1.

Introduction

Recently, the semiconductor nanomaterials have attracted a wide attention because of their

exotic optical, electrical, electronic, photocatalytic, mechanical, thermal, etc properties [1] and

variety of high-technological applications. Among various semiconductor nanomaterials, the II-

VI semiconductor ZnO possesses a special place due to its several interesting properties and

broad applications. Some of the interesting properties of ZnO are its wide band gap (3.37 eV),

large exciton binding energy (60 meV), high optical gain at room temperature, large saturation

velocity, non-toxicity, biocompatibility, piezoelectricity and pyroelectricity, easy and low-cost

synthesis, etc [2-14]. Because of these excellent properties, ZnO nanomaterials are widely used

for several applications, to name a few, solar cells, chemical and biosensors, ultraviolet (UV)

lasers, light emitting diodes (LEDs), photo-detectors, piezoelectric transducers and actuators,

hydrogen storage, photo catalysts and so on [1-8].

Doping of ZnO nanomaterials to certain extent considerably increases the surface defects

which can presumably shift the absorption towards visible region. The enhancement in optical

absorption in surface defects by doping has been studied by several research groups using

different transition metals such as Ni [15, 16], Cu [17], Co [18], Mn [19], Mo [20], V and W

[21], Fe [22], etc and representative elements such as Na, K, Li, N and B, etc [23-25]. These

dopants are usually introduced into ZnO matrix, occupying substitution or interstitial sites. In

addition to these elemental dopants, some works have also been done to dope rare earth metals

(Er, Yb, La, Nd and Ce) into the interstitial sites of ZnO crystals [26-29]. The rare-earth metal

doped semiconducting nanomaterials have shown wide range of applications in lasers,

amplifiers, thin film electroluminescent devices and optoelectronic/cathodoluminescent devices

[26-29]. It is believed that the rare earth ion doping can produce traps for photogenerated charge

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carrier and decrease the electron–hole pair recombination rate [30]. Thus, several methods such

as hydrothermal, spray pyrolysis, radio frequency sputtering, sol–gel, chemical spray, thermal

evaporation etc, were employed to prepare lanthanide doped ZnO nanomaterials and reported in

the literature [31-37]. However, most of the reported methods are time consuming and need

complicated equipments, expensive chemicals and operate only under particular and controlled

reactions conditions such as pH, growth time, concentrations, etc. Thus, it is still needed to

develop a convenient and cost effective method to synthesize well-crystalline lanthanide doped

ZnO nanomaterials.

Among various lanthanides, cerium (Ce) has been received much attentions as promising

dopant for metal oxide semiconducting materials due to several unique properties and

applications [35-39]. Recently, Lamba et al. [35] synthesized well-crystalline CeO2-ZnO

hexagonal nanodisks through simple and facile chemical process and utilized for photocatalytic

degradation of hazardous direct blue (DB)-15 dye under solar light irradiation. Chang et al. [36]

reported the effective photo-degradation of direct blue 86 (DB-86), food black-2 (FB-2) and

methyl orange (MO) dyes using Ce-doped ZnO photocatalyst under UV and visible light

irradiation. Dar et al. [37] synthesized Ce-doped ZnO nanorods by hydrothermal method and

used as electrode materials for hydroquinone chemical sensor. Chang et al. [38] also prepared

Ce-doped ZnO nanorods through solution method on Pt spiral electrodes for the detection of NO2

gas at low temperature. Very recently, Li et al. have demonstrated the growth of pure and Ce-

doped ZnO follow nanofibres and used those nanostructures for the fabrication of gas sensors

[39].

This paper reports a very simple, unique and rapid synthesis method to prepare Ce-doped

ZnO nanoparticles via solution combustion process. The advantage of solution combustion

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process is that, this synthesis process is rapid, facile, and simple. Moreover, the prepared

products are well-crystalline and possessing good structural and optical properties. The prepared

Ce-doped ZnO nanoparticles were characterized by several techniques and finally used as

efficient photocatalyst for photocatalytic degradation of harmful organic dye, i.e. Direct Red-23

dye.

2. Experimental details

2.1. Synthesis of Ce-doped ZnO nanoparticles

The synthesis of Ce-doped ZnO nanoparticles were carried out by facile solution

combustion method modified from the earlier reported ones [10, 11]. All the chemicals used in

the synthesis were purchased from CDH, India and used as received without further purification.

De-ionized (DI) water was used as solvent in all synthesis process. In a typical synthesis process,

0.02 M zinc nitrate hexahydrate was mixed well with 0.02 M dextrose, both dissolved in 10 ml

DI water, each, under continuous stirring at room-temperature. During stirring, specific amount

of cerric ammonium nitrate, depending upon the dopant concentrations, was added in the

resultant solution and stirring was continued for 30 min. After stirring, the resultant solution was

filtered and obtained filtrate was transferred to a china dish which was thereafter placed in a

preheated muffle furnace at 400°C. After 5- 8 min contents ignite results the formation of highly

spongy material which was crushed and annealed further at 600°C for 30 min. The doped ZnO

samples with 0.5%, 1.39%, 2.55%, 3.28%, 3.71% and 4.14 % Ce were named as CZ-1, CZ-2,

CZ-3, CZ-4, CZ-5, CZ-6, respectively. The samples obtained were then characterized in detail in

terms of their morphological, structural, compositional, optical and photocatalytic properties

using various analytical techniques.

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