从天然辉锑矿中制备硫化锑纳米棒及其性能探究

doi:10.15541/jim20180006

摘要/Abstract

摘要：

以天然辉锑矿为原料, 在聚乙二醇(PEG)和N,N-二甲基甲酰胺(DMF)的辅助下, 利用水热法合成了硫化锑(Sb₂S₃)纳米棒。探讨了Sb₂S₃纳米棒的形成机理, 并系统研究了不同制备条件对产物形貌与性能的影响。采用一系列表征方法对产物的晶型、成分、形貌、光电性能进行了探究, 并以可见光为光源、甲基橙为目标降解物评价了纳米Sb₂S₃的光催化活性。研究表明, 经160℃水热反应12 h可得到厚约50 nm的Sb₂S₃纳米片, 在氮氛中400℃热处理1 h后, 纳米片将转变为宽100~200 nm, 长2~3 μm的Sb₂S₃单晶纳米棒。制备的Sb₂S₃纳米棒为直接半导体, 能带间隙为1.66 eV。光催化测试表明, 制备的Sb₂S₃纳米棒在可见光下对甲基橙的光催化降解率高于商业Sb₂S₃试剂, 60 min后, 甲基橙的降解率达87.6%, 表现出明显的可见光活性。

关键词: 天然辉锑矿, Sb2S3纳米棒, 水热合成, 光催化性能

Abstract:

Antimony trisulfide (Sb₂S₃) nanorods were successfully synthesized via hydrothermal method with the assistance of polyethylene glycol (PEG) and N,N-dimethylformamide (DMF), using natural stibnite as precursor. The effects of experimental parameters on the morphology and the properties of the obtained Sb₂S₃ were systematically studied, and the possible formation mechanism of Sb₂S₃ nanorods in the preparation process was also discussed. Phase, compositions, morphology and photoelectric properties of the products were investigated by a series of characterization methods. The photocatalytic activity of nano Sb₂S₃ on the degradation of methyl orange were investigated under the visible light irradiation. The results showed that the Sb₂S₃ nanoflakes formed after hydrothermal synthesis at 160℃ for 12 h, and the nanoflakes would transform into nanorods eventually after N₂-annealing at 400℃ for 1 h. The obtained Sb₂S₃ nanorods with a single crystal structure are typically 2~3 μm in length, 100~200 nm in width, which are direct semiconductor with band gap of 1.66 eV. Photocatalytic degradation rate of the obtained Sb₂S₃ nanorods on methyl orange under visible light irradiation is higher than that of commercial Sb₂S₃, which is up to 87.6% after 60 min degradation, exhibiting obvious visible-light activity.

Key words: natural stibnite, nanorods, hydrothermal synthesis, photocatalytic properties

中图分类号:

TQ135

贾思齐, 蒋政, 迟莉娜, 叶瑛, 胡双双. 从天然辉锑矿中制备硫化锑纳米棒及其性能探究[J]. 无机材料学报, 2018, 33(11): 1213-1218.

JIA Si-Qi, JIANG Zheng, CHI Li-Na, YE Ying, HU Shuang-Shuang. Synthesis and Photoelectrocatalytic Performance of Sb₂S₃ Nanorods from Natural Stibnite[J]. Journal of Inorganic Materials, 2018, 33(11): 1213-1218.

图/表 8

表1 不同制备条件下样品编号表

Table 1 Number of product under different preparation conditions

Sample	PEG	Hydrothermal temperature/℃	Heat-treatment temperature/℃
S₁	?	80	-
S₂	?	120	-
S₃	?	160	-
S₄	?	160	200
S₅	?	160	300
S₆	?	160	400
S₇	-	160	400

图1 在不同水热温度下制备和不同温度热处理样品的XRD图谱

Fig. 1 XRD patterns for samples prepared at different hydrothermal temperatures and heat-treated at different temperatures

图2 在不同水热温度下制备的Sb2S3样品的SEM照片

Fig. 2 SEM images of Sb2S3 samples prepared at different hydrothermal temperatures^(a)S1; (b) S2; (c) S3

图3 不同温度热处理的Sb2S3样品的SEM照片

Fig. 3 SEM images of Sb2S3 samples heat-treated at different temperatures^(a)S4; (b) S5; (c) S6; (d) S7

图4 S6的(a)TEM、(b)HRTEM照片与(c)EDS能谱图

Fig. 4 (a) TEM and (b) HRTEM images and (c) EDS pattern of S6

图5 商业Sb2S3试剂与不同制备条件下的纳米Sb2S3的(a)紫外-可见吸收光谱图与(b)Tauc曲线图

Fig. 5 (a) UV-Vis spectra and (b) Tauc plots of nano Sb2S3 prepared at different conditions and commercial Sb2S3

图6 可见光下样品对甲基橙的催化降解曲线

Fig. 6 Photocatalytic degradation curves of samples on methyl orange under visible light irradiation

图7 样品S6在光催化反应(a)前(b)后的XRD图谱

Fig. 7 XRD patterns of sample S6 (a) before and (b) after photocatalytic reaction

参考文献 17

[1]	GAO CHUN-HUI, XU MING, BOON K N G, et al. In situ growth of Sb2S3 thin films by reactive sputtering on n-Si(100) substrates for top sub-cell of silicon based tandem solar cells.Materials Letters, 2017, 195: 186-189.
[2]	SAMOILENKO G V, ARIF M, BLINOV L N.Phase diagram and glass formation in the Sb2S3-AgI system.Glass Physics and Chemistry, 2005, 31(5): 656-660.
[3]	CHOCKALINGAM MARY J, NAGARAJO RAO K, RANJARAJANNED N, et al.Studies on sintered photoconductive layers of antimony trisulphide.Journal of Physics D: Applied Physics, 1970, 3(11): 1641-1644.
[4]	ZHOU XIAO-ZHONG, BAI LIAN-HUA, YAN JIAN, et al.Solvothermal synthesis of Sb2S3/C composite nanorods with excellent Li-storage performance.Electrochimica Acta, 2013, 108(10): 17-21.
[5]	MATTHIEU Y VERSAVEL, JOEL A HABER.Structural and optical properties of amorphous and crystalline antimony sulfide thin-films.Thin Solid Films, 2007, 515(18): 7171-7176.
	JULIANO C CARDOSO, CRAIG A GRIMES, FENG XIN JIAN, et al.Fabrication of coaxial TiO2/Sb2S3 nanowire hybrids for efficient nanostructured organic-inorganic thin film photovoltaics.Chemical Communications, 2012, 48(22): 2818-2820.
[6]	KRIISA M, KRUNKS M, ACIK I OJA, et al.The effect of tartaric acid in the deposition of Sb2S3 films by chemical spray pyrolysis.Materials Science in Semiconductor Processing, 2015, 40(1): 867-872.
[7]	MA JIAN-MIN, DUAN XIAO-CHUAN, LIAN JIA-BIAO, et al.Sb2S3 with various nanostructures: controllable synthesis, formation mechanism, and electrochemical performance toward lithium storage.Chemistry - A European Journal, 2010, 16(44): 13210-13217.
[8]	ZHU GANG-QIANG., LIU PENG, MIAO HONG-YAN, et al.Large-scale synthesis of ultralong Sb2S3 sub-microwires via a hydrothermal process.Materials Research Bulletin, 2008, 43(10): 2636-2642.
[9]	YONG GAO-BING, ZHU QI-AN, XIANG SHANG, et al.Synthesis of Sb2S3 nanorods by refluxing method and its photocatalytic performance.Acta Chimica Sinica, 2010, 68(21): 2199-2205.
[10]	OUNI B, ZOUINI M, HAJ LAKHDAR M, et al.Preparation and characterization of the rod-shaped stibnite.Materials Research Bulletin, 2015, 67(5): 191-195.
[11]	CHEN GUANG-YI, ZHANG WAN-XI, XU AN-WU.Synthesis and characterization of single-crystal Sb2S3 nanotubes via an EDTA-assisted hydrothermal route.Materials Chemistry and Physics, 2010, 123(1): 236-240.
[12]	LEONARDAS ŽIGAS, ALGIRDAS AUDZIJONIS, JONAS GRIGAS.Origin of weak ferroelectricity in semiconductive Sb2S3 crystal.Journal of Physics and Chemistry of Solids, 2017, 101(1): 5-9.
[13]	PABLO SALINAS-ESTEVANÉ, EDUARDO M SÁ NCHEZ.Preparation of Sb2S3 nanostructures by the ionic liquid-assisted sonochemical method.Crystal Growth & Design, 2010, 10(9): 3917-3924.
[14]	WANG GONG-HUA, CHEUNG CHIN LI.Building crystalline Sb2S3 nanowire dandelions with multiple crystal splitting motif.Materials Letters, 2012, 67(1): 222-225.
[15]	KLABUNDE K J.纳米材料化学. 陈建峰译. 北京: 化学化工出版社, 2004: 9-11.
[16]	ZHANG KE-LEI, LIU CUN-MING, HUANG FU-QIANG, et al.Study of the electronic structure and photocatalytic activity of the BiOCl photocatalyst.Applied Catalysis B: Environmental, 2006, 68(3): 125-129.
[17]	SUN MENG, LI DAN-ZHEN, LI WEN-JUAN, et al.New photocatalyst, Sb2S3, for degradation of methyl orange under visible- light irradiation.Journal of Physical Chemistry C, 2008, 112(46): 18076-18081.