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Acta Physico-Chimica Sinca  2016, Vol. 32 Issue (2): 543-550    DOI: 10.3866/PKU.WHXB201511194
ARTICLE     
Controllable Modulation of Morphology and Photocatalytic Performance of ZnO Nanomaterials via pH Adjustment
Hai-Feng HU1,2,Tao HE1,*()
1 CAS Key Laboratory of Nanosystem and Hierarchical Fabrication, National Center for Nanoscience and Technology, Beijing 100190, P. R. China
2 University of Chinese Academy of Sciences, Beijing 100049, P. R. China
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Abstract  

ZnO microstructures and nanostructures with controlled-morphology were synthesized by the hydrothermal method. All samples were prepared using precursors at different pH values and then annealed at 500 ℃ for 2 h. The samples were characterized by X-ray diffraction (XRD) patterns, scanning electron microscopy (SEM), transmission electron microscopy (TEM), ultraviolet-visible spectroscopy (UV-Vis), and BET specific surface area measurement. All samples were confirmed by XRD to be wurtzite ZnO. As the pH value of the precursor increased, sheet-like ZnO disappeared and rod-like ZnO was produced. The major surfaces of sheet-like and rod-like ZnO were polar and nonpolar crystal faces, respectively. At pH 6.5, Cl- was adsorbed onto the (002) polar face and inhibited the growth along the polar crystal face ({Zn2+}crystal surface). A microporous sheet ZnO was formed by annealing the obtained sheet-like Zn5(OH)8Cl2·H2O. When OH- was added into the precursor, Zn(OH)42- was generated via coordination with Zn2+, which was adsorbed onto the (002) polar face and promoted growth along the polar crystal face. Rod-like ZnO was thus produced. The obtained ZnO could photocatalytically reduce CO2 under illumination. Sheet-like ZnO exhibited better photocatalytic performance than rod-like ZnO. This may be because the polar crystal face shows better photocatalytic activity than the unpolar crystal face.



Key wordsZnO      pH value      Hydrothermal process      Morphology      Photoreduction of CO2     
Received: 14 October 2015      Published: 19 November 2015
MSC2000:  O649  
Fund:  the International Cooperation Department of Ministry of Science and Technology of China(2015DFG62610)
Corresponding Authors: Tao HE     E-mail: het@nanoctr.cn
Cite this article:

Hai-Feng HU,Tao HE. Controllable Modulation of Morphology and Photocatalytic Performance of ZnO Nanomaterials via pH Adjustment. Acta Physico-Chimica Sinca, 2016, 32(2): 543-550.

URL:

http://www.whxb.pku.edu.cn/10.3866/PKU.WHXB201511194     OR     http://www.whxb.pku.edu.cn/Y2016/V32/I2/543

Fig 1 X-ray diffraction patterns of the samples
Fig 2 SEM images of the samples
Fig 3 TEM and high resolution transmission electron microscopy (HRTEM) images of the samples
Fig 4 (a) UV-Vis and (b) optical bandgap spectra of ZnO powders with three morphologies
Fig 5 SEM images of hydrothermal product with initial pH 6.7
Fig 6 SEM images of hydrothermal products with initial pH 7.0
Fig 7 Schematic diagram of formation of ZnO morphology controlled by pH values
pH valueTurbidity of ZnO solutionPhotocatalytic product
deionized water4.0transparent solutionnone
acid base buffer solution7.5white suspensionCH4
Table 1 Comparison of photocatalytic reaction solution
Fig 8 CH4 yield (Y) of photocatalytic reduction CO2 over ZnO powders with three morphologies
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