Preparation of CdSe/graphene/TiO2 Nanotube Composite and Its Protection Properties for Metals
摘 要
采用循环伏安沉积法在TiO2纳米管表面构筑了石墨烯和CdSe,其中TiO2纳米管是由阳极氧化法制备而成。通过扫描电镜(SEM)及能谱(EDS)、X射线衍射分析(XRD)和紫外可见漫反射吸收光谱(UV-vis DRS)等测试方法观察了复合膜的表面形貌、晶型和光响应特征;通过测试可见光照射前后电极的开路电位(OCP)、电化学阻抗谱(EIS)等研究了复合膜对304不锈钢的阴极保护效果。结果表明,锐钛矿相的TiO2纳米管阵列膜排列紧密,孔径约为30~60 nm;石墨烯和立方晶相的CdSe均匀地覆盖在TiO2膜表面,在纳米管口与管壁均有分布;可见光照射下,与复合膜耦合的304不锈钢的电位可以从-180 mV降至-900 mV(SCE),与纯TiO2相比,电位更负。另外,切断电源后,复合膜能够对不锈钢起到延时保护作用并达到12 h以上,这说明复合膜能够有效地解决暗态下TiO2光生电子空穴对易复合的问题,改进TiO2对304不锈钢的光生阴极保护效果。
Abstract
The composite of CdSe/graphene/TiO2 nanotube film was fabricated by cyclic voltammetric deposition of graphene and CdSe on the surface of TiO2 prepared by anodic oxidation process. The composite was characterized by scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), UV-visible diffuse reflectance spectra (UV-vis DRS). The photocathodic protection properties of the composite for 304 stainless steel were examined by the open circuit potential (OCP) and electrochemical impedance spectroscopy (EIS). It′s shown that the anatase TiO2 nanotube films were arranged closely and the diameter ranged from 30 to 60 nm. Graphene and cubic CdSe covered the TiO2 evenly and distributed on the mouth and walls of the nanotube arrays. Under visible light illumination, the OCP of the 304 stainless steel coupled with the composite film dropped from -180 mV to -900 mV (SCE). Compared with pure TiO2, the photopotential of the composite film was more negative. When the light was cut off, the photocathodic protection of the composite could maintain more than 12 h. It indicates that this can solve the recombination of photoinduced electrons and holes within the TiO2 film.
中图分类号 TG174 O6466
所属栏目 涂层
基金项目 国家科技支撑计划项目(2012BAB15B01); 国际科技合作项目(2010DFR50860)
收稿日期 2014/8/30
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备注侯保荣(1942-),院士,博士,从事海洋腐蚀与防护的研究,
引用该论文: LI Hong,WANG Xiu-tong,ZHANG Liang,HOU Bao-rong. Preparation of CdSe/graphene/TiO2 Nanotube Composite and Its Protection Properties for Metals[J]. Corrosion & Protection, 2015, 36(4): 311
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参考文献
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【5】LI H,BAI X,LING Y,et al. Fabrication of titania nanotubes as cathode protection for stainless steel[J]. Electrochemical and Solid-State Letters,2006,9(5):B28-B31.
【6】FUJISAWA R,TSUJIKAWA S. Photo-protection of 304 stainless steel with TiO2 coating[J]. Passivation of Metals and Semiconductors,1995,185:1075-1081.
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【8】PARK H,KIM K Y,CHOI W. Photoelectrochemical approach for metal corrosion prevention using a semiconductor photoanode[J]. Journal of Physical Chemistry B,2002,106(18):4775-4781.
【9】TAFEN D N,LONG R,PREZHDO O V. Dimensionality of nanoscale TiO2 determines the mechanism of photoinduced electron injection from a CdSe nanoparticle[J]. Nano Letters,2014,14(4):1790-1796.
【10】HASSAN Y,CHUANG C H,KOBAYASHI Y,et al. Synthesis and optical properties of linker-free TiO2/CdSe nanorods[J]. Journal of Physical Chemistry C,2014,118(6):3347-3358.
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【12】ROBEL L,SUBRAMANIAN V,KUNO M,et al. Quantum dot solar cells:Harvesting light energy with CdSe nanocrystals molecularly linked to mesoscopic TiO2 films[J]. Journal of the American Chemical Society,2006,128(7):2385-2393.
【13】KIM S R,PARVEZ M K,CHHOWALLA M. UV-reduction of graphene oxide and its application as an interfacial layer to reduce the back-transport reactions in dye-sensitized solar cells[J]. Chemical Physics Letters,2009,483:124-127.
【14】BRENNAN L J,BYRNE M T,BARI M,et al. Carbon nanomaterials for dye-sensitized solar cell applications:A bright future[J]. Advanced Engineering Materials,2011,1:472-485.
【15】STANKOVICH S,DIKIN D A,DOMMETT G H B,et al. Graphene-based composite materials[J]. Nature,2006,442:282-286.
【16】GUO X Q,LIU W,CAO L X,et al. Graphene incorporated nanocrystalline TiO2 films for the photocathodic protection of 304 stainless steel[J]. Applied Surface Science,2013,283:498-504.
【17】HUMMERS W S,OFFEMAN R E. Preparation of graphitic oxide[J]. Journal of the American Chemical Society,1958,80(6):1339-1339.
【18】LI N,LIU G,ZHEN C,et al. Battery performance and photocatalytic activity of mesoporous anatase TiO2 nanospheres/Graphene composites by template-free self-assembly[J]. Advanced Functional Materials,2011,21(9):1717-1722.
【19】ZHAO Y,ZHAO D L,CHEN C L,et al. Enhanced photo-reduction and removal of Cr(VI) on reduced graphene oxide decorated with TiO2 nanoparticles[J]. Journal of Colloid and Interface Science,2013,405:211-217.
【20】李立群,刘爱萍,赵海新,等. TiO2/CdSe多层膜结构的制备及光电化学性能研究[J]. 物理学报,2012,61(10):1-6.
【21】张含平,林原,周晓文,等. CdSe敏化TiO2纳米晶多孔膜电极的制备及其光电性能研究[J]. 化工新型材料,2006,34(11):17-19.
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