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

引用本文: 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. doi: S1872-2067(19)63506-0 shu

Citation: 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. doi: S1872-2067(19)63506-0 shu

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

华中农业大学理学院, 湖北武汉 430070
基金项目:
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）.

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:

English

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

College of Science, Huazhong Agricultural University, Wuhan 430070, Hubei, China
Received Date: 27 February 2020
Revised Date: 30 March 2020
Fund Project:
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).

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:

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沈阳化工大学材料科学与工程学院沈阳 110142

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

English

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

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

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

English

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

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs