脒基钛(Ⅲ)配合物制备N/C-TiO_2薄膜及其光学性能研究
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摘要
以TiCl_3(3THF)为原料合成脒基钛(Ⅲ)配合物1,将其作为前驱体通过LPCVD沉积N/C-TiO_2薄膜。利用1HNMR、元素分析以及热重分析(TGA)探究配合物1的结构和热化学性质。结果表明,配合物1具有良好的热稳定性和合适的挥发性,满足CVD的要求。通过EDS和UV-Vis吸收光谱表征了薄膜的成分及光学性能,结果表明,当沉积温度为350℃时,N/C-TiO_2薄膜的N、C质量分数最高,其禁带宽度降低为2. 82 e V,对可见光的吸收最强。与纯的二氧化钛薄膜相比,N/C-TiO_2薄膜对亚甲基蓝的降解率显著提高到90%。
A titanium( Ⅲ) amidinate( 1) compound is synthesized from Ti Cl3( 3 THF) and is then used as a precursor to deposit on quartzes in a LPCVD reactor system to make N/C-TiO_2 films.Compound( 1) is characterized by1 HNMR spectrum,elemental analysis and thermogravimetric analysis( TGA) to evaluate its structure and thermal properties.TGA curves imply compound( 1) possesses suitable thermal stability and volatility and can meet the demands of CVD. The components and optical properties of N/C-TiO_2 films are investigated by EDS and UV-Vis absorption spectrums,respectively.The results demonstrate that when deposition happens at 350℃,N/C-TiO_2 film has the highest contents of N and C and exhibits a stronger ability to absorb visible light,and its energy band gap decreases to 2. 82 e V.The degradation rate of methylene blue by N/C-TiO_2 film improves significantly to 90%.
A titanium( Ⅲ) amidinate( 1) compound is synthesized from Ti Cl3( 3 THF) and is then used as a precursor to deposit on quartzes in a LPCVD reactor system to make N/C-TiO_2 films.Compound( 1) is characterized by1 HNMR spectrum,elemental analysis and thermogravimetric analysis( TGA) to evaluate its structure and thermal properties.TGA curves imply compound( 1) possesses suitable thermal stability and volatility and can meet the demands of CVD. The components and optical properties of N/C-TiO_2 films are investigated by EDS and UV-Vis absorption spectrums,respectively.The results demonstrate that when deposition happens at 350℃,N/C-TiO_2 film has the highest contents of N and C and exhibits a stronger ability to absorb visible light,and its energy band gap decreases to 2. 82 e V.The degradation rate of methylene blue by N/C-TiO_2 film improves significantly to 90%.
引文
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[3]Stefik M,Heiligtag F J,Niederberger M,et al.Improved nonaqueous synthesis of Ti O2for dye-sensitized solar cells[J]. ACS Nano,2013,7(10):8981-8989.
[4]Asahi R,Morikawa T,Ohwaki T,et al. Visible-light photocatalysis in nitrogen-doped titanium oxides[J]. Science,2001,293(5528):269-271.
[5]Guo Y,Zhang X,Weng W H,et al.Structure and properties of nitrogen-doped titanium dioxide thin films grown by atmospheric pressure chemical vapor deposition[J].Thin Solid Films,2007,515(18):7117-7121.
[6]Tseng Y H,Kuo C S,Huang C H,et al.Preparation of visible-lightresponsive nitrogen-carbon co-doped titania by chemical vapor deposition[J]. Zeitschrift für Physikalische Chemie,2010,224(6):843-856.
[7]Mamane H,Horovitz I,Lozzi L,et al.The role of physical and operational parameters in photocatalysis by N-doped Ti O2sol-gel thin films[J].Chemical Engineering Journal,2014,257:159-169.
[8]Baker M A,Fakhouri H,Grilli R,et al.Effect of total gas pressure and O2/N2flow rate on the nanostructure of N-doped Ti O2thin films deposited by reactive sputtering[J]. Thin Solid Films,2014,552:10-17.
[9]Dunnill C,Parkin I.N-Doped titania thin films prepared by atmospheric pressure CVD using t-butylamine as the nitrogen source:Enhanced photocatalytic activity under visible light[J]. Chemical Vapor Deposition,2009,15(7-9):171-174.
[10]O'Neill S A,Clark R J H,Parkin I P,et al.Anatase thin films on glass from the chemical vapor deposition of titanium(Ⅳ)chloride and ethyl acetate[J].Chemistry of Materials,2003,15(1):46-50.
[11]Du L,Yu S,Liu X,et al.An aminopyridinato Mn(Ⅱ)compound as a novel CVD precursor for manganese-containing films[J]. New Journal of Chemistry,2018,42(6):4553-4558.
[12]Quesada-Cabrera R,Sotelo-Vzquez C,Quesada-Gonzlez M,et al.On the apparent visible-light and enhanced UV-light photocatalytic activity of nitrogen-doped Ti O2thin films[J]. Journal of Photochemistry and Photobiology A:Chemistry,2017,333:49-55.
[13]Sarantopoulos C,Gleizes A N,Maury F.Chemical vapor deposition and characterization of nitrogen doped Ti O2thin films on glass substrates[J].Thin Solid Films,2009,518(4):1299-1303.
[14]Wu G,Nishikawa T,Ohtani B,et al.Synthesis and characterization of carbon-doped Ti O2nanostructures with enhanced visible light response[J].Chemistry of Materials,2007,19(18):4530-4537.
[15]Alexandrov S E,Baryshnikova M V,Filatov L A,et al. Chemical Vapour Deposition of nitrogen-doped titanium dioxide thin films[J].Journal of Nanoscience and Nanotechnology,2011,11(9):8274-8278.
[16]Sotelo-Vazquez C,Quesada-Cabrera R,Darr J A,et al. Single-step synthesis of doped Ti O2stratified thin-films by atmosphericpressure chemical vapour deposition[J].Journal of Materials Chemistry A,2014,2(19):7082-7087.
[17]Duminica F D,Maury F,Hausbrand R. N-doped Ti O2coatings grown by atmospheric pressure MOCVD for visible light-induced photocatalytic activity[J]. Surface and Coatings Technology,2007,201(22-23):9349-9353.
[18]Randeniya L K,Bendavid A,Martin P J,et al.Photoelectrochemical and structural properties of Ti O2and N-doped Ti O2thin films synthesized using pulsed direct current plasma-activated chemical vapor deposition[J]. The Journal of Physical Chemistry C,2007,111(49):18334-18340.
[19]Kim S J,Xu K,Parala H,et al.Intrinsic Nitrogen-doped CVD-grown Ti O2thin films from all-N-coordinated Ti precursors for photoelectrochemical applications[J]. Chemical Vapor Deposition,2013,19(1-3):45-52.
[20]Ma Q,Guo H,Gordon R G,et al.Surface chemistry of copper(I)acetamidinates in connection with Atomic Layer Deposition(ALD)processes[J].Chemistry of Materials,2011,23(14):3325-3334.
[21]Jones N A,Liddle S T,Wilson C,et al. Titanium(Ⅲ)alkoxy-Nheterocyclic carbenes and a safe,low-cost route to Ti Cl3(THF)3[J].Organometallics,2007,26(3):755-757.
[22]Lim B S,Rahtu A,Park J S,et al.Synthesis and characterization of volatile,thermally stable,reactive transition metal amidinates[J].Inorganic Chemistry,2003,42(24):7951-7958.
[23]Wright S F,Dollimore D,Dunn J G,et al. Determination of the vapor pressure curves of adipic acid and triethanolamine using thermogravimetric analysis[J].Thermochimica Acta,2004,421(1-2):25-30.
[24]Wu P G,Ma C H,Shang J K.Effects of nitrogen doping on optical properties of Ti O2thin films[J].Applied Physics A,2005,81(7):1411-1417.
[25]Morikawa T,Asahi R,Ohwaki T,et al.Band-gap narrowing of titanium dioxide by nitrogen doping[J]. Japanese Journal of Applied Physics,2001,40(6A):L561-L563.