暴露高活性晶面的TiO_2纳米管的制备及生物活性
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摘要
采用多次阳极氧化技术,在金属钛表面制备(001)晶面族择优生长的TiO_2纳米管阵列,研究电解液成分对锐钛矿TiO_2不同晶面相对比例的影响并考察其生物学活性。采用扫描电镜(SEM)、X射线衍射(XRD)等方法分析纳米管阵列的形貌特征和晶体结构,通过生物矿化CaP盐的沉积和蛋白吸附实验评价样品晶面对生物活性的影响。结果表明:通过改变电解液中H_2O的含量,能够便捷调控锐钛矿TiO_2纳米管中不同晶面的相对比例。当H_2O含量为2%(体积分数)时,制备得到的TiO_2纳米管阵列(004)晶面的织构系数T_(c(004))可达4.76。而具有(001)优势晶面族的TiO_2纳米管,在类人体环境中能够为生物矿化和蛋白吸附提供更多的活性位点,加速羟基磷灰石的沉积并增加蛋白吸附量,表现出更优异的生物学活性。
TiO_2 nanotubes arrays with dominant(001) facets were fabricated by multi-anodic oxidation technology. The influence factor of the electrolyte composition on the ratio of different facets for anatase TiO_2 and the bioactivity were investigated. Besides, the characterization of the surface morphologies and crystal structures were analyzed by scanning electron microscope(SEM) and X-ray diffraction(XRD),etc. Finally, the bioactivity was estimated by the CaP salt deposition vis biomin-eralization process and protein adsorption experiment. The results show that the relative proportions of different facets in the TiO_2 nanotubes can be adjusted by changing the content of H_2O in the electrolyte. The(004) facet texture coefficient of TiO_2 nanotubes arrays prepared in 2%H_2O(volume fraction) electrolyte reaches up to 4.76. The TiO_2 nanotubes with dominant(001) facets can accelerate the deposition of hydroxyapatite and raise the amount of protein adsorption in the humanoid environment by providing more active sites for biomineralization and protein adsorption. The TiO_2 nanotubes with a higher proportion of(001) facets have the more excellent biological activity.
TiO_2 nanotubes arrays with dominant(001) facets were fabricated by multi-anodic oxidation technology. The influence factor of the electrolyte composition on the ratio of different facets for anatase TiO_2 and the bioactivity were investigated. Besides, the characterization of the surface morphologies and crystal structures were analyzed by scanning electron microscope(SEM) and X-ray diffraction(XRD),etc. Finally, the bioactivity was estimated by the CaP salt deposition vis biomin-eralization process and protein adsorption experiment. The results show that the relative proportions of different facets in the TiO_2 nanotubes can be adjusted by changing the content of H_2O in the electrolyte. The(004) facet texture coefficient of TiO_2 nanotubes arrays prepared in 2%H_2O(volume fraction) electrolyte reaches up to 4.76. The TiO_2 nanotubes with dominant(001) facets can accelerate the deposition of hydroxyapatite and raise the amount of protein adsorption in the humanoid environment by providing more active sites for biomineralization and protein adsorption. The TiO_2 nanotubes with a higher proportion of(001) facets have the more excellent biological activity.
引文
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[2] URE?A J,TSIPAS S,JIMéNEZ-MORALES A,et al. Cellular behaviour of bone marrow stromal cells on modified Ti-Nb surfaces[J].Materials & Design,2018,140:452-459.
[3] 戈军伟,陈梁锋,李亚男,等. 高(001)晶面锐钛矿二氧化钛纳米材料的合成与应用[J]. 应用化工,2015,44(4):739-745. GE J W,CHEN L F,LI Y N,et al. Synthesis and application of anatase TiO2 with exposed (001) facet[J]. Applied Chemical Industry,2015,44 (4):739-745.
[4] GONG X Q,SELLONI A. Reactivity of anatase TiO2 nanopa-rticles:the role of the minority (001) surface[J]. The Journal of Physical Chemistry B,2005,109(42):19560-19562.
[5] 李智,葛少华. 纳米二氧化钛在生物医学中的应用进展[J]. 口腔医学,2017,37(1):85-88. LI Z,GE S H. Research progress on the application of nano-sized dioxide titanium in biomedicine field[J]. Stomatology,2017,37(1):85-88.
[6] WEN C Z,JIANG H B,QIAO S Z,et al. Synthesis of highrea-ctive facets dominated anatase TiO2[J]. Journal of Materials Chemistry,2011,21(20):7052-7061.
[7] ZHOU J,YIN L,LI H,et al. Heterojunction of SrTiO3/TiO2 nanotubes with dominant (001) facets:synthesis,formation mech-anism and photoelectrochemical properties[J]. Materials Science in Semiconductor Processing,2015,40:107-116.
[8] 陈昱,王京钰,李维尊,等. 新型二氧化钛基光催化材料的研究进展[J]. 材料工程,2016,44(3):103-113. CHEN Y,WANG J Y,LI W Z,et al. Research progress in TiO2-based photocatalysis material[J]. Journal of Materials Engin-eering,2016,44(3):103-113.
[9] GORDON T R,CARGNELLO M,PAIK T,et al. Nonaqueous synthesis of TiO2 nanocrystals using TiF4 to engineer morph-ology,oxygen vacancy concentration,and photocatalytic activity[J]. Journal of the American Chemical Society,2012,134(15):6751-6761.
[10] HERMAN G,SIEVERS M,GAO Y. Structure determination of the two-domain (1×4) anatase TiO2 (001) surface[J]. Physical Review Letters,2000,84(15):3354-3357.
[11] XU H,REUNCHAN P,OUYANG S,et al. Anatase TiO2 single crystals exposed with high-reactive {111} facets toward efficient H2 evolution[J]. Chemistry of Materials,2013,25(3):405-411.
[12] ONG W J,TAN L L,CHAI S P,et al. Highly reactive {001} facets of TiO2-based composites:synthesis,formation mechanism and characterization[J]. Nanoscale,2014,6(4):1946-2008.
[13] YANG Z,MA Z,PAN D,et al. Enhancing the performance of front-illuminated dye-sensitized solar cells with highly [001] oriented,single-crystal-like TiO2 nanotube arrays[J]. Ceramics International,2014,40(1):173-180.
[14] JUNG M H,KO K C,LEE J Y. Single crystalline-like TiO2 nanotube fabrication with dominant (001) facets using poly(vinylpyrrolidone) for high efficiency solar cells[J]. The Journal of Physical Chemistry C,2014,118(31):17306-17317.
[15] YANG H G,SUN C H,QIAO S Z,et al. Anatase TiO2 single crystals with a large percentage of reactive facets[J]. Nature,2008,453(7195):638-641.
[16] ACEVEDOP P,GONZALEZ F,GONZALEZ G,et al. The effect of anatase crystal orientation on the photoelectrochemical performance of anodic TiO2 nanotubes[J]. Phys Chem Chem Phys,2014,16(47):26213-26220.
[17] MA X,DAI Y,GUO M,et al. Insights into the role of surface distortion in promoting the separation and transfer of photog-enerated carriers in anatase TiO2[J]. The Journal of Physical Chemistry C,2013,117(46):24496-24502.
[18] LI H,ZHOU J,ZHANG X,et al. Constructing stable NiO/N-doped TiO2 nanotubes photocatalyst with enhanced visible-light photocatalytic activity[J]. Journal of Materials Science:Materials in Electronics,2015,26(4):2571-2578.
[19] ZHONG J S,WANG Q Y,ZHOU J,et al. Highly efficient photoelectrocatalytic removal of RhB and Cr(Ⅵ) by Cu nanop-articles sensitized TiO2 nanotube arrays[J]. Applied Surface Science,2016,367:342-346.
[20] YANG Z,MA Z,PAN D,et al. Enhancing the performance of front-illuminated dye-sensitized solar cells with highly [001] oriented,single-crystal-like TiO2 nanotube arrays[J]. Ceramics International,2014,40(1):173-180.
[21] LEE S,PARK I J,KIM D H,et al. Crystallographically preferred oriented TiO2 nanotube arrays for efficient photovoltaic energy conversion[J]. Energy & Environmental Science,2012,5(7):7989-7995.
[22] ARIOSA D,ELHORDOY F,DALCHIELE E A,et al. Texture vs morphology in ZnO nano-rods:on the X-ray diffraction characterization of electrochemically grown samples[J]. Journal of Applied Physics,2011,110(12):124901-124909.
[23] MA Q,LI M,HU Z,et al. Enhancement of the bioactivity of titanium oxide nanotubes by precalcification[J]. Materials Letters,2008,62(17/18):3035-3038.
[24] ROHANIZADEH R,ALSADEQ M,LEGEROS R Z. Prepara-tion of different forms of titanium oxide on titanium surface:effects on apatite deposition[J]. J Biomed Mater Res A,2004,71(2):343-352.
[25] SVETINA M,COLOMBI C L,SBAIZERO O,et al. Deposition of calcium ions on rutile (110):a first-principles investigation[J]. Acta Materialia,2001,49(12):2169-2177.
[26] CHANG M C,TANAKA J. FT-IR study for hydroxyapatite/collagen nanocomposite cross-linked by glutaraldehyde[J]. Biomaterials,2002,23(24):4811-4818.
[27] ZHANG H,LIU X,LI Y,et al. {001} facets dominated anatase TiO2:morphology,formation/etching mechanisms and perfor-mance[J]. Science China Chemistry,2012,56(4):402-417.