·1490· 工程科学学报，第37卷，第11期 0.6 7]Mishra S K,Srivastava A K.Kumar D,et al.Microstructural and electrochemical impedance characterization of bio-functionalized ultrafine ZnS nanocrystals-reduced graphene oxide hybrid for im- 0.4 munosensor applications.Nanoscale,2013,5(21):10494 [8]Tian Y,Huang G F.Tang L J,et al.Size-controllable synthesis and enhanced photocatalytic activity of porous ZnS nanospheres. .2 -I mmol .L,5 d Mater Lett,2012,83:104 ◆1mmol-L-.20d -2 mmol.L,5 d Zhao Q R.Xie Y,Zhang Z C,et al.Sizeselective synthesis of -2 mmol.L.20 d zinc sulfide hierarchical structures and their photocatalytic activi- 0 10 20 30 ty.Cryst Grouth Des,2007,7(1)153 时间min [10]Liu Y,Hu J C,Zhou T F,et al.Self-assembly of lavered wurtz- 图6不同实验条件制备疏化锌光催化降解率曲线对比图 ite ZnS nanorods/nanowires as highly efficient photocatalysts.J Fig.6 Degradation rates of methyl orange at different intervals with a Mater Chem,2011,21(41):16621 series of ZnS catalysts [11]Xiong S L,Xi BJ,Wang C M,et al.Tunable synthesis of vari- ous wurtzite ZnS architectural structures and their photocatalytic PET衬底柔韧性良好，能裁减成任意的形状，可以随意 properties.Ado Funct Mater,2007,17(15):2728 折叠弯曲，这些优势使硫化锌能适用于微纳或复杂的 012]Hu J S,Ren LL,Guo Y G,et al.Mass production and high 应用环境.而且组装在衬底上的硫化锌作为催化剂使 photocatalytic activity of ZnS nanoporous nanoparticles.Ange 用，可以避免对待处理体系产生污染，也使得催化剂的 Chem,2005,44(8):1269 [13]Chen Y,Yin R H,Wu Q S.Solvothermal synthesis of well-dis- 回收利用简化，大大降低了光催化降解有机物的成本 perse ZnS nanorods with efficient photocatalytic properties.J 3结论 Nanomater,2012,2012(1):560310 [14]Yu S H,Yoshimura M.Shape and phase control of ZnS nano- 在自组装分子层作用下，纤锌矿硫化锌纳米晶膜 crystals:template fabrication of wurtzite ZnS single-crystal 通过油一水液一液界面反应实现了室温条件下在柔性 nanosheets and ZnO flake-ike dendrites from a lamellar molecu- lar precursor ZnS.(NH2 CH2CH2 NH2)os.Ade Mater,2002, 聚合物衬底上的组装.硫化锌纳米晶膜的组装是油一 14(4):296 水液一液界面与自组装硅烷分子层协同作用的结果. 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X,Wu L.Hu L.ZnS nanostructure arrays:a developing forming:from amorphous calcium carbonate,nanostacks to hexa- material star.Ade Mater,2011,23 (5):585 gonal tablets.Cryst Grouth Des,2008,8 (5):1509 6]Shi L,Xu Y M,Li Q.Shape-selective synthesis and optical prop- 24]Xiang J H,Zhu P X,Masuda Y,et al.Fabrication of self-as- erties of highly ordered one-dimensional zns nanostructures.Cryst sembled monolayers (SAMs)and inorganic micropattern on fexi- Growth Des,2009,9(5):2214 ble polymer substrate.Langmuir,2004,20 (8):3278工程科学学报，第 37 卷，第 11 期 图 6 不同实验条件制备硫化锌光催化降解率曲线对比图 Fig． 6 Degradation rates of methyl orange at different intervals with a series of ZnS catalysts PET 衬底柔韧性良好，能裁减成任意的形状，可以随意 折叠弯曲，这些优势使硫化锌能适用于微纳或复杂的 应用环境． 而且组装在衬底上的硫化锌作为催化剂使 用，可以避免对待处理体系产生污染，也使得催化剂的 回收利用简化，大大降低了光催化降解有机物的成本． 3 结论 在自组装分子层作用下，纤锌矿硫化锌纳米晶膜 通过油--水液--液界面反应实现了室温条件下在柔性 聚合物衬底上的组装． 硫化锌纳米晶膜的组装是油-- 水液--液界面与自组装硅烷分子层协同作用的结果． 该纳米晶膜能在紫外光辅助下，作为光催化剂达到对 有机质分子的降解作用，降解率主要与硫化锌纳米晶 膜的表面积相关． 该方法是一种简便、绿色的一步反 应法，且实现了无添加剂条件下，高温稳定相纤锌矿在 聚合物衬底上的室温制备，它为在温和液相条件下合 成纳米结构的半导体功能膜提供了一条新的便捷的 途径． 参 考 文 献 ［1］ Fang X S，Bando Y，Liao M Y，et al． An efficient way to assem￾ble ZnS nanobelts as ultraviolet-light sensors with enhanced photo￾current and stability． Adv Funct Mater，2010，20( 3) : 500 ［2］ Chen Z G，Cheng L N，Xu H Y，et al． ZnS branched architec￾tures as optoelectronic devices and field emitters． Adv Mater， 2010，22( 21) : 2376 ［3］ Samant K M，Suroshe J S，Garje S S． One-pot solvothermal coating of carbon spheres with ZnS nanocrystallites and their use in the photo￾degradation of dyes． Eur J Inorg Chem，2014，2014( 3) : 499 ［4］ Zhou W，Schwartz D T，Baneyx F． Single-pot biofabrication of zinc sulfide immuno-quantum dots． J Am Chem Soc，2010，132 ( 13) : 4731 ［5］ Fang X，Wu L，Hu L． ZnS nanostructure arrays: a developing material star． Adv Mater，2011，23 ( 5) : 585 ［6］ Shi L，Xu Y M，Li Q． Shape-selective synthesis and optical prop￾erties of highly ordered one-dimensional zns nanostructures． Cryst Growth Des，2009，9( 5) : 2214 ［7］ Mishra S K，Srivastava A K，Kumar D，et al． Microstructural and electrochemical impedance characterization of bio-functionalized ultrafine ZnS nanocrystals-reduced graphene oxide hybrid for im￾munosensor applications． Nanoscale，2013，5( 21) : 10494 ［8］ Tian Y，Huang G F，Tang L J，et al． Size-controllable synthesis and enhanced photocatalytic activity of porous ZnS nanospheres． Mater Lett，2012，83: 104 ［9］ Zhao Q Ｒ，Xie Y，Zhang Z G，et al． Size-selective synthesis of zinc sulfide hierarchical structures and their photocatalytic activi￾ty． Cryst Growth Des，2007，7( 1) : 153 ［10］ Liu Y，Hu J C，Zhou T F，et al． Self-assembly of layered wurtz￾ite ZnS nanorods/ nanowires as highly efficient photocatalysts． J Mater Chem，2011，21( 41) : 16621 ［11］ Xiong S L，Xi B J，Wang C M，et al． Tunable synthesis of vari￾ous wurtzite ZnS architectural structures and their photocatalytic properties． Adv Funct Mater，2007，17( 15) : 2728 ［12］ Hu J S，Ｒen L L，Guo Y G，et al． Mass production and high photocatalytic activity of ZnS nanoporous nanoparticles． Angew Chem，2005，44( 8) : 1269 ［13］ Chen Y，Yin Ｒ H，Wu Q S． Solvothermal synthesis of well-dis￾perse ZnS nanorods with efficient photocatalytic properties． J Nanomater，2012，2012( 1) : 560310 ［14］ Yu S H，Yoshimura M． Shape and phase control of ZnS nano￾crystals: template fabrication of wurtzite ZnS single-crystal nanosheets and ZnO flake-like dendrites from a lamellar molecu￾lar precursor ZnS·( NH2 CH2 CH2 NH2 ) 0. 5 ． Adv Mater，2002， 14( 4) : 296 ［15］ Qadri S B，Skelton E F，Hsu D，et al． Size-induced transition￾temperature reduction in nanoparticles of ZnS． Phys Ｒev B， 1999，60 ( 13) : 9191 ［16］ Wang Z W，Daemen L L，Zhao Y S，et al． Morphology-tuned wurtzite-type ZnS nanobelts． Nat Mater，2005，4( 12) : 922 ［17］ Jiang L F，Yang M，Zhu S Y，et al． Phase evolution and mor￾phology control of ZnS in a solvothermal system with a single pre￾cursor． J Phys Chem C，2008，112( 39) : 15281 ［18］ Biswas S，Kar S． Fabrication of ZnS nanoparticles and nanorods with cubic and hexagonal crystal structures: a simple solvother￾mal approach． Nanotechnology，2008，19( 4) : 045710 ［19］ Zhao Y W，Zhang Y，Zhu H，et al． Low-temperature synthesis of hexagonal ( wurtzite ) ZnS nanocrystals． J Am Chem Soc， 2004，126( 22) : 6874 ［20］ Dawood F，Schaak Ｒ． ZnO-templated synthesis of wurtzite-type ZnS and ZnSe nanoparticles． J Am Chem Soc，2009，131: 424 ［21］ Banerjee I A，Yu L，Matsui H． Ｒoom-temperature wurtzite ZnS nanocrystal growth on Zn finger-like peptide nanotubes by con￾trolling their unfolding peptide structures． J Am Chem Soc， 2005，127( 46) : 16002 ［22］ Pokroy B，Fitch A N，Zolotoyabko E． Structure of biogenic arag￾onite ( CaCO3 ) ． Cryst Growth Des，2007，7( 9) : 1580 ［23］ Qiao L，Feng Q L，Lu S S． In vitro growth of nacre-like tablet forming: from amorphous calcium carbonate，nanostacks to hexa￾gonal tablets． Cryst Growth Des，2008，8 ( 5) : 1509 ［24］ Xiang J H，Zhu P X，Masuda Y，et al． Fabrication of self-as￾sembled monolayers ( SAMs) and inorganic micropattern on flexi￾ble polymer substrate． Langmuir，2004，20 ( 8) : 3278 · 0941 ·