Abstract
A simple and efficient two-step hybrid electrochemical–thermal route was developed for the synthesis of large quantity of ZnO nanoparticles using aqueous sodium bicarbonate electrolyte and sacrificial Zn anode and cathode in an undivided cell under galvanostatic mode at room temperature. The bath concentration and current density were varied from 30 to 120 mmol and 0.05 to 1.5 A/dm2. The electrochemically generated precursor was calcined for an hour at different range of temperature from 140 to 600 °C. The calcined samples were characterized by XRD, SEM/EDX, TEM, TG-DTA, FT-IR, and UV–Vis spectral methods. Rietveld refinement of X-ray data indicates that the calcined compound exhibits hexagonal (Wurtzite) structure with space group of P63mc (No. 186). The crystallite sizes were in the range of 22–75 nm based on Debye–Scherrer equation. The TEM results reveal that the particle sizes were in the order of 30–40 nm. The blue shift was noticed in UV–Vis absorption spectra, the band gaps were found to be 5.40–5.11 eV. Scanning electron micrographs suggest that all the samples were randomly oriented granular morphology.
Similar content being viewed by others
References
Andres PR, Bielefeld JD, Henderson JI, Janes DB, Kolagunta VR, Kubiak PC, Mahoney JW, Osifchin GR (1996) Self-assembly of a two-dimensional superlattice of molecularly linked metal clusters. Science 273:1690–1693
Bae SY, Seo HW, Park J (2004) Vertically aligned sulfur-doped ZnO nanowires synthesized via chemical vapor deposition. J Phy Chem B 108:5206–5210
Baolong Y, Guilan Z, Guoqing T, Xiaochun W, Wenju C (1995) Electronic spin resonance properties of ZnO nanocrystalline. Acta Phys Chim Sin 11(7):587–589; in Chinese
Berube LP, Esperance GL (1989) A quantitative method of determining the degree of texture of zinc electrodeposits. J Electrochem Soc 136:2314
Caijun X (2003) Nanocrystalline build material. Chemical Industrial Press, Beijing, pp 51–51
Chen BJ, Sun XW, Xu CX, Tay BK (2004) Growth and characterization of zinc oxide nano/micro-fibers by thermal chemical reactions and vapor transport deposition in air. Phys E 21:103–107
Deng HM, Ding J, Shi Y, Liu XY, Wang J (2001) Ultrafine Zinc oxide powders prepared by precipitation/mechanical milling. J Mater Sci 36:3273–3276
Faal Hamedani N, Farzaneh F (2006) Synthesis of ZnO nanocrystals with hexagonal (Wurtzite) structure in water using microwave irradiation. J Sci Islam Repub Iran 17(3):231–234
Gao-Qing Y, Huan-feng J, Chang L, Shi-Jun L (2007) Shape- and size-controlled electrochemical synthesis of cupric oxide nanocrystals. J Cryst Growth 303:400–406
Helen Annal Therese G, Kamath PV (2000) Electrochemical synthesis of metal oxides and hydroxides. Chem Mater 12(5):1195–1204
Hengxiang G, Yunyao H, Qifeng W, Guojuan J, Zebo F, Yinyue W (2004) Polycrystalline ZnO films deposited on glass by RF reactive sputtering. Semicond Photonics Technol 10(2):97–100
Ho Jung C, Cheng Zhu L, Yongsheng W, Chang-Sik S, Seong-Il K, Young-Hwan K, In-Hoon C (2004) Optical properties of ZnO nanocrystals synthesized by using sol–gel method. J Korean Phys Soc 45(4):959–962
Jiaqiang X, Qingyi P, Yuan S, Zhanchai L (1998) Emulsion synthesis microstructure and gas sensing properties of nanocrystalline ZnO ceramics. Chin J Inorg Chem 14(3):355–359; in Chinese
Joseph S, Kamath PV (2007) Electrodeposition of Cu2O coatings on stainless steel substrates-control over orientation and morphology. J Electrochem Soc 154(7):E102–E106
Kakiuchi K, Hosono E, Kimura T, Imai H, Fujihara S (2006) Fabrication of mesoporous ZnO nanosheets from precursor templates grown in aqueous solutions. J Sol–Gel Sci Technol 39:63–72
Kamath VP (2002) Photophysical, photochemical and photocatalytic aspects of metal nanoparticles. J Phys Chem B106:7729–7744
Li YJ, Duan R, Shi PB, Qin GG (2004) Synthesis of ZnO nanoparticles on Si substrates using a ZnS source. J Cryst Growth 260:309–315
Li YQ, Fu SY, Mai YW (2006) Preparation and characterization of transparent ZnO/epoxy nanocomposites with high-UV shielding efficiency. Polymer 47:2127–2132
Lian G, Wei L (2002) Nanocrystalline ceramics. Chemical Industrial Press, Beijing, pp 45–48
Liewhiran C, Phanichphant S (2006) Nano-sized ZnO particles coated on fly ash. J Microsc Soc Thailand 20(1):49–56
Liqiang J, Zili X, Jing S, Xiaojun S, Weimin C, Haichen G (2002) The preparation and characterization of ZnO ultrafine particles. Mater Sci Eng 332(7):356–362
Nakata Y, Okada T, Maeda M (2002) Deposition of ZnO film by pulsed laser deposition at room temperature. Appl Surf Sci 197:368–370
Perenboom JAAJ, Wyder P, Meier P (1981) Electronic properties of small metallic particles. Phys Rep 78:173–292
Prasad BE, Kamath PV, Sarala U (2008) Electrochemical synthesis of macroporous oxide coatings on stainless-steel substrates. J Amer Ceram Soc 91(12):3870–3874
Qingfeng L, Hongxiang W, Zhudong H (2004) ZnO nanoneedles fabricated by a simple approach and their optical properties. Trans Nonferrous Met Soc China 14(5):973–976
Rao CNR (1963) Chemical applications of infrared spectroscopy. Academic Press, New York
Rao KJ, Mahesh K, Kumar S (2005) A strategic approach for preparation of oxide nanomaterials. Bull Mater Sci 28(1):19–24
Sang B, Konagai M (1996) Growth of transparent conductive oxide ZnO films by atomic layer deposition. J Appl Phys 35:602–605
Scherrer P (1918) Nachr ges wiss Gottingen. Math Phys 2:98–100
Shiwen D, Shaoyan Z, Shujuan L, Yu D, Quanying K, Yanchao L (2002) Synthesis and photocatalyzing property of nano-ZnO. Chin J Inorg Chem 18(10):1015–1018; in Chinese
Sihai C, Xinmin R (1999) Mechanism study on the formation of ZnO nanoparticle in ethanol solution. Acta Phys Chim Sin 11(2):171–174; in Chinese
Srinivasan G, Kumar J (2006) Optical and structural characterisation of zinc oxide thin films prepared by sol-gel process. Cryst Res Technol 41(9):893–896
Stolt L, Hedstrom J, Kessler J, Ruckh M, Velthaus KO, Schock HW (1993) ZnO/CdS/CuInSe2 thin-film solar cells with improved performance. Appl Phys Lett 62:597–599
Thomas JM (1988) Colloidal metals: past, present and future. J Pure Appl Chem 60:1517–1528
Vafaee M, Ghamsari MS (2007) Preparation and characterization of ZnO nanoparticles by a novel sol–gel route. Mater Lett 61:3265–3268
Vayssieres L (2003) Growth of arrayed nanorods and nanowires of ZnO from aqueous solutions. Adv Mater 15:464–466
Wan Q, Yu K, Wang TH, Lin CL (2003) Low-field electron emission from tetrapod-like ZnO nanostructures synthesized by rapid evaporation. Appl Phys Lett 83(11):2253–2255
Wang ZL (2004) Nanostructures of zinc oxide. Mater Today 7:26–33
Wang JX, Sun XW, Wei A, Lei Y, Cai XP, Li CM, Dong ZL (2006) Zinc oxide nanocomb biosensor for glucose detection. Appl Phys Lett 88:233106(1–3)
Weizhong Y, Dali Z, Guangfu Y, Runsheng W, Yun Z (2005) Characterization of ZnO based varistor derived from nano ZnO powders and ultrafine dopants. J Mater Sci Technol 21(2):183–186
Wenliang W, Dongsheng L, Xiangyang H, Zhenmin S, Jiwu W, Caihua Z (2001) Ultrasonic radiation precipitation preparation and characterization on nanocrystalline zinc oxide. Chem Res Appl 13(2):157–159; in Chinese
Xianxi Z, Xiaojuan W, Guanjie Z, Jianzhuang J (2002) Nanocrystalline ZnO preparation through basic zinc carbonate calcinations. Chin J Inorg Chem 18(10):1038–1040; in Chinese
Xitang Z, Jiaqi Z, Jinjie X, Tengfeng X, Dejun W, Yubai B, Tiejin L, Jiannian Y (1999) Studies of surface photovoltage spectroscopy on quantum-sized ZnO nanoparticles. Chem J Chin Univ 20(12):1945–1947
Xu CX, Sun XW, Chen BJ, Sun CQ, Tay BK (2004) Nanostructural ZnO fabricated by vapor-phase transport in air. Int J Mod Phys B 18(2):225–232
Yan Z (2003) Nanocrystalline catalytic technology. Chemical Industrial Press, Beijing, p 68
Yifeng C, Motang T, Shenghai Y, Baoping Z, Jianguang Y (2004) Preparation of tetrapod-like ZnO whiskers from waste hot dipping zinc. J Cent South Univ Technol 11(1):51–54
Yongjun H (2004) Synthesis of ZnO nanoparticles with narrow size distribution under pulsed microwave heating. China Particuol 2(4):168–170
Yongning H, Xiaoliang S, Lidun M (1996) Synthesis and characterization of nanocrystalline-sized zinc oxide. Chin J Appl Chem 13(4):92–94; in Chinese
Yoo YZ, Jin ZW, Chikyow T, Fukumura T, Kawasaki M, Koinuma H (2002) S doping in ZnO film by supplying ZnS species with pulsed-laser-deposition method. Appl Phys Lett 81:3798
Zhaorigetu S, Yao H, Garidi (2006) Preparation and characterization of nanocrystalline ZnO by direct precipitation method. Front Chem China 3:277–280
Acknowledgments
The authors thank to Kuvempu University Karnataka, India for providing the lab facilities to bring about this work, and also Department of Science and Technology (DST), New Delhi, Government of India (GOI) for providing financial support by Major Research Project (No. S.R/S3/ME/014/2007).
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Chandrappa, K.G., Venkatesha, T.V., Vathsala, K. et al. A hybrid electrochemical–thermal method for the preparation of large ZnO nanoparticles. J Nanopart Res 12, 2667–2678 (2010). https://doi.org/10.1007/s11051-009-9846-0
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11051-009-9846-0