Facile synthesis and photocatalytic activity of cocoon-shaped CuO nanostructures

doi:10.1016/j.matlet.2015.05.014

Materials Letters

Volume 156, 1 October 2015, Pages 138-141

https://doi.org/10.1016/j.matlet.2015.05.014 Get rights and content

Highlights

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Facile growth of CuO nanococoons.
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Efficient utilization of CuO nanococoons for the photocatalytic degradation of Acridine Orange (AO).
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Effective degradation of AO when utilize CuO nanococoons.

Abstract

Well-crystalline cocoon-shaped CuO nanostructures were synthesized by simple solution process and used as an efficient heterogeneous photocatalyst for the degradation of harmful organic dye under UV light irradiations at room-temperature. The as-synthesized CuO nanococoons were characterized in detail using several techniques which revealed that the prepared nanostructures are well-crystalline, grown in very high density and possessing monoclinic crystal structure. Further, as a photocatalyst, the CuO nanococoons exhibited reasonable photocatalytic degradation toward harmful organic dye, i.e. acridine orange (AO). The kinetic study revealed that the photocatalytic degradation of AO using CuO nanococoons as photocatalyst follows a pseudo-first order kinetics.

Introduction

Among various metal oxide semiconductor nanomaterials, recently the CuO, a p-type semiconductor, has attracted a great attention due to its unique properties and wide applications [1], [2]. The properties of CuO include high thermal and photochemical stabilities, high-temperature superconductivity, electrochemical activity, non-toxicity, cost-effective fabrication and so on [3], [4]. CuO, with a narrowband gap (1.2–1.5 eV) and other properties, has been extensively used in lithium ion batteries [5], gas-sensors [6], biosensors [7], magnetic-storage devices [8], solar-cells [9], heterogeneous photocatalysis [10], etc. Because of excellent properties and wide applications, variety of CuO nanomaterials including nanourchins, nanorods, nanofibers, nanosheets, nanoleaves, microspheres, etc. have been synthesized by number of synthetic techniques and reported in the literature [1], [2], [3], [4], [5], [6], [7], [8], [9], [10]. Recently, several CuO nanomaterials were used as heterogeneous photocatalyst for the photocatalytic degradation of organic dyes and chemicals as it is believed that for reasonable photocatalytic efficiencies, the semiconductor material must possess high surface area andporosity and lower band-gap for better dye adsorption and easy formation of electron–hole pair recombinants (excitons), respectively. Thus, the use of CuO with smaller band gap can ease the formation of excitons through a rapid recombination of free electrons of the empty conduction band with the positive holes of the valence band. Bathochromic shift thus induced enhances the photocatalytic activities. Electron–hole pair recombination helps the involvement of photo-generated electrons to participate in redox reaction on the surface of the semiconductor nanomaterials generating OH free radicals responsible for dye degradation [11]. Sonia et al. [2] observed the photo-degradation of methylene blue and methylene violet dyes under UV-light illumination using CuO nanoleaves. Mageshwari et al. [10] synthesized flower-shaped hierarchical CuO microspheres and evaluated their photocatalytic activities for the degradation of methyl orange and methylene blue dyes under UV light illumination. Tamuly et al. [12] studied the photocatalytic activities of bio-derived CuO nanoparticles for the degradation of methyl red dye. In addition to CuO, cuprous oxide (Cu₂O) nanostructures have also been utilized as photocatalyst for the degradation of a number of harmful dyes and reported in the literature [13], [14]. The morphology of the nanomaterials is one of the key factors for the better photocatalytic activities as morphology directly affects the surface volume ratio. In order to have morphologies with high surface/volume ratio many synthetic processes are reported. Among these various synthetic processes, low temperature synthesis of metal oxide nanomaterials is considered as easy and fast synthesis process. [15], [16].

This paper reports a facile, high yield, low-temperature synthesis and detailed characterizations of CuO nanococoons and their utilization as an efficient photocatalyst for the photocatalytic degradation of a very harmful and widely used acridine orange (AO) dye. Interestingly, a significant photocatalytic degradation of AO was observed when CuO nanococoons were used as photocatalyst.

Section snippets

Experimental details

Well-crystalline CuO nanococoons were synthesized by simple aqueous solution process using cupric chloride (CuCl₂·2H₂O), ethylenediamine (C₂H₈N₂) (structure-directing agents) and ammonium hydroxide (NH₄OH) (to maintain the proper pH of the growth solution) at low-temperature of 75±5 °C. In a typical reaction process, 0.01M CuCl₂·2H₂O and 0.001M C₂H₈N₂, made in 50 ml deionized (DI) water, were mixed under stirring at room-temperature. The pH=12 was adjusted for the solution by adding few drops of

Results and discussions

To examine the general morphologies, the prepared CuO powder was examined by field emission scanning electron microscopy (FESEM) and shown in Fig. 1. The observed FESEM images confirmed that the prepared CuO possess cocoons-shaped morphologies which are grown in very high density (Fig. 1(a)). The nanococoons are somewhat possessing spindle-like morphologies in which the central part is wide while the corners are narrow. The typical diameters of the nanococoons at the centre and corners are ~70±5

Conclusion

Well-crystalline CuO nanococoons were synthesized by low-temperature solution process and used as effective photocatalytic for the photocatalytic degradation of AO, a harmful aromatic dye. The detailed characterizations revealed that the prepared CuO nanococoons are well-crystalline and possessing monoclinic crystal structure. Because of the unique morphology and well-crystallinity which might import the effective electron/hole separation and might generate the large number of oxy radicals, the

Acknowledgments

This project was funded by the Deanship of Scientific Research (DSR), Najran University, Najran, under grant no. NU/ESCI/14/22. The author, therefore, greatly acknowledge with thanks DSR, Najran University for technical and financial support.

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Facile synthesis and photocatalytic activity of cocoon-shaped CuO nanostructures

Highlights

Abstract

Introduction

Section snippets

Experimental details

Results and discussions

Conclusion

Acknowledgments

Physica E

Sci Adv Mater

Powder Technol.

J Nanosci Nanotechnol

J Phys Chem C

CrystEngComm

J Mater Chem A

Cryst Res Technol

Mater Res Bull

Opt Mater Express

J. Alloy Compd