基于钼酸铋的碘掺杂辅助氧空位可控引入及其高效活化分子氧和矿化五氯酚作用

doi:10.1016/S1872-2067(19)63506-0

催化学报 ›› 2020, Vol. 41 ›› Issue (10): 1544-1553.DOI: 10.1016/S1872-2067(19)63506-0

基于钼酸铋的碘掺杂辅助氧空位可控引入及其高效活化分子氧和矿化五氯酚作用

汪圣尧, 熊中亮, 杨楠, 丁星, 陈浩

华中农业大学理学院, 湖北武汉 430070

收稿日期:2020-02-27 修回日期:2020-03-30 出版日期:2020-10-18 发布日期:2020-08-15
通讯作者: 陈浩, 丁星
基金资助:
国家自然科学基金（51872107，21607047，51572101，51902121）；湖北省自然科学基金（2016CFB193，2019CFB322）；中央高校基本科研业务费专项基金（2662015QD047，2662016PY088，2662015PY047）.

Iodine-doping-assisted tunable introduction of oxygen vacancies on bismuth tungstate photocatalysts for highly efficient molecular oxygen activation and pentachlorophenol mineralization

Shengyao Wang, Zhongliang Xiong, Nan Yang, Xing Ding, Hao Chen

College of Science, Huazhong Agricultural University, Wuhan 430070, Hubei, China

Received:2020-02-27 Revised:2020-03-30 Online:2020-10-18 Published:2020-08-15
Supported by:
This work was supported by the National Natural Science Foundation of China (51872107, 21607047, 51572101, 51902121), Natural Science Foundation of Hubei Province (2016CFB193, 2019CFB322), and Fundamental Research Funds for the Central Universities (2662015QD047, 2662016PY088, 2662015PY047).

摘要/Abstract

摘要： 氧空位引入是设计带隙和电子结构以显著提高半导体光催化效率的有效策略之一.氧空位不仅可以有效地捕获载流子而加速光生电子空穴对的分离，还可以捕获电子作为惰性气体分子活化的活性位点.在分子水平上阐明氧空位在光催化中的固有功能也逐渐引起了研究者们的广泛兴趣.近年来，诸多文献报道原生氧空位可以很容易地通过局域电子对氧气进行充电，这表明光催化是分子氧在氧空位上的活化是克服三重态O₂自旋禁制反应生成活性氧物种的可靠选择.由此产生的活性氧物种，如羟基自由基（^·OH）、超氧阴离子自由基（^·O₂^-）和单线态氧（¹O₂），通常比O₂更具有氧化性.尽管在构建氧空位方面已有系列开创性的工作报道，但在光催化材料上氧空位浓度的调控策略仍处于起步阶段，依然具有很大的探索空间.因此，建立一种可控引入氧空位的方法，并揭示氧空位在增强分子氧活化中的潜在作用具有重要科学意义.我们利用还原性的乙二醇为溶剂，通过简便的溶剂热法合成了氧空位浓度可控的碘掺杂钨酸铋.在理论计算预测的基础上，采用X射线粉末衍射（XRD）、透射电子显微技术（TEM）、X射线光电子能谱（XPS）、电感耦合等离子体光谱（ICP）、拉曼光谱（Raman）和电子顺磁共振波谱（EPR）等多种表征手段研究了碘掺杂对钨酸铋氧空位构筑及理化性质的影响.
理论计算结果表明，未改性钨酸铋需要2.94eV的能量驱使晶格氧原子逸出形成氧空位，而表面碘掺杂可以将该能垒降至1.20eV，证明了碘掺杂可以降低钨酸铋氧空位的形成能，从而促进钨酸铋上氧空位的生成.受此启发，我们利用溶剂热法合成了系列碘掺杂钨酸铋，XRD和形貌分析表明碘的引入并未改变钨酸铋的结构.而XPS和ICP分析证实了碘的成功引入.EPR结果显示随着碘含量的增加，钨酸铋的氧空位浓度也逐渐提高，证明了碘的引入促进了氧空位的产生.通过对五氯酚钠的光催化降解实验，我们进一步研究了碘诱导产生的氧空位对材料光催化活性的影响.结果表明，所有碘掺杂的钨酸铋在可见光辐照下都表现出更高的五氯酚钠降解活性，优化后的碘掺杂钨酸铋在2h内对五氯酚钠的总有机碳去除率即可超过90%.为进一步分析碘掺杂钨酸铋光催化活性提高的原因，我们分别对样品进行了比表面测试、氧气吸附量测试及能带位置和活性物种分析.结果表明，碘元素的掺杂虽然没有明显拓展钨酸铋的吸收带边，但是可以提高钨酸铋材料在可见光区的光吸收能力，促进材料对光的利用率.更重要的是，氧空位的引入显著增强了钨酸铋对氧气的化学吸附，因而增强了其在可见光下通过活化分子氧作用，进而产生更多的超氧自由基和单线态氧促进光催化五氯酚降解.该研究为实现可控构筑含氧空位光催化材料用于环境污染物降解提供了新的思路.

关键词: 碘掺杂, 氧空位, 钨酸铋, 光催化, 分子氧活化, 五氯酚钠

Abstract: In this work, the tunable introduction of oxygen vacancies in bismuth tungstate was realized via a simple solvothermal method with the assistance of iodine doping. With the predictions afforded by theoretical calculations, the as-prepared bismuth tungstate was characterized using various techniques, such as X-ray diffraction, Raman spectroscopy, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, electron spin resonance spectroscopy, and UV-Vis diffuse reflectance spectroscopy. The different concentrations of the oxygen vacancies on bismuth tungstate were found to be intensely correlated with iodine doping, which weakened the lattice oxygen bonds. Owing to the sufficient oxygen vacancies introduced in bismuth tungstate as a result of iodine doping, the molecular oxygen activation was remarkably enhanced, thus endowing bismuth tungstate with high activity for the photocatalytic degradation of sodium pentachlorophenate. More encouraging is the total organic carbon removal rate of sodium pentachlorophenate over iodine-doped bismuth tungstate that exceeded 90% in only 2 h and was 10.6 times higher than that of the pristine bismuth tungstate under visible light irradiation. Moreover, the mechanism, through which the degradation of sodium pentachlorophenate over iodine-doped bismuth tungstate is enhanced, was speculated based on the results of radical detection and capture experiments. This work provides a new perspective for the enhanced photocatalytic degradation of organochlorine pesticides from the oxygen vacancy-induced molecular oxygen activation over iodine-doped bismuth tungstate.

Key words: Iodine doping, Oxygen vacancy, Bismuth tungstate, Photocatalyst, Molecular oxygen activation, NaPCP

汪圣尧, 熊中亮, 杨楠, 丁星, 陈浩. 基于钼酸铋的碘掺杂辅助氧空位可控引入及其高效活化分子氧和矿化五氯酚作用[J]. 催化学报, 2020, 41(10): 1544-1553.

Shengyao Wang, Zhongliang Xiong, Nan Yang, Xing Ding, Hao Chen. Iodine-doping-assisted tunable introduction of oxygen vacancies on bismuth tungstate photocatalysts for highly efficient molecular oxygen activation and pentachlorophenol mineralization[J]. Chinese Journal of Catalysis, 2020, 41(10): 1544-1553.

×
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(19)63506-0

https://www.cjcatal.com/CN/Y2020/V41/I10/1544

参考文献

[1] P. Abhilash, N. Singh, J. Hazard. Mater., 2009, 165, 1-2.
[2] J. Liu, J. Diamond, Nature, 2005, 435, 1179-1186.
[3] Y. Xing, Y. Lu, R. W. Dawson, Y. Shi, H. Zhang, T. Wang, W. Liu, H. Ren, Chemosphere, 2005, 60, 731-739.
[4] F. P. Carvalho, Environ. Sci. Polic., 2006, 9, 685-692.
[5] J. Fu, B. Mai, G. Sheng, G. Zhang, X. Wang, P. Peng, X. Xiao, R. Ran, F. Cheng, X. Peng, Z. Wang, U. Tang, Chemosphere, 2003, 52, 1411-1422.
[6] T. Bøhn, M. Cuhra, T. Traavik, M. Sanden, J. Fagan, R. Primicerio, Food Chem., 2014, 153, 207-215.
[7] P. H. Howard, J. Saxena, H. Sikka, Environ. Sci. Technol., 1978, 12, 398-407.
[8] R. Andreozzi, V. Caprio, A. Insola, R. Marotta, Catal. Today, 1999, 53, 51-59.
[9] S. Esplugas, D. M. Bila, L. G. T. Krause, M. Dezotti, J. Hazard. Mater., 2007, 149, 631-642.
[10] T. An, H. Yang, W. Song, G. Li, H. Luo, W. J. Cooper, J. Phys. Chem. A, 2010, 114, 2569-2575.
[11] J. M. Herrmann, Catal. Today, 1999, 53, 115-129.
[12] A. Fujishima, K. Honda, Nature, 1972, 238, 37-38.
[13] J. Di, J. Xia, M. Ji, B. Wang, S. Yin, Q. Zhang, Z. Chen, H. Li, ACS Appl. Mater. Interfaces, 2015, 7, 20111-20123.
[14] M. Pelaez, N. T. Nolan, S. C. Pillai, M. K. Seery, P. Falaras, A. G. Kontos, P. S. Dunlop, J. W. Hamilton, J. A. Byrne, K. O'shea, Appl. Catal. B-Environ., 2012, 125, 331-349.
[15] J. Li, Y. Yu, L. Zhang, Nanoscale, 2014, 6, 8473-8488.
[16] Z. Wang, Y. Huang, M. Chen, X. Shi, Y. Zhang, J. Cao, W. Ho, S. C. Lee, ACS Appl. Mater. Interfaces, 2019, 11, 10651-10662.
[17] Y. Huang, P. Wang, Z. Wang, Y. Rao, J. J. Cao, S. Pu, W. Ho, S. C. Lee, Appl. Catal. B-Environ., 2019, 240, 122-131.
[18] M. Chen, Y. Huang, J. Yao, J. J. Cao, Y. Liu, Appl. Surf. Sci., 2018, 430, 137-144.
[19] S. Wang, X. Yang, X. Zhang, X. Ding, Z. Yang, K. Dai, H. Chen, Appl. Surf. Sci., 2017, 391, 194-201.
[20] S. Wang, X. Ding, X. Zhang, H. Pang, X. Hai, G. Zhan, W. Zhou, H. Song, L. Zhang, H. Chen, Adv. Funct. Mater., 2017, 27, 1703923.
[21] J. Zhang, S. Wang, F. Liu, X. Fu, G. Ma, M. Hou, Z. Tang, Acta Phys.-Chem. Sin., 2019, 35, 885-895.
[22] S. Gu, L. Wang, J. Zhang, Chin. J. Chem., 2017, 35, 153-158.
[23] X. Yang, Y. Wang, X. Xu, Y. Qu, X. Ding, H. Chen, Chin. J. Catal., 2017, 38, 260-269.
[24] J. Wang, Z. Wang, B. Huang, Y. Ma, Y. Liu, X. Qin, X. Zhang, Y. Dai, ACS Appl. Mater. Interfaces, 2012, 4, 4024-4030.
[25] M. Setvín, U. Aschauer, P. Scheiber, Y. F. Li, W. Hou, M. Schmid, A. Selloni, U. Diebold, Science, 2013, 341, 988-991.
[26] E. Carter, A. F. Carley, D. M. Murphy, J. Phys. Chem. C, 2007, 111, 10630-10638.
[27] X. Xu, X. Ding, X. Yang, P. Wang, S. Li, Z. Lu, H. Chen, J. Hazard. Mater., 2019, 364, 691-699.
[28] Z. Zhang, W. Wang, E. Gao, M. Shang, J. Xu, J. Hazard. Mater., 2011, 196, 255-262.
[29] Q. Wu, R. Van De Krol, J. Am. Chem. Soc., 2012, 134, 9369-9375.
[30] Y. Lv, Y. Liu, Y. Zhu, Y. Zhu, J. Mater. Chem. A, 2014, 2, 1174-1182.
[31] L. Ye, K. Deng, F. Xu, L. Tian, T. Peng, L. Zan, Phys. Chem. Chem. Phys., 2012, 14, 82-85.
[32] Y. He, X. Jin, W. Li, S. Yang, B. Lu, Chin. J. Inog. Chem., 2019, 35, 996-1004
[33] H. Huang, S. Tu, C. Zeng, T. Zhang, A. H. Reshak, Y. Zhang, Angew. Chem. Int. Ed., 2017, 56, 11860-11864.
[34] R. Long, K. Mao, X. Ye, W. Yan, Y. Huang, J. Wang, Y. Fu, X. Wang, X. Wu, Y. Xie, J. Am. Chem. Soc., 2013, 135, 3200-3207.
[35] N. Zhang, X. Li, H. Ye, S. Chen, H. Ju, D. Liu, Y. Lin, W. Ye, C. Wang, Q. Xu, J. Am. Chem. Soc., 2016, 138, 8928-8935.
[36] H. Fu, C. Pan, W. Yao, Y. Zhu, J. Phys. Chem. B, 2005, 109, 22432-22439.
[37] C. Zhang, Y. Zhu, Chem. Mater., 2005, 17, 3537-3545.
[38] H. Fu, L. Zhang, W. Yao, Y. Zhu, Appl. Catal. B-Environ., 2006, 66, 100-110.
[39] R. Shi, G. Huang, J. Lin, Y. Zhu, J. Phys. Chem. C, 2009, 113, 19633-19638.
[40] C. Jovalekic, L. Atanasoska, V. Petrovic, M. Ristic, J. Mater. Sci., 1991, 26, 3553-3564.
[41] G. Kresse, J. Furthmüller, Phys. Rev. B, 1996, 54, 11169-11186.
[42] G. Kresse, D. Joubert, Phys. Rev. B, 1999, 59, 1758-1775.
[43] P. E. Blöchl, Phys. Rev. B, 1994, 50, 17953-17979.
[44] J. P. Perdew, K. Burke, M. Ernzerhof, Phys. Rev. Lett., 1996, 77, 3865.
[45] L. Wang, Z. Wang, L. Zhang, C. Hu, Chem. Eng. J., 2018, 352, 664-672.
[46] G. Zhang, Z. Hu, M. Sun, Y. Liu, L. Liu, H. Liu, C. P. Huang, J. Qu, J. Li, Adv. Funct. Mater., 2015, 25, 3726-3734.
[47] Y. Zhou, Y. Zhang, M. Lin, J. Long, Z. Zhang, H. Lin, J. C. S. Wu, X. Wang, Nat. Commun., 2015, 6, 8340.
[48] S. Wang, X. Hai, X. Ding, K. Chang, Y. Xiang, X. Meng, Z. Yang, H. Chen, J. Ye, Adv. Mater., 2017, 29, 1701774.
[49] X. Ding, K. Zhao, L. Zhang, Environ. Sci. Technol., 2014, 48, 5823-5831.

基于钼酸铋的碘掺杂辅助氧空位可控引入及其高效活化分子氧和矿化五氯酚作用

Iodine-doping-assisted tunable introduction of oxygen vacancies on bismuth tungstate photocatalysts for highly efficient molecular oxygen activation and pentachlorophenol mineralization

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]	乔秀清, 李晨, 王紫昭, 侯东芳, 李东升. TiO_2-_x@C/MoO₂肖特基结: 合理设计及高效电荷分离提升光催化性能[J]. 催化学报, 2023, 51(8): 66-79.
[14]	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.
[15]	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.