氮铋共掺杂TiO2的合成及其可见光催化性能研究

doi:10.7517/j.issn.1674-0475.2013.06.411

摘要/Abstract

摘要：

以纳米管钛酸为钛的前驱体,Bi(NO₃)₃·5H₂O为N源和Bi源,采用水热法制备了N、Bi共掺杂的TiO₂;并以甲基橙为目标降解物考察了所制备样品的可见光催化性能(λ≥420 nm).利用XRD、XPS、UV-Vis DRS、TEM等技术对不同条件下制备的产物进行了表征.结果表明,所得样品主要为锐钛矿型,粒径20 nm左右,掺杂的Bi主要以Bi₂O₃和BiONO₃两种形式存在.N元素除了以NO₃^-的形式存在于BiONO₃中,还有少量N以间隙氮掺杂于TiO₂中形成Ti—O—N键.N、Bi共掺杂的TiO₂在可见光下表现出了优越的光催化性能,其中水热温度为130 ℃,Bi/Ti摩尔比为1%时,催化活性最高.催化活性的提高源于N和Bi的掺杂增加了样品对可见光的利用效率,降低了光生电子空穴的复合速率.

关键词: 纳米管钛酸, 氮铋共掺杂, 水热法, 二氧化钛, 可见光催化

Abstract:

N, Bi-codoped TiO₂ samples were prepared by hydrothermal method using nanotubube titanic acid as the precursor of Ti and Bi(NO₃)₃·5H₂O as the bismuth and N source, respectively. The photodegradation of methyl orange (MO) was tested as a model pollutant to evaluate the photocatalytic activity of N, Bi-codoped TiO₂ under visible light irradiation (λ≥420 nm). The photocatalysts were characterized by X-Ray diffraction (XRD), transmission electron microscope (TEM), diffused reflectance spectra (DRS), X-ray photoelectron spectroscopy (XPS). The results indicated that the main phase of the samples was anatase, and the average grain size was 20 nm. The doped-Bi existed in the form of Bi₂O₃and BiONO₃. As for the doped-N species, a part of N element existed in the form of NO₃^- of BiONO₃, and another existed in the interstitial position of the TiO₂ lattice to form the Ti-O-N bond in codoped samples. N, Bi-codoped TiO₂exhibited remarkable photocatalytic activity under visible light irradiation. The codoped-TiO₂ prepared at 130 ℃(Bi/Ti=1%,molar ratio) showed the highest photocatalytic activity. The enhanced photocatalytic activity of N, Bi-codoped TiO₂ was more likely ascribed to the fact that doped-N and Bi increased the utilization efficiency of visible light, and while decreased the recombination rates of photogenerated electrons and holes.

Key words: nanotube titanic acid, N, Bi-codoped, hydrothermal method, titanium dioxide, visible light photocatalytic activity

中图分类号:

李海燕, 钱俊杰, 刘金凤, 李秋叶, 张敏, 杨建军. 氮铋共掺杂TiO₂的合成及其可见光催化性能研究[J]. 影像科学与光化学, 2013, 31(6): 411-420.

LI Hai-yan, QIAN Jun-jie, LIU Jin-feng, LI Qiu-ye, ZHANG Min, YANG Jian-jun. Study on the Synthesis of N, Bi-codoped TiO₂ Nanoparticles and Their Visible Light Photocatalytic Performance[J]. Imaging Science and Photochemistry, 2013, 31(6): 411-420.

参考文献

[1] Choi W, Termin A, Hoffmann M R. The role of metal ion dopants in quantum-sized TiO₂: correlation between photoreactivity and charge carrier recombination dynamics[J]. The Journal of Physical Chemistry, 1994, 98(51): 13669-13679.

[2] 吴树新, 马智, 秦永宁,等. 过渡金属掺杂二氧化钛光催化性能的研究[J].感光科学与光化学, 2005, 23(2): 94-101. Wu S X, Ma Z, Qin Y N, et al. Study on photocatalytic activity of transition metal oxide doped TiO₂ photocatalysts[J]. Photographic Science and Photochemistry, 2005, 23(2): 94-101.

[3] Wang Y Q, Cheng H M, Zhang L, et al. The preparation, characterization, photoelectrochemical and photocatalytic properties of lanthanide metal-ion-doped TiO₂ nanoparticles[J]. Journal of Molecule Cataysis A: Chemical, 2000, 151(1-2): 205-216.

[4] Yamashita H, Harada M, Misaka J, et al. Degradation of propanol diluted in water under visible light irradiation using metal ion-implanted titanium dioxide photocatalysts[J]. Journal of Photochemistry and Photobiology A: Chemistry, 2002, 148(1-3): 257-261.

[5] Li F B, Li X Z, Hou M F, et al. Enhanced photocatalytic activity of Ce³⁺-TiO₂ for 2-mercaptobenzothiazole degradation in aqueous suspension for odour control[J]. Applied Catalysis A: General, 2005, 285(1-2): 181-189.

[6] Choi J, Park H, Hoffmann M R. Effects of single metal-ion doping on the visible-light photoreactivity of TiO₂[J]. The Journal of Physical Chemistry C, 2010, 114(2): 783-792.

[7] Wu J C S, Chen C H. A visible-light response vanadium-doped titania nanocatalyst by sol-gel method[J]. Journal of Photochemistry and Photobiology A: Chemistry, 2004, 163(3): 509-515.

[8] Wu Q P, Zheng Q, Krol R van de. Creating oxygen vacancies as a novel strategy to form tetrahedrally coordinated Ti⁴⁺ in Fe/TiO₂ nanoparticles[J]. The Journal of Physical Chemistry C, 2012, 116(12): 7219-7226.

[9] Fan X X, Chen X Y, Zhu S P, et al. The structural, physical and photocatalytic properties of the mesoporous Cr-doped TiO₂[J]. Journal of Molecule Cataysis A: Chemical, 2008, 284(1-2): 155-160.

[10] Takeuchi M, Yamashita H, Matsuoka M, et al. Photocatalytic decomposition of NO under visible light irradiation on the Cr-ion-implanted TiO₂ thin film photocatalyst[J]. Catalysis Letters, 2000, 67(2-4): 135-137.

[11] Anpo M. Use of visible light. Second-generation titanium oxide photocatalysts prepared by the application of an advanced metal ion-implantation method[J]. Pure and Applied Chemistry, 2000, 72(9): 1787-1702.

[12] Asahi R, Morikawa T, Ohwaki T, et al. Visible-light photocatalysis in nitrogen-doped titanium oxides[J]. Science, 2001, 293(5528): 269-271.

[13] Valentin C D, Pacchioni G, Selloni A, et al. Characterization of paramagnetic species in N-doped TiO₂ powders by EPR spectroscopy and DFT calculations[J]. The Journal Physical Chemistry B, 2005, 109(23): 11414-11419.

[14] Ohno T, Murakami N, Tsubota T, et al. Development of metal cation compound-loaded S-doped TiO₂ photocatalysts having a rutile phase under visible light[J]. Applied Catalysis A: General, 2008, 349(1-2): 70-75.

[15] Kang I C, Zhang Q W, Yin S, et al. Preparation of a visible sensitive carbon doped TiO₂ photo-catalyst by grinding TiO₂ with ethanol and heating treatment[J]. Applied Catalysis B: Environmental, 2008, 80(1-2):81-87.

[16] Li D, Haneda H, Labhsetwar N K, et al. Visible-light-driven photocatalysis on fluorine-doped TiO₂ powders by the creation of surface oxygen vacancies[J]. Chemical Physics Letters, 2005, 401(4-6): 579-584.

[17] Joung S, Amemiya T, Murabayashi M, et al. Low temperature preparation and visible light photocatalytic activity of mesoporous carbon-doped crystalline TiO₂[J]. Applied Catalysis B: Environmental, 2007, 69(3-4): 138-144.

[18] Luo H M, Takata T, Lee Y, et al. Photocatalytic activity enhancing for titanium dioxide by co-doping with bromine and chlorine[J]. Chemistry of Materials, 2004, 16(5): 846-849.

[19] Liu G, Chen Z G, Dong C L, et al. Visible light photocatalyst:iodine-doped mesoporous titania with a bicrystalline framework[J]. The Journal Physical Chemistry B, 2006, 110(42):20823-20828.

[20] Li F F, Jiang Y S, Xia M S, et al. Effect of the P/Ti ratio on the visible-light photocatalytic activity of P-doped TiO₂[J]. The Journal Physical Chemistry C, 2009, 113(42): 18134-18141.

[21] 陈永刚, 刘素文, 冯光建, 等. 氮镧共掺杂TiO₂ 纳米粉的溶剂热法制备及其可见光催化性能[J]. 硅酸盐通报, 2009, 28(1): 63-66,75. Chen Y G, Liu S W, Feng G J, et al. Preparation of N, La-doped TiO₂ nanopowder by sovolthermal method and its catalytic properties of visible light[J]. Bulletin of the Chinese Ceramic Society, 2009, 28(1): 63-66,75.

[22] Wang C, Ao Y H, Wang P F, et al. Preparation of cerium and nitrogen co-doped titania hollow spheres with enhanced visible light photocatalytic performance[J]. Powder Technology, 2011, 210(3): 203-207.

[23] 刘万兵,邓健,赵玉宝,等. 铁氮共掺杂纳米TiO₂复合膜的制备、光谱分析及光催化活性研究[J]. 光谱学与光谱分析.2009, 29(5): 1394-1397. Liu W B, Deng J, Zhao Y B, et al. Preparation, spectral analysis and photocatalytic activities of TiO₂ films codoped with iron and nitrogen[J]. Spectroscopy and Spectral Analysis, 2009, 29(5): 1394-1397.

[24] Gu D E, Yang B C, Hu Y D. V and N co-doped nanocrystal anatase TiO₂ photocatalysts with enhanced photocatalytic activity under visible light irradiation[J]. Catalysis Communications, 2008, 9(6): 1472-1476.

[25] Iliev V, Tomova D, Rakovsky S. Nanosized N-doped TiO₂ and gold modified semiconductors -photocatalysts for combined UV-visible light destruction of oxalic acid in aqueous solution[J]. Desalination, 2010, 260(1-3): 101-106.

[26] Li D Z, Chen Z X, Chen Y L, et al. A new route for degradation of volatile organic compounds under visible light: using the bifunctional photocatalyst Pt/TiO_2-xN_<em>x in H₂O₂ atmosphere[J]. Environmental Science ＆ Technology, 2008, 42(6): 2130-2135.

[27] 华南平, 吴遵义, 杜玉扣, 等. Pt、N共掺杂TiO₂在可见光下对三氯乙酸的催化降解作用 [J]. 物理化学学报, 2005, 21(10): 1081-1085. Hua N P, Wu Z Y, Du Y K, et al. Titanium dioxide nanoparticles codoped with Pt and N for photodegradation of Cl₃CCOOH[J]. Acta Physico-Chimica Sinica, 2005, 21(10): 1081-1085.

[28] Kang Q M, Yuan B L, Xu J G, et al. Synthesis, characterization and photocatalytic performance of TiO₂ codoped with bismuth and nitrogen[J]. Catalysis Letters, 2011, 141(9): 1371-1377.

[29] Zhang S L, Zhou J F, Zhang Z J, et al. Morphological structureand physicochemical properties of nanotube TiO₂[J]. Chinese Science Bulletin, 2000, 45(16): 1533-1536.

[30] Yang J J, Jin Z S, Wang X D, et al. Study on composition, structure and formation process of nanotube Na₂Ti₂O₄(OH)₂[J]. Dalton Transactions, 2003, 20: 3898-3901.

[31] Han X G, Kuang Q, Jin M S, et al. Synthesis of titania nanosheets with a high percentage of exposed (001) facets and related photocatalytic properties[J]. Journal of America Chemistry Society, 2009, 131(9): 3152-3153.

[32] 郑燕青,施尔畏,元如林,等. 二氧化钛晶粒的水热制备及其形成机理研究[J].中国科学E辑, 1999, 29(3): 206-213. Zheng Y Q, Shi E W, Yuan R L, et al. Study on hydrothermal preparation and formation mechanism of Titania grains[J]. Science in China (Series E), 1999, 29(3): 206-213.

[33] Lv K, Zuo H S, Sun J, et al. (Bi, C and N) codoped TiO₂ nanoparticles[J]. Journal of Hazardous Materials, 2009, 161(1): 396-401.

[34] Cui G J, Xu Z X, Wang Y, et al. A new method to prepare the novel a natase TiO₂[J]. Surface Review and Letters, 2008, 15(4): 509-513.

[35] Irie H, Watanabe Y, Hashimoto K. nitrogen-concentration dependence on photocatalytic activity of TiO₂-xNx powders[J]. The Journal of Physical Chemistry B, 2003, 107(23): 5483-5486.

[36] Sato S, Nakamura R, Abe S. Visible-light sensitization of TiO₂ photocatalysts by wet-method N doping[J]. Applied Catalysis A: General, 2005, 284(1-2): 131-137.

[37] Honda F, Hirokawa K. A photoelectron spectroscopic observation of iron surfaces exposed to N₂, N₂O, NO, NO₂, and air at 200 torr or 1 atm[J]. Journal of Electron Spectroscopy and Related Phenomena, 1976, 8(3): 199-211.

[38] Zhou J K, Zou Z G, Ray A K, et al. Preparation and characterization of polycrystalline bismuth titanate Bi₁₂TiO₂₀ and its photocatalytic properties under visible light irradiation[J].Industry ＆ Engineering Chemistry Research, 2007, 46(3):745-749.

[39] Wang Y, Wang Y, Meng Y L, et al. A highly efficient visible-light-activated photocatalyst based on bismuth- and sulfur-codoped TiO₂[J]. The Journal Physical Chemistry C, 2008, 112(17): 6620-6626.

氮铋共掺杂TiO₂的合成及其可见光催化性能研究

Study on the Synthesis of N, Bi-codoped TiO₂ Nanoparticles and Their Visible Light Photocatalytic Performance

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

本文评价

[1]	李玥, 宋育泽, 陶雁忠, 高风仙, 汤宁. CdS/TiO₂复合纳米网的制备及光催化性能研究[J]. 影像科学与光化学, 2018, 36(3): 275-282.
[2]	吴世康. 光催化中表面等离子体与半导体间的电子转移与能量转移[J]. 影像科学与光化学, 2018, 36(1): 1-13.
[3]	张庆宝, 刘强. 可见光催化需氧氧化在有机合成中的应用[J]. 影像科学与光化学, 2017, 35(5): 614-625.
[4]	桂梦茜, 俞洋, 朱诚逸, 刘宏芳, 王锋. 基于金属钴配合物的均相光催化还原二氧化碳研究进展[J]. 影像科学与光化学, 2017, 35(5): 649-657.
[5]	刘思迪, 张俊虎. 利用二氧化钛静电纺丝和透明质酸甲基丙烯酸酯构筑用于细胞培养的纤维凝胶结构[J]. 影像科学与光化学, 2016, 34(3): 281-287.
[6]	杨小龙, 潘月, 邢明阳, 张金龙. TiO₂-SiO₂二维大孔薄膜的制备及其光催化活性研究[J]. 影像科学与光化学, 2015, 33(5): 383-393.
[7]	张纪伟, 金振声, 张经纬, 李秋叶, 张治军. 富含本征缺陷的新型锐钛矿TiO₂纳米管的制备[J]. 影像科学与光化学, 2015, 33(4): 285-291.
[8]	李秋叶, 金振声. 可见光“全”分解水的类纳光电化学(PEC)电池模型[J]. 影像科学与光化学, 2015, 33(2): 99-107.
[9]	张美林, 金峰, 郑美玲, 刘洁, 段宣明. 水热法生长方式对ZnO纳米棒阵列结构和性能的影响[J]. 影像科学与光化学, 2015, 33(2): 136-143.
[10]	曾婷婷, 宣俊, 陈加荣, 陆良秋, 肖文精. 可见光促进的光氧化还原催化的三氟甲基化反应[J]. 影像科学与光化学, 2014, 32(5): 415-432.
[11]	梁文静, 高学旺, 邢令宝, 孟庆元, 钟建基, 雷涛, 佟振合, 吴骊珠. 新型多吡啶Pt(Ⅱ)配合物可见光催化的N-苯基四氢异喹啉交叉脱氢偶联反应[J]. 影像科学与光化学, 2014, 32(5): 447-454.
[12]	李波, 黄忠兵, 孟宪伟, 唐芳琼. L-半胱氨酸改性Fe₃O₄纳米粒子的水热合成及其应用[J]. 影像科学与光化学, 2014, 32(2): 163-170.
[13]	张鹏, 于彦龙, 匡元江, 姚江宏, 曹亚安. Si掺杂TiO₂催化剂的结构与可见光催化活性研究[J]. 影像科学与光化学, 2013, 31(4): 295-304.
[14]	曹静, 罗邦德, 徐本燕, 林海莉, 陈士夫. 离子交换法制备AgBr/Ag₂WO₄复合催化剂及其可见光催化性能[J]. 影像科学与光化学, 2012, 30(2): 110-117.
[15]	王攀, 曹婷婷, 方艳芬, 罗光富, 李瑞萍, 黄应平. Hg掺杂CdS的制备及可见光降解有毒有机污染物[J]. 影像科学与光化学, 2011, 29(1): 11-23.