从天然辉锑矿中制备硫化锑纳米棒及其性能探究
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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(Sb_2S_3)纳米棒。探讨了Sb_2S_3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Sb_2S_3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Sb_2S_3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2～3μm的Sb_2S_3单晶纳米棒。制备的Sb_2S_3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Sb_2S_3纳米棒在可见光下对甲基橙的光催化降解率高于商业Sb_2S_3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。
Antimony trisulfide(Sb_2S_3) 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 Sb_2S_3 were systematically studied, and the possible formation mechanism of Sb_2S_3 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 Sb_2S_3 on the degradation of methyl orange were investigated under the visible light irradiation. The results showed that the Sb_2S_3 nanoflakes formed after hydrothermal synthesis at 160℃ for 12 h, and the nanoflakes would transform into nanorods eventually after N_2-annealing at 400℃ for 1 h. The obtained Sb_2S_3 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 Sb_2S_3 nanorods on methyl orange under visible light irradiation is higher than that of commercial Sb_2S_3, which is up to 87.6% after 60 min degradation, exhibiting obvious visible-light activity.
Antimony trisulfide(Sb_2S_3) 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 Sb_2S_3 were systematically studied, and the possible formation mechanism of Sb_2S_3 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 Sb_2S_3 on the degradation of methyl orange were investigated under the visible light irradiation. The results showed that the Sb_2S_3 nanoflakes formed after hydrothermal synthesis at 160℃ for 12 h, and the nanoflakes would transform into nanorods eventually after N_2-annealing at 400℃ for 1 h. The obtained Sb_2S_3 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 Sb_2S_3 nanorods on methyl orange under visible light irradiation is higher than that of commercial Sb_2S_3, which is up to 87.6% after 60 min degradation, exhibiting obvious visible-light activity.
引文
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[17]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.
[18]SUN MENG,LI DAN-ZHEN,LI WEN-JUAN,et al.New photocatalyst,Sb2S3,for degradation of methyl orange under visiblelight irradiation.Journal of Physical Chemistry C,2008,112(46):18076-18081.
[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,RANJARA-JANNED 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.
[6]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.
[7]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.
[8]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.
[9]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.
[10]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.
[11]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.
[12]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.
[13]LEONARDAS?IGAS,ALGIRDAS AUDZIJONIS,JONASGRIGAS.Origin of weak ferroelectricity in semiconductive Sb2S3crystal.Journal of Physics and Chemistry of Solids,2017,101(1):5-9.
[14]PABLO SALINAS-ESTEVANé,EDUARDO M SáNCHEZ.Preparation of Sb2S3 nanostructures by the ionic liquid-assisted sonochemical method.Crystal Growth&Design,2010,10(9):3917-3924.
[15]WANG GONG-HUA,CHEUNG CHIN LI.Building crystalline Sb2S3 nanowire dandelions with multiple crystal splitting motif.Materials Letters,2012,67(1):222-225.
[16]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.
[17]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.
[18]SUN MENG,LI DAN-ZHEN,LI WEN-JUAN,et al.New photocatalyst,Sb2S3,for degradation of methyl orange under visiblelight irradiation.Journal of Physical Chemistry C,2008,112(46):18076-18081.