One-Pot Synthesis of Cu2ZnSnSe4 Nanoplates and their Visible-Light-Driven Photocatalytic Activity
© The Author(s) 2018
Received: 6 October 2017
Accepted: 28 December 2017
Published: 10 January 2018
A SeO2 ethanol solution as the facile precursor has been used for the preparation of quaternary Cu2ZnSnSe4 (CZTSe) nanoplates. Monodispersed single-phase CZTSe nanoplates have been prepared successfully by a facile one-pot thermal chemical method. The as-prepared CZTSe nanoplates show uniform morphology with a bandgap of ~ 1.4 eV. As a proof of concept, the CZTSe nanoplates have been used as a visible-light-driven photocatalyst for Rhodamine B dye degradation and show high photocatalytic activity and stability. The excellent dye removal is mainly ascribed to the efficient light utilization of CZTSe nanoplates.
Chemical pollutants in natural water have aroused extensive attention due to its serious damage to the environment, and photocatalytic degradation technique based on semiconductors by employing solar energy has been considered as a promising solution to this problem . However, typical photocatalysts, such as TiO2 and ZnO, can only absorb ultraviolet (UV) light. In fact, about 50% solar energy is mainly concentrated in the visible light region while UV light accounts for less than 4% of the solar spectrum . To utilize visible light and improve the photocatalytic activity, various efficient photocatalysts have been explored and applied in organic pigment degradation, water splitting, and solar cell absorbers . Among several photocatalysts, copper-based ternary and quaternary chalcogenide semiconductors, such as Cu2SnS3, CuInxGa1-xSe2, and Cu2ZnSnS4, have been of broad interest owing to their outstanding optoelectronic properties with large absorption coefficient (> 104 cm−1), good stability, and suitable bandgap energy (1.0–1.5 eV) [4–9].
Cu2ZnSnSe4 (CZTSe) nanocrystals and thin films with inexpensive, non-toxic, and earth-abundant constituent elements have been investigated extensively in recent years [8, 10–15]; however, there are a few reports related to the study of nanoplate morphology [16, 17]. Hot-injection and one-pot thermal chemical method are usually applied to the synthesis the CZTSe nanostructures [18–21]. However, the Se precursors used in these methods are expensive, toxic, or unstable. Herein, a facile Se precursor which dissolves SeO2 powder in ethanol is developed in this study.
Here, we report a one-pot thermal chemical method of CZTSe nanoplate synthesis using a facile Se precursor. The visible-light-driven photocatalytic activity and recycle performance of CZTSe nanoplates were investigated. The CZTSe nanoplates have potential in wastewater treatment.
Synthesis of CZTSe Nanoplates
All chemicals used in this work were purchased from Aladdin and used directly. Typically, 1.0 mmol Cu(acac)2, 0.5 mmol Zn(OAc)2·2H2O, 0.5 mmol SnCl2·2H2O, and 2.0 mmol SeO2 dissolved in 4 mL ethanol were added into 20 mL oleylamine (OLA) in a 100-mL three-neck flask. The mixture was degassed at 130 °C for 1 h, purged with Ar for 30 min, and then heated to 280 °C for 1 h. The nanoplates were washed with hexane and ethanol three times by centrifugation at 8000 rpm for 5 min. The black powder was collected and dried at 60 °C under vacuum. Before photocatalytic reaction, the nanoplates were hydrophilic treated with Na2S to remove the long-chain OLA ligands .
Powder X-ray diffraction (XRD, D/max 2200, Rigaku, Japan) using Cu Kα radiation (40 kV, 100 mA) and a Raman spectrometer (Inviareflex, Renishaw, UK) coupled with a 514 nm laser were applied to analyze the phase of the samples. Transmission electron microscopy (TEM, JEM-2100F, JEOL., Japan) and scanning electron microscopy (SEM, Quatan 250FEG, FEI, USA) measurements were performed to characterize the morphologies of the samples. The UV-vis absorption spectra of CZTSe nanoplate powder and Rhodamine B (RhB) aqueous solution were recorded on a UV/vis spectrometer by using the integrating sphere and cuvette, respectively (Lambda, Perkin Elmer, USA).
Photocatalytic Activity Measurements
Visible-light-driven photocatalytic activity of the CZTSe nanoplates was evaluated by photodegradation of the RhB aqueous solution (10 mg/L) at ambient temperature. A 300-W Xe lamp equipped with a 420 nm cutoff filter was used as a visible light source. Typically, 50 mg photocatalyst was added into 100 mL of RhB aqueous solution. The solution was continuously stirred in the dark for 12 h to ensure the adsorption-desorption equilibrium before irradiation. The concentration of the residual RhB was monitored at a sequence of time intervals by the UV-vis spectrometer at 554 nm to calculate the degradation rate based on the Beer-Lambert Law.
Results and Discussion
A SeO2 ethanol solution as the facile precursor has been used for the preparation of quaternary CZTSe nanoplates. Monodisperse CZTSe nanoplates have been prepared successfully by a facile one-pot thermal chemical method. As a proof of concept, the CZTSe nanoplates have been used as visible light response photocatalyst for RhB dye degradation. The efficient dye removal is mainly ascribed to the efficient light utilization of CZTSe nanoplates.
This work was supported by a grant from the Ministry of Education Innovation Team Development Program of China (No. IRT16R57, YL), a grant from the Shaanxi province science and technology resource integrated program (No. 2016TZC-G-5-6, RW), and a research fund for Young Talent Recruiting Plans of Xi’an Jiaotong University (No. YX1J007, RW).
ZZH carried out the experiments and drafted the manuscript. RQW and ZZH participated in the design of the study and performed the analysis. NL, AHS, and HHW participated in the measurements. RQW, YL, FM, and ZZH supervised the overall study and polished the manuscript. All authors read and approved the final manuscript.
The authors declare that they have no competing interests.
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