铟掺杂钨位增强钨酸铋氧空位光催化效率

王泽普; 付念; 于涵; 徐晶威; 何祺; 郑树凯; 丁帮福; 闫小兵

doi:10.7498/aps.68.20191010

摘要

以硝酸铋、硝酸铟、钨酸铵、柠檬酸、聚乙二醇为原料和表面活性剂, 通过溶胶-凝胶法合成纯的和铟掺杂正交晶系钨酸铋. X射线衍射表征得到所有样品都是纯相且无杂质相. 光催化降解罗丹明B实验发现, 铟掺杂样品降解能力高于纯相, 其最佳掺杂含量为7%摩尔比. 扫描电子显微镜和X射线光电子能谱表征发现, 光催化性能提高主要是由于氧空位数目增多导致, 而形貌发生蓬松改变起到促进作用. 利用第一性原理计算, 单一氧空位模型形成能小于Bi1_In + V_O和Bi2_In + V_O共掺杂模型形成能, 而大于W_In + V_O形成能. 这个结果表示铟替代钨位促进氧空位产生. 电子结构计算发现, 氧空位在带隙和导带底附近引入新的局域态, 促进光吸收而增强光催化性能. 本文通过理论模拟和实验表征钨酸铋氧空位光催化性能调控归因于铟进入钨位而非铋位.

关键词:

钨酸铋 /
铟掺杂 /
氧空位 /
形成能

Abstract

Pure and In-doped orthorhombic Bi₂WO₆ are synthesized by sol-gel method through using raw materials Bi(NO₃)₃·5H₂O, In(NO₃)₃·6H₂O, (NH₄)₂WO₄ and surfactants citric acid, polyethylene glycol. All samples are in pure phase without impurity phase as indicated by X-ray diffraction characterization. The In-doped sample degradation efficiency for rhodamine B is higher than that for pure phase with the optimal content 7% mole ratio. Because indium impurity adhering to Bi₂WO₆ nucleus surface may affect the crystallization range, the sample morphology gradually becomes fluffy and regular, which is reveled through scanning electron microscopy analysis. This morphology change plays an important role in electron-hole transport process as well as contact area of carrier and organic molecule. Using X-ray photoelectron spectroscopy (XPS) characterization and Gaussian fitting, it is found that the O 1s XPS peak of pure and In-doped sample each contain three peak sites. The low energy peak around 530 eV originates from W—O and Bi—O bond. The high peak is ascribed to lattice oxygen defect and its intensity is enhanced gradually with the increase of In content. Thus the increase of oxygen vacancies is the main reason for this photocatalytic performance improvement. Comparing with the impurity-free sample, the visible absorption of In-doped Bi₂WO₆ is enhanced and the corresponding band gap slightly decreases, which is indicated by diffraction reflection spectroscopy measurement. The reduction of forbidden band width further enhances the photocatalytic performance. After configuration relaxation and self-consistence calculation, the formation energy obtained from a single oxygen vacancy model is less than those from the Bi1_In + V_O and the Bi2_In + V_O co-doping models, and greater than the W_In + V_O formation energy. This result indicates that indium replacing W site can promote the generating of oxygen vacancies. The calculation of the 18%-hybridization function electronic structure shows that the Bi₂WO₆ has indirect band gap semi-conduction with energy gap 2.76 eV, which is consistent with the experimental value 2.79 eV. A series of new local states appears in the band gap and near conduction band bottom based on the oxygen vacancy model. These local states promote light absorption and enhance photocatalytic performance. In conclusion, the enhanced photocatalytic performance of Bi₂WO₆ is attributed to the indium entering into the tungsten site rather than the bismuth site as indicated by the experimental and theoretical result.

Keywords:

作者及机构信息

1.
河北大学电子信息工程学院, 保定　071002

2.
河北大学物理科学与技术学院, 保定　071002

通信作者: 郑树凯, zhshk@126.com ; 丁帮福, dbf1982@126.com ;

基金项目: 河北省高等学校科学技术研究项目(批准号: ZD2017008)、河北大学高层次人才基金(批准号: 521000981118)和国家自然科学基金(批准号: 61674050)资助的课题

Authors and contacts

1.
College of Electronic Information Engineering, Hebei University, Baoding 071002, China

2.
College of Physics Science and Technology, Hebei University, Baoding 071002, China

Corresponding author: Zheng Shu-Kai, zhshk@126.com ; Ding Bang-Fu, dbf1982@126.com ;

Funds: Project supported by the Science and Technology Research Project of Hebei Higher Education Institution, China (Grant No. ZD2017008), the High-level Talents Funds of Hebei University, China (Grant No. 521000981118), and the National Natural Science Foundation of China (Grant No. 61674050)

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参考文献

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施引文献

图 1 溶胶-凝胶法制备钨酸铋粉体实验流程图

Fig. 1. Schematic diagram of sol-gel method for bismuth tungstate powder preparation.

下载: 全尺寸图片幻灯片

图 2 ICSD模拟和不同浓度铟掺杂钨酸铋XRD图谱(a)和优化完正交钨酸铋结构模型(b)

Fig. 2. XRD patterns of the ICSD simulation and different concentration In-doped bismuth tungstate (a), as well as optimized orthogonal bismuth tungstate structure model (b).

下载: 全尺寸图片幻灯片

图 3 样品微观形貌结构图　(a)纯相, (b) 5 at%, (c) 7 at%, (d) 10 at% In-Bi₂WO₆

Fig. 3. Microscopic morphology of samples: (a) Pure phase, (b) 5 at%, (c) 7 at%, and (d) 10 at% In-Bi₂WO₆

下载: 全尺寸图片幻灯片

图 4 不同铟掺杂钨酸铋的降解效率(a)和一级反应速率常数柱状图(b)

Fig. 4. Degradation efficiency of In-doped bismuth tungstate (a) and the first-order reaction rate constant (b).

下载: 全尺寸图片幻灯片

图 5 纯相(a)和7%铟掺杂(b) Bi₂WO₆的O 1 s XPS光谱以及Gaussian分峰

Fig. 5. O1 s XPS spectra and Gaussian peaks of pure phase (a) and 7% In-doped Bi₂WO₆ (b).

下载: 全尺寸图片幻灯片

图 6 纯的和7 at%铟掺杂样品的漫反射光谱(a)和K-M方程拟合的带隙值(b)

Fig. 6. Diffuse reflectance spectra of pure and 7 at% In-doped samples (a) and band gap values fitted by K-M equation (b).

下载: 全尺寸图片幻灯片

图 7 (a)四种模型结构示意图及其(b)相应形成能变化趋势

Fig. 7. Schematic diagram of four model structures (a) and corresponding formation energy variation (b).

下载: 全尺寸图片幻灯片

图 8 纯相(a), (b)和单一氧空位(c), (d)模型电子结构　(a), (c) 能带图; (b), (d) 态密度图

Fig. 8. Pure phase (a), (b) and single oxygen vacancy (c), (d) model electronic structure: (a), (c) Energy band diagram; (b), (d) density of states (DOS).

下载: 全尺寸图片幻灯片

[1]	Ait Ahsaine H, Ezahri M, Benlhachemi A, Bakiz B, Villain S, Guinneton F, Gavarri J R 2016 Ceram. Int. 42 8552 Google Scholar
[2]	Ait Ahsaine H, El Jaouhari A, Slassi A, Ezahri M, Benlhachemi A, Bakiz B, Guinnetonc F, Gavarric J R 2016 RSC Adv. 6 101105 Google Scholar
[3]	Song X C, Zheng Y F, Ma R, Zhang Y Y, Yin H Y 2011 J. Hazard. Mater. 192 186
[4]	盛珈怡, 李晓金, 许宜铭 2014 物理化学学报 30 508 Google Scholar Sheng J Y, Li X J, Xu Y M 2014 Acta Phys. Chim. Sin. 30 508 Google Scholar
[5]	Wang J J, Tang L, Zeng G G, Liu Y N, Zhou Y Y, Deng Y C, Wang J J, Peng B 2017 ACS Sustainable Chem. Eng. 5 1062 Google Scholar
[6]	Kong X Y, Choo Y Y, Chai S P, Soh A K, Mohamedc A R 2016 Chem. Commun. 52 14242 Google Scholar
[7]	卢青, 华罗光, 陈亦琳, 高碧芬, 林碧洲 2015 无机材料学报 30 413 Lu Q, Hua L G, Chen Y L, Gao B F, Lin B Z 2015 J. Inorg. Mater. 30 413
[8]	许雪棠, 王凡, 黄恒俊, 季璐璐, 蒙晶棉, 邓鸿骥 2017 中国专利 CN 106390992 A Xu X T, Wang F, Huang H J, Ji L L, Meng J M, Deng H J 2017 Chinese Patent CN 106390992 A (in Chinese)
[9]	Lü Y H, Yao W Q, Zong R L, Zhu Y F 2016 Sci. Rep. 6 19347 Google Scholar
[10]	Liu Y, Wei B, Xu L L, Gao H, Zhang M Y 2015 Chem. Cat. Chem. 7 4076
[11]	Gu H, Ding J, Zhong Q, Zeng Y Q, Song F J 2019 Inter. J. Hydrogen. Energ. 44 11808 Google Scholar
[12]	郝亮, 张慧娜, 闫建成, 程丽君, 关苏军, 鲁云 2018 天津科技大学学报 33 1 Hao L, Zhang H N, Yan J C, Cheng L J, Guan S J, Lu Y 2018 J. Tianjin Univ. Sci. Tech. 33 1
[13]	Zhang Z J, Wang W Z, Gao E P, Shang M, Xu J H 2011 J. Hazard. Mater. 196 255 Google Scholar
[14]	Tan G Q, Huang J, Zhang L L, Ren H J, Xia A 2014 Ceram. Inter. 40 11671 Google Scholar
[15]	Ding B F, Han C, Zheng L R, Zhang J Y, Wang R M, Tang Z L 2015 Sci. Rep. 5 9443 Google Scholar
[16]	Shannon R D 1976 Acta Cryst. A 32 751 Google Scholar
[17]	李洪全, 郑树凯, 丁帮福, 闫小兵 2018 中国粉体技术 24 19 Li H Q, Zheng S K, Ding B F, Yan X B 2018 Chin. Powder. Sci. Tech. 24 19
[18]	Nie Z P, Ma D K, Fang G Y, Chen W, Huang S M 2016 J. Mater. Chem. A 4 2438 Google Scholar
[19]	Zhou Y, Tian Z P, Zhao Z Y, Liu Q, Kou J H, Chen X Y, Gao J, Yin S C, Zou Z G 2011 ACS Appl. Mater. Interface 3 3594
[20]	王亚军, 于海洋, 李泽雪, 郭梁 2018 材料研究学报 32 149 Google Scholar Wang Y J, Yu H Y, Li Z X, Guo L 2018 Chin. J. Mater. Res. 32 149 Google Scholar

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铟掺杂钨位增强钨酸铋氧空位光催化效率