Microwave fabrication of Cu2ZnSnS4 nanoparticle and its visible light photocatalytic properties
- Zhihua Zhou†1,
- Pingan Zhang†1,
- Yuelai Lin1,
- Eric Ashalley1,
- Haining Ji1,
- Jiang Wu1,
- Handong Li1 and
- Zhiming Wang1Email author
© Zhou et al.; licensee Springer. 2014
Received: 22 August 2014
Accepted: 2 September 2014
Published: 9 September 2014
Cu2ZnSnS4 nanoparticle with an average diameter of approximately 31 nm has been successfully synthesized by a time effective microwave fabrication method. The crystal structure, surface morphology, and microstructure of the Cu2ZnSnS4 nanoparticle were characterized. Moreover, the visible light photocatalytic ability of the Cu2ZnSnS4 nanoparticle toward degradation of methylene blue (MB) was also studied. About 30% of MB was degraded after 240 min irradiation when employing Cu2ZnSnS4 nanoparticle as a photocatalyst. However, almost all MB was decomposed after 90 min irradiation when introducing a small amount of H2O2 as a co-photocatalyst. The enhancement of the photocatalytic performance was attributed to the synergetic effect between the Cu2ZnSnS4 nanoparticle and H2O2. The detailed photocatalytic degradation mechanism of MB by the Cu2ZnSnS4 was further proposed.
Organic dyes widely used in textile and plastic industries are one of the chief sources of contaminants in wastewater. They have induced serious environmental problems due to their potential toxicity to living organisms. Degradation and total removal of such contaminants are keys to ensuring a protected environment. A photocatalytic technique is considered to be a promising method for treating organic dyes in wastewater . However, an obvious challenge for degradation of organic dyes is that most photocatalysts, such as TiO2 or BiVO4[2, 3], are only effective in the UV range. To broaden their light absorption range, various methods including dye sensitizing , metal doping  non-metal doping [6, 7], and noble metal decorating  have been developed. However, stable and efficient dyes are rare and expensive. Moreover, dopant impurity atoms in photocatalysts often serve as recombination centers for photogenerated holes and electrons . To avoid these problems, great efforts have also been put into the development of alternative undoped photocatalysts which work under visible light irradiation. Until now, many materials with attractive visible light photocatalytic performance, such as Bi2TiO4F2, Bi2O3, AgNbO3, and graphene oxide enwrapped Ag/AgX (X = Br, Cl) nanocomposite  have been investigated. However, the supply of rare elements of Ag, Bi, and Nb is a critical issue for widespread use. Thus, it is crucial to investigate alternative cost-effective visible-light-driven photocatalysts.
Cu2ZnSnS4 is a direct bandgap p-type semiconductor with a high optical absorption coefficient of about 105 cm−1[14, 15]. Its elements are environmentally friendly and abundant in the earth's crust. As its bandgap is around 1.5 eV, it can absorb most of the visible light. It has been reported that Cu2ZnSnS4 possesses high photocorrosion resistance in air and aqueous solution . Both of these superior properties of Cu2ZnSnS4 enrich its potential use in solar-energy-related applications.
In this work, we have fabricated the Cu2ZnSnS4 nanoparticle by a facile microwave fabrication method. The advantages of this method are the following: it is economical of time and cost effective. The crystal structure and surface morphology of the prepared Cu2ZnSnS4 nanoparticle were characterized. Moreover, the photocatalytic performance of the Cu2ZnSnS4 nanoparticle toward the degradation of methylene blue (MB) under visible light irradiation was also investigated. The Cu2ZnSnS4 nanoparticle showed noteworthy visible light photocatalytic ability.
The Cu2ZnSnS4 nanoparticle was synthesized by a facile microwave fabrication method. Cu(CH3COO)2 · H2O, Zn(CH3COO)2, Sn(CH3COO)2, and thiocarbamide with a molar ratio of 2:1:1:4 were employed as source materials. All the reagents were analytically pure and bought from Sinopharm Chemical Reagent Co., Ltd, Shanghai, China. Typically, 1.123 g of the source materials was dissolved in 20 mL ethylene glycol solution as precursor. Then the precursor was stirred gently and heated in a microwave reactor (MCR-3, Gongyi City Yuhua Instrument Co., Ltd, Gongyi City, China) at 180°C for 10 min. After the vacuum filtration and drying process, the Cu2ZnSnS4 nanoparticle sample was obtained.
The crystal structure of the Cu2ZnSnS4 nanoparticle was investigated by X-ray diffraction (XRD; D/max-2200/PC, Rigaku, Tokyo, Japan) and Raman spectroscopy (Senterra, Bruker, Billerica, USA). The surface morphology and microstructure of the Cu2ZnSnS4 were measured by scanning electron microscopy (SEM; JSM 5800LV, JEOL, Tokyo, Japan) and transmission electron microscopy (TEM; JEM-2100, JEOL, Tokyo, Japan).
The photocatalytic properties of the prepared Cu2ZnSnS4 nanoparticle were investigated by employing MB as a model dye. The Cu2ZnSnS4 nanoparticle (20 mg) was dispersed in 100 mL of MB aqueous solution (10 mg/L). Prior to irradiation, the MB solution over the catalyst was gently stirred in the dark for 30 min to reach equilibrium adsorption state. Then the solution was illuminated with a 100-W xenon light source (Shanghai Yaming Lighting Co., Ltd., Shanghai, China). The concentration change of MB was monitored by measuring UV-vis absorption of the extracted MB solution at regular intervals. The characteristic peak absorbance of MB at 665 nm was used to determine its concentration. In addition, the photocatalytic properties of the Cu2ZnSnS4 nanoparticle with the assistance of 0.1 mL H2O2 (30% aqueous solution) were further investigated in the same measurement process. For comparison, a control experiment without adding Cu2ZnSnS4 and H2O2 was also carried out.
Results and discussion
In summary, the Cu2ZnSnS4 nanoparticle was successfully synthesized by a facile microwave fabrication method. The prepared Cu2ZnSnS4 nanoparticle exhibited a polycrystalline structure with an average diameter of approximately 31 nm. The photocatalytic performance of the Cu2ZnSnS4 nanoparticle toward degradation of MB in aqueous solution was also investigated. Due to the top of the valence band of Cu2ZnSnS4, pure Cu2ZnSnS4 nanoparticle showed a poor visible light photocatalytic ability. However, when employing a small amount of H2O2 as electron scavenger, the photocatalytic performance was greatly enhanced. The first-order reaction rate constant k 1 toward the degradation MB reached as high as 0.04 min−1. The synergetic effect between the Cu2ZnSnS4 nanoparticle and H2O2 was a key to promote the photodegradation efficiency.
This work was supported by the Fundamental Research Funds for the Central Universities 2672012ZYGX2012J042, the 973 Program (2013CB933800), and the National Natural Science Foundation of China (51272038).
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