碳掺杂TiO2纳米管电极的简易制备及其光电化学性能

doi:10.15541/jim20140576

摘要/Abstract

摘要：

通过阳极氧化方法制备了TiO₂纳米管薄膜, 在NaHCO₃存在下对该薄膜进行热处理得到碳掺杂TiO₂(C-TiO₂)纳米管薄膜, 通过X射线衍射仪(XRD)、扫描电子显微镜(SEM)、X射线光电子能谱(XPS)、紫外-可见漫反射光谱、电化学阻抗谱(EIS)和Mott-Schottky等方法对得到的薄膜进行表征。XRD结果表明C-TiO₂纳米管薄膜中的TiO₂主要为锐钛矿晶型; SEM结果显示薄膜存在纳米管结构; XPS分析表明C-TiO₂纳米管薄膜中的C以替代型掺杂形式进入到TiO₂晶格中; 光电化学性能测试显示, 相对于TiO₂纳米薄膜, C-TiO₂阻抗减小, 平带电位由-0.28 V负移至-0.38 V, 具有更好的紫外-可见光和可见光响应, 紫外-可见光下的光电流是未掺杂的1.7倍。利用阳极氧化的Ti丝作为光阳极和Pt丝作为对电极组装了染料敏化太阳能电池并进行了性能测试, 结果表明, 经过碳掺杂的Ti /TiO₂丝为光阳极电池的短路电流密度和电池效率分别达到0.17 mA/cm²和3.8%, 较未掺杂的Ti/TiO₂丝为光阳极的电池的短路电流密度和电池效率均增大, 表明适量的碳掺杂有利于提高电池效率。

关键词: TiO2, 阳极氧化, C掺杂, 光电化学

Abstract:

Nanostructured carbon-doped titanium dioxide were fabricated by thermal treatment of anodized titanium dioxide nanotube with the presence of NaHCO₃. The resulted samples were characterized via X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, UV-Vis diffuse reflectance spectra, electrochemical impedance spectroscopy and photoelectrochemistry methods. Anatase type TiO₂ nanotubes and almost no influence from C doping were observed from XRD and SEM results. XPS spectra showed that the O was partly replaced by C in the resulted carbon-doped titanium dioxide nanotubes. Enhanced photocurrents were identified for the C-TiO₂ nanotube and 1.7 times was observed in comparison to the TiO₂. Electrochemical impedance spectroscopy indicates the decrease of charge transfer resistance and flat band potential also negative shift from -0.28 V to -0.38 V. Needle- shaped dye sensitized solar cells were developed by using anodized Ti and Pt wire. Improved photovoltaic performance was demonstrated by the photocurrent density-photovoltage curves for DSSCs when the anodized Ti wire was thermal treated with the presence of NaHCO₃. The short-circuit current and energy conversion efficiency were up to 0.17 mA/cm²and 3.8%, respectively.

Key words: TiO2, anodic oxidation, carbon doping, photoelectrochemistry

中图分类号:

O644

赵鹏, 李忠, 崔晓莉. 碳掺杂TiO₂纳米管电极的简易制备及其光电化学性能[J]. 无机材料学报, 2015, 30(6): 599-604.

ZHAO Peng, LI Zhong, CUI Xiao-Li. Facile Preparation Carbon-Doped TiO₂ Nanotube Electrodes and Its Enhanced Photoelectrochemical Response[J]. Journal of Inorganic Materials, 2015, 30(6): 599-604.

图/表 9

图1 TiO2纳米管(a) and C-TiO2纳米管(b)的SEM照片

Fig. 1 SEM images of TiO2 (a) and C-TiO2 nanotubes (b)

图2 TiO2 (a)和C-TiO2(b)和Ti 基底(c)的XRD图谱

Fig. 2 XRD patterns of TiO2 (a), C-TiO2 (b) and titanium substrate (c)

图3 TiO2(a)及C-TiO2 (b)纳米管的XPS分析结果

Fig. 3 XPS spectra of TiO2 (a) and C-TiO2(b) The full-scale XPS spectra (A); high resolution XPS spectra of Cls (B), Ti2p (C), Ols(D)

图4 TiO2 (a)和C-TiO2(b)纳米管的UV-Vis漫反射光谱图

Fig. 4 UV-Vis diffuse reflectance spectra of TiO2 (a) and C-TiO2 (b) nanotube

图5 TiO2 (a)和C-TiO2(b)薄膜电极在开路电压下的EIS的Nyquist(A)和Bode曲线(B)

Fig. 5 EIS Nyquist (A) and Bode (B) plots for TiO2 (a) and C-TiO2 (b) thin film electrodes at open circuit potential

图6 TiO2 (a)和C-TiO2 (b)纳米管电极的Mott-Schottky曲线

Fig. 6 Mott-Schottky plots for TiO2 (a) and C-TiO2 (b) nanotube electrodes

图7 TiO2(a)和C-TiO2(b)在紫外-可见光(A)和可见光(B)下的光电流曲线

Fig. 7 Photocurrent-transient curves of TiO2 (a) and C-TiO2(b) electrodes under UV-Vis (A) and visible light (B) illumination

图8 TiO2(a)和C-TiO2(b)针状光电池的光电流密度和光电压关系曲线

Fig. 8 Photocurrent density-photovoltage (J-V) curves for needle-shaped DSSCs of TiO2 (a) and C-TiO2 (b) thin film electrodes

表1 TiO2 (a)和C-TiO2 (b)针状光电池的光伏性能参数

Table1 Photovoltaic performances for needle-shaped DSSCs of TiO2 and C-TiO2 thin film electrodes

Cell	V_oc/V	J_sc/(mA•cm^-2)	FF	η /%
TiO₂	0.60	0.08	0.29	1.38%
C-TiO₂	0.72	0.17	0.32	3.82%

参考文献 24

[1]	LIU ZHAO-YUE, MISRA MANO.Dye-sensitized photovoltaic wires using highly ordered TiO2 nanotube arrays.ACS Nano, 2010, 4(4): 2196-2200.
[2]	AHMED M A, EL-KATORI EMAD E, GHARNI ZARHA H. Photocatalytic degradation of methylene blue dye using Fe2O3/ TiO2 nanoparticles prepared by Sol-Gel method. J. Alloys Compd., 2013, 553: 19-29.
[3]	CHEN QI-FENG, SHI WEI-MEI, JIANG DONG, et al.Visible- light-activated Ni-Si co-doped TiO2 with photocatalytic performance.Acta Chimica Sinica, 2010, 68(4): 301-308.
[4]	CUI XIAO-LI, GU HAI-JIE, LU JUN, et al.Nanostructured carbon-doping anodic TiO2 from TiC and Its photoelectrochemical properties. Nanosci. Nanotechnol., 2007, 7(9): 3140-3145.
[5]	LI HAI-YAN, WANG DE-JUN, FAN HAI-MEI, et al.Synthesis of highly efficient C-doped TiO2 photocatalyst and its photo- generated charge-transfer properties. Colloid Interface Sci., 2011, 354: 175-180.
[6]	LI YAN-HONG,CAO WEN-BIN,WEI YI, et al.Preparation of nitrogen- doped nano-TiO2 powders.Journal of Inorganic Materials, 2006, 21(5): 1067-1072.
[7]	SUN MING-XUAN, SONG PENG, LI JING, et al.Preparation, characterization and applications of novel carbon and nitrogen codoped TiO2 nanoparticles from annealing TiN under CO atmosphere.Mater. Res. Bull., 2013, 48(10): 4271-4276.
[8]	KHAN SHAHED U M, AL-SHAHRY MOFAREH, INGLER WILLIAM B. Efficient photochemical water splitting by a chemically modified n-TiO2.Science, 2002, 297(5590): 2243-2245.
[9]	SAKTHIVELS, KISCH HORST.Daylight photoeatalysis by carbon-modified titanium dioxide.Angew. Chem. Int. Ed., 2003, 42(40): 4908-4911.
[10]	ZHU LEI, CUI XIAO-LI, SHEN JIE, et al.Visible Light Photoelectrochemical response of carbon-doped TiO2 thin films prepared by DC reactive magnetron sputtering.Acta Physico-Chimica Sinica, 2007, 23(11): 1662-1666.
[11]	LI XIANG-QING, KANG SHI-ZHAO, TANG YUN-QIU, et al.Preparation and visible light photocatalytic activity of carbon doped titanium dioxide nanotubes.Chinese Journal of Applied Chemistry, 2013, 30(2): 178-184.
[12]	BABU K FIROZ, MARXE K, KULANDAINTHAN M ANBU.Anodically fabricated TiO2 nanopores for electrocatalytic reduction of aldehydes. J. Electroanal. Chem., 2011, 663(2): 79-83.
[13]	LIN XIAO-XIA, JI XIANG, FU DE-GANG, et al.Photocatalytic properties of magnetic activated carbon supported F-doped TiO2.Journal of Inorganic Materials, 2013, 28(9): 997-1002.
[14]	WU JIN- MING, SONG XIAO-MEI, YAN MI.Alkaline hydrothermal synthesis of homogeneous titania microspheres with urchin-like nanoarchitectures for dye effluent treatments.J. Hazard. Mater., 2011, 194: 338-344.
[15]	SUN MING-XUAN, CUI XIAO-LI.Needle-shaped 3D dye-sensitized solar cells using anodized Ti wire and Pt nanoparticles/carbon fiber electrodes.J. Power Sources, 2013, 223: 74-78.
[16]	LIN XIAO-XIA, RONG FEI, JI XIANG, et al.Carbon-doped mesoporous TiO2 film and its photocatalytic activity. MicroporousMesoporous Mater., 2011, 142(1): 276-281.
[17]	SHEN JING-JING, LIU CHANG, ZHU YU-DAN, et al.Photocatalytic properties of mesoporous TiO2 prepared by hydrothermal method.Acta Physico-Chimica Sinica, 2009, 25(5): 1013-1018.
[18]	SHI Z M, YE X Y, LIANG K M, et al.XPS analysis of light elements (C, N) remaining in Sol-Gel derived TiO2 films. Mater. Sci. Lett., 2003, 22(18): 1255-1258.
[19]	CHU DAO-BAO, YUAN XI-MEI, QIN GUO-XU, et al.Efficient carbon-doped nanostructured TiO2 (anatase) film for photoelectrochemical solar cells. J. Nanopart.Res., 2008, 10(2): 357-363.
[20]	SANTERRE F, EL KHAKANI M A, CHAKER M, et al. Properties of TiC thin films grown by pulsed laser deposition.Appl. surf. sci., 1999, 148(1/2): 24-33.
[21]	HUO LI, DING KE-QIANG, WANG QING-FEI, et al.Electrochemistry studies on Fe3+ doped TiO2 films electrode.Nanomaterial and Structure, 2005, 42(2): 69-77.
[22]	GAO JIA-CHENG, XIE FENG-YU, ZHANG MIN.Influence of heat treatment on the photoelectron-chemical performance of Zn2+-doping TiO2.Journal of Functional Materials, 2013, 44(6): 826-830.
[23]	WANG BAO-HUI, WANG DE-JUN, LI TIE-JIN.Studies on photoelectrochemical properties of porous silicon.Chemical Journal of Chinese Universities, 1997, 18(4): 621-624.
[24]	SUN MING-XUAN, CUI XIAO-LI.Anodically grown Si-W codoped TiO2 nanotubes and its enhanced visible light photoelectrochemical response.Electrochem. Commun., 2012, 20: 133-136.

碳掺杂TiO₂纳米管电极的简易制备及其光电化学性能

Facile Preparation Carbon-Doped TiO₂ Nanotube Electrodes and Its Enhanced Photoelectrochemical Response

RichHTML

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

图/表 9

参考文献 24

相关文章 15

编辑推荐

Metrics

本文评价

[1]	王如意, 徐国良, 杨蕾, 邓崇海, 储德林, 张苗, 孙兆奇. p-n异质结BiVO₄/g-C₃N₄光阳极的制备及其光电化学水解性能[J]. 无机材料学报, 2023, 38(1): 87-96.
[2]	张亚萍,雷宇轩,丁文明,于濂清,朱帅霏. 双铁电复合材料的制备及其光电化学性能研究[J]. 无机材料学报, 2020, 35(9): 987-992.
[3]	郑雪, 江睿, 李谦, 王伟哲, 徐智谋, 彭静. 类阳极氧化铝纳米结构LED的研究[J]. 无机材料学报, 2020, 35(5): 561-566.
[4]	张亚萍, 丁文明, 朱海丰, 黄承兴, 于濂清, 王永强, 李哲, 徐飞. 电还原MoSe₂修饰TiO₂纳米管光电化学性能研究[J]. 无机材料学报, 2019, 34(8): 797-802.
[5]	魏科年, 刘展, 左士祥, 严向玉, 吴凤芹, 李霞章, 姚超, 刘孝恒. 高性能CeO₂/片状CdS复合光电极材料的制备及在光阴极保护中应用[J]. 无机材料学报, 2019, 34(12): 1334-1340.
[6]	盛鹏, 赵广耀, 徐丽, 刘双宇, 王博, 刘海镇, 马光, 韩钰, 陈新. 铝沉积还原制备蓝色二氧化钛[J]. 无机材料学报, 2018, 33(9): 942-948.
[7]	刘灿军, 陈述, 李洁. CdS/TiO₂纳米晶薄膜的原位法制备及光电化学性能研究[J]. 无机材料学报, 2018, 33(12): 1343-1348.
[8]	郑遗凡, 张露露, 王锴, 潘再法. 混合尖晶石型Zn₆Ga₈TiO₂₀:Cr³⁺荧光粉的合成、结构表征与发光性能[J]. 无机材料学报, 2018, 33(1): 9-13.
[9]	高鑫, 刘祥萱, 朱左明, 谢拯, 佘兆斌. NiFe₂O₄/TiO₂纳米棒阵列薄膜光电化学性能和光催化性能研究[J]. 无机材料学报, 2016, 31(9): 935-942.
[10]	万建风, 胡德圣, 卢朋辉, 林碧洲, 陈亦琳, 高碧芬. 具有高活性(001)晶面的TiO₂纳米方块的制备及光催化性能[J]. 无机材料学报, 2016, 31(8): 845-849.
[11]	尹月锋, 梁桂杰, 张强, 潘峥, 李望南, 李在房. 基于Pechini溶胶-凝胶法的染料敏化太阳能电池的优化[J]. 无机材料学报, 2016, 31(7): 739-744.
[12]	李玲, 肖俊莹, 崔米豆, 太优一, 庞永文, 韩松, 李晓苇. 高效CdS量子点敏化B/S共掺杂纳米TiO₂太阳能电池的制备及光电性能研究[J]. 无机材料学报, 2016, 31(6): 627-633.
[13]	张广心, 董雄波, 郑水林. 纳米TiO₂/硅藻土复合材料光催化降解作用研究[J]. 无机材料学报, 2016, 31(4): 407-412.
[14]	张亚萍, 张安玉, 于濂清, 董开拓, 李焰, 郝兰众. AgX(Cl, Br)-TiO₂复合材料光电化学研究[J]. 无机材料学报, 2016, 31(3): 269-273.
[15]	于濂清, 黄承兴, 张亚萍, 董开拓, 郝兰众. MoS₂修饰TiO₂纳米管阵列光电化学性能研究[J]. 无机材料学报, 2016, 31(11): 1237-1241.