therefore, it is important to glycol (EG) was poured into the Cu(OH)2 suspension. Subsequently, the
synthesize Cu2O with special nanostructures, which may widen its suspension was heated to 65 °C for 3 h without stirring. Finally, Cu2O
application in various fields. nanorods were obtained, followed by centrifugal separation, washing
To date, a variety of chemical methods has been developed for the with absolute alcohol and drying in vacuum at 40 °C for 6 h.
controlled synthesis of several interesting Cu2O nanostructures, The product was characterized by powder X-ray diffraction (XRD)
including particles [12], clusters [13], cubes [14], hollow spheres [15], using a Bruker D8 Advanced X-ray diffractometer with Cu Kα radiation.
flowers [16], cages [17], octahedra [18], and bi-pyramids [19]. Recently, Transmission electron microscopy (TEM) was performed on a Philips
several reports were published on synthesis of one-dimensional (1D) Tecnai 12 transmission electron microscope. X-ray photoelectron
Cu2O nanostructures, such as wires [20,21], tubes [22], and whiskers spectroscopy (XPS) pattern was recorded on an Escalab MkII X-ray
[23,24], due to their special structures, large surface areas, and unique photoelectron spectrometer using Mg Kα X-ray as the excitation source.
properties. Most methods for the synthesis of 1D Cu2O demand tedious
procedures, high temperatures, and special conditions. 3. Results and discussion
We report a simple and novel wet chemical approach for the
synthesis of Cu2O nanorods obtained by reducing bamboo leaf-shaped The Cu2O nanorods were produced by the following reactions:
Cu(OH)2 precursors with sodium hypophosphite as a reducing agent
in an H2O/EG mixing solution at 65 °C. The synthesis is simple, 2þ −
Cu þ 2OH →CuðOHÞ2 ð1Þ
inexpensive, and highly repeatable.
− −
2CuðOHÞ2 þ H2 PO2 →Cu2 O þ H2 PO3 þ 2H2 O ð2Þ

In the experiment, NaH2PO2 was used as the reducing agent. The


⁎ Corresponding author. Tel./fax: +86 0517 83525085. reducing ability of sodium hypophosphite is closely related to
E-mail address: xujm68@126.com (J. Xu). temperature. The reducing ability of NaH2PO2 increases at higher

0167-577X/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2011.03.094
1872 Z. Cheng et al. / Materials Letters 65 (2011) 1871–1874

Fig. 1. (a) XRD pattern and (b) TEM image of the prepared Cu(OH)2 precursor.

Fig. 2. (a) XRD pattern and (b)XPS spectrum of the product prepared at 65 °C. (c)–(f) TEM images of Cu2O nanorods at different magnifications.
Z. Cheng et al. / Materials Letters 65 (2011) 1871–1874 1873

Fig. 3. (a) XRD pattern and (b) TEM image of the product prepared at 50 °C.

temperatures [25]. Copper can be produced by the complete reduction 20 nm and lengths of 150–200 nm. The images demonstrate the high
of Cu(OH)2 at higher temperature, as shown in Eq. (3): yield of Cu2O nanorods obtained from the synthesis. The high-
− −
resolution TEM image of the Cu2O nanorods (Fig. 2f) exhibits the
CuðOHÞ2 þ 2H2 PO2 →Cu þ 2H2 PO3 þ H2 ð3Þ lattice fringes, which suggest that the Cu2O nanorods are composed of
To avoid the formation of Cu, the reaction must be carried out at interconnected 3–5 nm crystallites. This observation agrees with the
sufficiently low temperature. structure calculated from the XRD pattern.
In the present study, EG was used as the co-solvent. It can Comparative experiments were done to investigate the influence of
coordinate with free copper (II) ions to form a chain-like intermediate temperature while other experimental conditions were unchanged.
and direct the formation of Cu2O nanorods [21]. Moreover, oxygen When the reaction temperature was reduced to 50 °C, rod-like Cu2O
atoms in EG can easily form hydrogen bonds, which can also align the mixed with bamboo leaf-shaped Cu(OH)2 was obtained (Fig. 3a and b).
growth of the Cu2O nanocrystallites along one direction [26]. This indicates that the Cu(OH)2 could not be thoroughly reduced to
Fig. 1 shows the XRD pattern and TEM image of the Cu(OH)2 Cu2O. When the temperature was raised to 80 °C, pure copper instead
precursor. The diffraction peaks (Fig. 1a) could be indexed to the of Cu2O was observed, as shown in the XRD pattern (Fig. 4a). Copper
orthorhombic Cu(OH)2 phase (JCPDS 13-0420). The Cu(OH)2 precur- was also formed by the in situ reduction of Cu(OH)2, possibly due to
sor had a dominant bamboo leaf-shaped morphology with an average the high rate of the reduction (Fig. 4b). Repeated experiments confirm
length of 300 nm and width of 100 nm (Fig. 1b). that pure Cu2O nanorods could be synthesized within 55–70 °C.
Fig. 2a shows the XRD pattern of the Cu2O nanorods synthesized at
65 °C. The diffraction peaks of this product could be indexed to the 4. Conclusion
cubic Cu2O phase (JCPDS 05-0667). No impurity peaks were observed.
Broadening of the peaks indicates the small crystal size of the In summary, Cu2O nanorods were synthesized using Cu(OH)2
products. Fig. 2b presents the photoelectron spectrum of the Cu 2p precursors via a simple wet chemical method with good repeatability.
core level for the Cu2O nanorods. After correction for the C1s reference To obtain pure Cu2O rather than Cu(OH)2 or Cu, the temperature
(284.6 eV), two peaks assigned to the 2p1/2 and 2p3/2 energy level range for Cu(OH)2 reduction should be controlled to 55–70 °C.
were found at 952.70 and 932.84 eV, respectively. The two peaks Detailed characterizations revealed that the synthesized Cu2O
correspond to Cu2O, as previously reported [27]. The morphologies of nanorods were uniform and had diameters of 10–20 nm and lengths
the Cu2O nanorods at different magnifications are shown in Fig. 2c–f. of 150–200 nm. This material has potential applications in various
The prepared Cu2O nanorods were uniform and had diameters of 10– areas, such as catalysis, absorption, and gas sensing.

Fig. 4. (a) XRD pattern and (b) TEM image of the product prepared at 80 °C.
1874 Z. Cheng et al. / Materials Letters 65 (2011) 1871–1874

Acknowledgments [9] Hara M, Kondo T, Komoda M, Ikeda S, Shinohara K, Tanaka A, et al. Chem Commun
1998;3:357–8.
[10] McShane CM, Choi KS. J Am Chem Soc 2009;131:2561–9.
The authors are grateful for the financial supports of the Natural [11] Kim JY, Park JC, Kim A, Kim AY, Lee HJ, Song H, et al. Eur J Inorg Chem 2009;28:
Science Foundation of Jiangsu Education Committee (10KJB430003), 4219–23.
[12] Zhang JT, Liu JF, Peng Q, Wang X, Li YD. Chem Mater 2006;18:867–71.
Technological Research Foundation of Huai'an City (HAG2010073), [13] Zahmakiran M, Özkar S. Mater Lett 2009;63:1033–6.
the National Natural Science Foundation of China (20975043), and [14] Zahmakiran M, Özkar S, Kodaira T, Shiomi T. Mater Lett 2009;63:400–2.
Jiangsu Higher Institutions Key Basic Research Projects of Natural [15] Zhu HT, Wang JX, Xu GY. Cryst Growth Des 2009;9:633–8.
[16] Liang ZH, Zhu YJ. Mater Lett 2005;59:2423–5.
Science (07KJA15012). [17] Kuo CH, Huang MH. J Am Chem Soc 2008;130:12815–20.
[18] Jing SY, Xing SX, Wu Y, Wang YF, Zhao B, Zhao C. Mater Lett 2007;61:2281–3.
[19] Jimenez-Cadana G, Comina E, Ferroni M, Sberveglieri G. Mater Lett 2010;64:469–71.
References [20] Wang WZ, Oomman KV, Ruan C, Paulose M, Grimes CA. J Mater Res 2003;18:
2756–9.
[1] Hakim SH, Shanks BH. Chem Mater 2009;21:2027–38. [21] Liu XY, Xiong SL, Liu YK, Chai LL, Bao KY, Qian YT. Mater Chem Phys 2009;114:
[2] Polshettiwar V, Baruwati B, Varma RS. ACS Nano 2009;3:728–36. 213–6.
[3] Park J, Kim J, Kwon H, Song H. Adv Mater 2009;21:803–7. [22] Xu J, Tang YB, Zhang WX, Lee CS, Yang ZH, Lee ST. Cryst Growth Des 2009;9:
[4] Dinh CT, Nguyen TD, Kleitz F, Do TO. ACS Nano 2009;3:3737–43. 4524–8.
[5] Fan HM, You GJ, Li Y, Zheng Z, Tan HR, Shen ZX, et al. J Phys Chem C 2009;113: [23] Qu YL, Li XY, Chen GH, Zhang HJ, Chen YY. Mater Lett 2008;62:886–8.
9928–35. [24] Yu Y, Du FP, Yu JC, Zhuang YY, Wong PK. J Solid State Chem 2004;177:4640–7.
[6] Liu J, Wang SZ, Wang Q, Gung BY. Sens Actuators B Chem 2009;143:253–60. [25] Qu SM, Huang XT, Cai GY. Adv Mater Res 2011;179–180:334–8.
[7] White B, Yin M, Hall A, Le D, Stolbov S, Rahman T, et al. Nano Lett 2006;6:2095–8. [26] Zhu JW, Wang YP, Wang X, Yang XJ, Lu LD. Powder Tech 2008;181:249–54.
[8] Ho JY, Huang MH. J Phys Chem C 2009;113:14159–64. [27] Yang M, Zhu JJ. J Crystal Growth 2003;256:134–8.

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