La掺杂BiFeO3对苯酚光催化降解性能的影响

doi:10.1016/S1872-2067(16)62449-X

催化学报 ›› 2016, Vol. 37 ›› Issue (8): 1283-1292.DOI: 10.1016/S1872-2067(16)62449-X

La掺杂BiFeO₃对苯酚光催化降解性能的影响

孟婉婉, 胡瑞生, 杨军, 杜燕飞, 李景佳, 王宏叶

内蒙古大学化学化工学院稀土材料化学与物理重点实验室, 内蒙古呼和浩特 010021

收稿日期:2016-01-21 修回日期:2016-04-23 出版日期:2016-07-29 发布日期:2016-08-01
通讯作者: Ruisheng Hu
基金资助:
国家自然科学基金（21166015）.

Influence of lanthanum-doping on photocatalytic properties of BiFeO₃ for phenol degradation

Wanwan Meng, Ruisheng Hu,Jun Yang, Yanfei Du, Jingjia Li, Hongye Wang

Key Laboratory of Rare Earth Materials Chemistry and Physics, School of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021, Inner Mongolia, China

Received:2016-01-21 Revised:2016-04-23 Online:2016-07-29 Published:2016-08-01
Contact: Ruisheng Hu
Supported by:
This work was supported by the National Natural Science Foundation of China (21166015).

摘要/Abstract

摘要：

苯酚是一种稳定、毒性大且难降解的有机物，对人类和生态环境产生很大威胁，因此急需研发出能有效移除工业废水中苯酚污染物的方法.其中，绿色、高效的光催化氧化技术得到研究人员青睐.在半导体光催化剂中，BiFeO₃具有带隙窄（2.2-2.5eV）、化学稳定性好及成本低等优点，被看作是最有潜力的光催化剂.但是，BiFeO₃存在光生电子空穴对复合率高，制备过程中易形成杂质相的缺点，使得其光催化活性很差，限制了BiFeO₃在光催化领域的应用.异种离子的引入能产生杂质能级或裁剪半导体带隙，同时促进光生载流子分离，故可考虑采用离子掺杂改性BiFeO₃的手段来抑制杂质相生成，提高载流子分离，从而提高BiFeO₃的光催化性能.本文以柠檬酸为络合剂，通过一步溶胶凝胶法合成了系列样品Bi_1-xLa_xFeO₃（摩尔分数x = 0， 0.10， 0.15， 0.20）.通过X射线衍射（XRD）、扫描电镜（SEM）、能谱（EDS）、透射电镜（TEM）、X射线光电子能谱（XPS）、紫外可见漫反射（UV-Vis DRS）及荧光光谱（PL）等手段对不同样品的物相、形貌、表面价态和光学性能进行了表征.并通过活性物种捕获实验和羟基自由基（^·OH）产生实验分析了Bi_0.85La_0.15FeO₃样品在苯酚降解过程中的主要活性物种和降解机理.相对于单相BiFeO₃，La改性BiFeO₃催化剂的光降解苯酚性能均有提高，其中La最佳掺杂量为0.15.在模拟太阳光下照射180min后，Bi_0.85La_0.15FeO₃的光催化活性达到96%，同时COD去除率达到81.53%，并表现出好的循环使用活性和稳定性.研究发现，该光催化过程中主要的活性物种为^·OH.XRD，SEM，TEM和EDS结果表明，La元素掺杂进BiFeO₃结构中，且各元素分布均匀，同时，适量La元素掺杂能有效抑制杂质相Bi₂₅FeO₄₀的形成，而且La掺杂BiFeO₃样品的颗粒尺寸略有减小，有利于电子空穴转移.XPS显示，La改性BiFeO₃样品的表面有氧空位形成，将有利于有机物的吸附和降解；另外，羟基氧和吸附氧含量增大，有利于活性氧物种形成.UV-VisDRS和PL测试证明，La改性后的样品对可见光的响应增强，样品带隙变窄，产生杂质能级，抑制了光生载流子复合，有利于产生更多载流子来促进活性物种形成，从而提高光催化活性.氧物种捕获实验说明，在Bi_0.85La_0.15FeO₃参与的苯酚降解过程中的主要活性物种是^·OH，同时^·OH的产生实验也证明了在光照下^·OH在Bi_0.85La_0.15FeO₃光催化剂表面持续产生，并提出了光催化降解机理.

关键词: 溶胶-凝胶法, 镧掺杂, BiFeO₃, 光催化, 苯酚

Abstract:

A series of BiFeO₃ and lanthanum-doped BiFeO₃ photocatalysts were synthesized by a facile sol-gel method using citric acid as complexing agent, and used to remove phenol in industrial wastewater under simulated sunlight irradiation. The samples were characterized by X-ray diffraction, energy dispersive spectroscopy, X-ray photoelectron spectroscopy, UV-Vis diffuse reflectance spectroscopy and photoluminescence spectroscopy. The introduction of La effectively suppressed the generation of an impurity phase. All the metals (La, Bi and Fe) are well distributed. Under simulated sunlight irradiation, the La-doped BiFeO₃ photocatalysts exhibited superior photocatalytic activity to pure BiFeO₃. The 15% La-doped BiFeO₃ photocatalyst exhibited the best activity, with a degradation rate of 96% and COD removal rate of 81.53% after irradiation for 180 min, and it showed good recycling stability. The enhanced photocatalytic ability of 15% La-doped BiFeO₃ was attributed to the increase of adsorbed surface hydroxyl groups, enhancement of visible light absorption and reduction of electron-hole recombination. We confirmed that the primary active species was ^·OH by adding different scavengers during the photodegradation of phenol and proposed a reaction mechanism based on these experiments.

Key words: Sol-gel method, La-doping, Bismuth ferrite, Photocatalysis, Phenol

孟婉婉, 胡瑞生, 杨军, 杜燕飞, 李景佳, 王宏叶. La掺杂BiFeO₃对苯酚光催化降解性能的影响[J]. 催化学报, 2016, 37(8): 1283-1292.

Wanwan Meng, Ruisheng Hu,Jun Yang, Yanfei Du, Jingjia Li, Hongye Wang. Influence of lanthanum-doping on photocatalytic properties of BiFeO₃ for phenol degradation[J]. Chinese Journal of Catalysis, 2016, 37(8): 1283-1292.

×
扫码分享

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(16)62449-X

https://www.cjcatal.com/CN/Y2016/V37/I8/1283

参考文献

[1] G. R. Reddy, S. Balasubramanian, K. Chennakesavulu, RSC Adv., 2015, 5, 81013-81023.
[2] X. C. Luo, G. Q. Zhu, J. H. Peng, X. M. Wei, M. Hojamberdiev, L. Jin, P. Liu, Appl. Surf. Sci., 2015, 351, 260-269.
[3] J. H. Li, W. Zhao, Y. Guo, Z. B. Wei, M. S. Han, H. He, S. G. Yang, C. Sun, Appl. Surf. Sci., 2015, 351, 270-279.
[4] I. H. Chowdhury, S. Ghosh, M. K. Naskar, Ceram. Int. A, 2016, 42, 2488-2496.
[5] D. Barreca, G. Carraro, M. E. A. Warwick, K. Kaunisto, A. Gasparotto, V. Gombac, C. Sada, S. Turner, G. Van Tendeloo, C. Maccato, P. Fornasiero, CrystEngComm, 2015, 17, 6219-6226.
[6] P. Benjwal, K. K. Kar, RSC Adv., 2015, 5, 98166-98176.
[7] T. Soltani, M. H. Entezari, Ultrason. Sonochem., 2013, 20, 1245-1253.
[8] S. Park, J. Park, R. Selvaraj, Y. Kim, J. Ind. Eng. Chem., 2015, 31, 269-275.
[9] B. Qin, Y. B. Zhao, H. Li, L. Qiu, Z. Fan, Chin. J. Catal., 2015, 36, 1321-1325.
[10] M. Humayun, A. Zada, Z. J. Li, M. Z. Xie, X. L. Zhang, Y. Qu, F. Raziq, L. Q. Jing, Appl. Catal. B, 2016, 180, 219-226.
[11] F. Niu, D. Chen, L. S. Qin, N. Zhang, J. Y. Wang, Z. Chen, Y. X. Huang, ChemCatChem, 2015, 7, 3279-3289.
[12] Y. N. Huo, M. Miao, Y. Zhang, J. Zhu, H. X. Li, Chem. Commun., 2011, 47, 2089-2091.
[13] F. Niu, D. Chen, L. S. Qin, T. Gao, N. Zhang, S. Wang, Z. Chen, J. Y. Wang, X. G. Sun, Y. X. Huang, Sol. Energy Mater. Sol. Cells, 2015, 143, 386-396.
[14] S. Chauhan, M. Kumar, S. Chhoker, S. C. Katyal, H. Singh, M. Jewariya, K. L. Yadav, Solid State Commun., 2012, 152, 525-529.
[15] A. S. Priya, I. B. S. Banu, S. Anwar, J. Magn. Magn. Mater., 2016, 401, 333-338.
[16] A. S. Naeimi, E. Dehghan, D. Sanavi Khoshnoud, A. Gholizadeh, J. Magn. Magn. Mater., 2015, 393, 502-507.
[17] Y. Li, X. Y. Liu, Y. X. Sun, S. Sheng, H. R. Liu, P. Y. Yang, S. J. Yang, J. Alloys Compd., 2015, 644, 602-606.
[18] E. Jimenez-Relinque, M. Castellote, Cem. Concr. Res., 2015, 74, 108-115.
[19] J. G. Wu, J. Wang, D. Q. Xiao, J. G. Zhu, Appl. Surf. Sci., 2011, 257, 7226-7230.
[20] X. M. Zhang, M. Gao, Y. L. Gu, H. L. Bao, X. L. Li, X. T. Zhou, W. Wen, J. Phys. Chem. C, 2012, 116, 20230-20238.
[21] Y. C. Jiao, M. F. Zhu, F. Chen, J. L. Zhang, Chin. J. Catal., 2013, 34, 585-592.
[22] C. X. Hao, F. S. Wen, J. Y. Xiang, H. Hou, W. M. Lü, Y. F. Lü, W. T. Hu, Z. Y. Liu, Mater. Res. Bull., 2014, 50, 369-373.
[23] X. Q. Liu, J. J. Lü, S. Wang, X. Li, J. Y. Lang, Y. G. Su, Z. L. Chai, X. J. Wang, J. Alloys Compd., 2015, 622, 894-901.
[24] Y. P. Xie, G. S. Wang, J. Colloid Interface Sci., 2014, 430, 1-5.
[25] H. Y. Li, J. F. Liu, J. J. Qian, Q. Y. Li, J. J. Yang, Chin. J. Catal., 2014, 35, 1578-1589.
[26] P. Ballirano, A. Pacella, C. Cremisini, E. Nardi, M. Fantauzzi, D. Atzei, A. Rossi, G. Cametti, Microporous Mesoporous Mater., 2015, 211, 49-63.
[27] M. Mullet, V. Khare, C. Ruby, Surf. Interface Anal., 2008, 40, 323-328.
[28] H. Y. Chuai, D. F. Zhou, X. F. Zhu, Z. H. Li, W. P. Huang, Chin. J. Catal., 2015, 36, 2194-2202.
[29] S. M. Ke, P. Lin, X. R. Zeng, H. T. Huang, L. M. Zhou, Y. W. Mai, Ceram. Int., 2014, 40, 5263-5268.
[30] L. F. Da Silva, O. F. Lopes, A. C. Catto, W. Avansi, M. I. B. Bernardi, M. S. Li, C. Ribeiro, E. Longo, RSC Adv., 2016, 6, 2112-2118.
[31] T. T. Wang, J. Y. Lang, Y. J. Zhao, Y. G. Su, Y. X. Zhao, X. J. Wang, CrystEngComm, 2015, 17, 6651-6660.
[32] H. J. Li, Y. Zhou, W. G. Tu, J. H. Ye, Z. G. Zou, Adv. Funct. Mater., 2015, 25, 998-1013.
[33] S. Issarapanacheewin, K. Wetchakun, S. Phanichphant, W. Kangwansupamonkon, N. Wetchakun, Mater. Lett., 2015, 156, 28-31.
[34] L. Yu, X. F. Yang, J. He, Y. He, D. S. Wang, J. Alloys Compd., 2015, 637, 308-314.
[35] Y. G. Su, L. M. Peng, J. W. Guo, S. S. Huang, L. Lü, X. J. Wang, J. Phys. Chem. C, 2014, 118, 10728-10739.
[36] J. G. McEvoy, W. Q. Cui, Z. S. Zhang, Appl. Catal. B, 2014, 144, 702-712.
[37] S. Q. Han, J. Li, K. L. Yang, J. Lin, Chin. J. Catal., 2015, 36, 2119-2126.
[38] S. Tonda, S. Kumar, O. Anjaneyulu, V. Shanker, Phys. Chem. Chem. Phys., 2014, 16, 23819-23828.
[39] W. J. Fa, P. Wang, B. Yue, F. L. Yang, D. P. Li, Z. Zheng, Chin. J. Catal., 2015, 36, 2186-2193.
[40] S. G. Kumar, K. S. R. K. Rao, Appl. Surf. Sci., 2015, 355, 939-958.
[41] L. Yu, X. F. Yang, J. He, Y. He, D. S. Wang, J. Mol. Catal. A, 2015, 399, 42-47.
[42] L. Song, X. Y. Zhao, L. X. Cao, J. W. Moon, B. H. Gu, W. Wang, Nanoscale, 2015, 7, 16695-16703.

La掺杂BiFeO₃对苯酚光催化降解性能的影响

Influence of lanthanum-doping on photocatalytic properties of BiFeO₃ for phenol degradation

PDF

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

参考文献

相关文章 15

编辑推荐

Metrics

[1]	赵彬彬, 钟威, 陈峰, 王苹, 别传彪, 余火根. 高晶化g-C₃N₄光催化剂: 合成、结构调控和光催化产氢[J]. 催化学报, 2023, 52(9): 127-143.
[2]	唐小龙, 李锋, 李方, 江燕斌, 余长林. 单原子催化剂在光催化和电催化合成过氧化氢中的研究进展[J]. 催化学报, 2023, 52(9): 79-98.
[3]	蔡铭洁, 刘艳萍, 董珂欣, 陈晓波, 李世杰. 漂浮型Bi₂WO₆/C₃N₄/碳布S型异质结光催化材料用于高效净化水体环境[J]. 催化学报, 2023, 52(9): 239-251.
[4]	王思恺, 闵祥婷, 乔波涛, 颜宁, 张涛. 单原子催化: 追寻催化领域的“圣杯”[J]. 催化学报, 2023, 52(9): 1-13.
[5]	江梓聪, 程蓓, 张留洋, 张振翼, 别传彪. 氧化锌基梯型异质结光催化剂[J]. 催化学报, 2023, 52(9): 32-49.
[6]	刘博文, 蔡家杰, 张建军, 谭海燕, 程蓓, 许景三. MOF/CdS梯型光催化剂同时进行苯甲醇氧化和析氢反应及其机理研究[J]. 催化学报, 2023, 51(8): 204-215.
[7]	宋明明, 宋相海, 刘鑫, 周伟强, 霍鹏伟. ZnIn₂S₄/MOF-808微球结构S型异质结光催化剂的制备及其光还原CO₂性能研究[J]. 催化学报, 2023, 51(8): 180-192.
[8]	邵秀丽, 李可, 李静萍, 程强, 王国宏, 王楷. 揭示NiS@Ta₂O₅纳米纤维中梯型电荷转移路径及光催化CO₂转化性能[J]. 催化学报, 2023, 51(8): 193-203.
[9]	李嘉明, 李源, 王小田, 杨直雄, 张高科. TiO₂上原子分散的Fe位点促进光催化CO₂还原: 增强的催化活性、 DFT计算和机制洞察[J]. 催化学报, 2023, 51(8): 145-156.
[10]	阎菲, 张由子, 刘思碧, 邹睿卿, Jahan B Ghasemi, 李炫华. 供体-受体型卟啉基金属有机框架实现有效电荷分离高效光催化析氢[J]. 催化学报, 2023, 51(8): 124-134.
[11]	孙利娟, 王伟康, 路平, 刘芹芹, 王乐乐, 唐华. 纳米高熵合金实现光催化剂肖特基势垒的调控用于光催化制氢与苯甲醇氧化耦合反应[J]. 催化学报, 2023, 51(8): 90-100.
[12]	刘海峰, 黄祥, 陈加藏. 电子态调控促进氢气无损耗纯化中CO的光致富集和氧化[J]. 催化学报, 2023, 51(8): 49-54.
[13]	袁鑫, 范海滨, 刘杰, 覃龙州, 王剑, 段秀, 邱江凯, 郭凯. 连续流技术在光氧化还原催化转化的最新进展[J]. 催化学报, 2023, 50(7): 175-194.
[14]	余治晗, 关晨, 岳晓阳, 向全军. 碳环渗入的结晶氮化碳S型同质结及其光催化析氢[J]. 催化学报, 2023, 50(7): 361-371.
[15]	李慧杰, 池漫洲, 辛兴, 王瑞杰, 刘天府, 吕红金, 杨国昱. 异金属取代的多金属氧酸盐@光响应型金属-有机框架用于高选择性光催化CO₂还原[J]. 催化学报, 2023, 50(7): 343-351.