一锅法合成在可见光下具有高效降解草甘膦的牡丹状Bi2S3/BiVO4(040)复合光催化剂

引用本文: 唐强勇, 霍蕊, 区烺颖, 罗秀丽, 吕嫣然, 徐悦华. 一锅法合成在可见光下具有高效降解草甘膦的牡丹状Bi₂S₃/BiVO₄(040)复合光催化剂[J]. 催化学报, 2019, 40(4): 580-589. doi: S1872-2067(19)63296-1 shu

Citation: Qiang-Yong Tang, Rui Huo, Lang-Ying Ou, Xiu-Li Luo, Yan-Ran Lv, Yue-Hua Xu. One-pot synthesis of peony-like Bi₂S₃/BiVO₄(040) with high photocatalytic activity for glyphosate degradation under visible light irradiation[J]. Chinese Journal of Catalysis, 2019, 40(4): 580-589. doi: S1872-2067(19)63296-1 shu

一锅法合成在可见光下具有高效降解草甘膦的牡丹状Bi₂S₃/BiVO₄(040)复合光催化剂

华南农业大学材料与能源学院, 广东广州 510642

摘要: 草甘膦是一种广谱除草剂，2015年世界卫生组织国际癌症研究机构宣布草甘膦可能对人类致癌（2A类）.单斜白钨矿型BiVO₄是一种较广泛研究的可见光光催化剂，但由于其光生电子和空穴迁移慢且容易复合而导致其光催化活性低.此外，有研究表明，BiVO₄的（040）晶面易于光生载流子分离，从而提高其光催化性能.Bi₂S₃的带隙能为1.27eV，能被全可见光（400-800 nm）激发.Bi₂S₃的导带和价带位置与BiVO₄匹配，能形成异质结，从而提高其光催化活性.
本文以EDTA为导向剂，L-半胱氨酸为硫源和软模板，采用一锅水热法制备了单斜白钨矿型BiVO₄，主要以（040）晶面为暴露面的Bi₂S₃/BiVO₄复合光催化剂.采用钼锑抗分光光度法测定草甘膦最终光催化降解产物之一PO₄^3-浓度，来计算草甘膦的降解率.X射线衍射（XRD）结果表明，Bi₂S₃/BiVO₄复合光催化剂只含Bi₂S₃和BiVO₄两种成分，没有其他晶相存在.场发射扫描电子显微镜（FESEM）显示，纯BiVO₄为片状结构，随着Bi₂S₃复合量增加，Bi₂S₃/BiVO₄的形貌为小片组成的牡丹状；但Bi₂S₃复合量进一步增加，Bi₂S₃/BiVO₄颗粒聚集严重.XRD，FESEM和高分辨透射电子显微镜（HRTEM）结果表明，Bi₂S₃复合量对Bi₂S₃/BiVO₄样品（040）和（121）面晶生长及形貌有显著影响.Bi₂S₃的复合提高了Bi₂S₃/BiVO₄对可见光的吸收能力，经计算BiVO₄和Bi₂S₃带隙能分别为2.42和1.27eV.随着Bi₂S₃复合量增加，Bi₂S₃/BiVO₄的光催化活性逐渐提高，至1 mmol时最高，对草甘膦的降解率为纯BiVO₄的2.2倍；但随着Bi₂S₃复合量进一步增加，Bi₂S₃/BiVO₄的光催化活性反而下降，可能是由于Bi₂S₃量太多包覆在BiVO₄表面而Bi₂S₃光催化性能很差的缘故.
瞬态光电流测试和电化学阻抗谱的结果证实，Bi₂S₃/BiVO₄比BiVO₄具有更有效的电荷分离和更快的界面电荷转移能力.活性成分捕获剂实验表明，加入空穴捕获剂EDTA或电子捕获剂K₂Cr₂O₇完全抑制了草甘膦的降解.ESR谱证明羟基自由基·OH的存在.通过计算，得出BiVO₄的价带电位（E_VB=2.87eVvs.NHE）比Bi₂S₃（E_VB=1.69eVvs.NHE）正，而Bi₂S₃（E_VB=0.42eVvs.NHE）的导带电位比BiVO₄（E_VB=0.45eVvs.NHE）负，能带匹配，即光生电子从Bi₂S₃迁移至BiVO₄，光生空穴从BiVO₄迁移至Bi₂S₃，从而将光生电子与空穴有效分离利用，达到提高其光催化性能的目的.Bi₂S₃/BiVO₄样品对草甘膦的光催化降解活性提高，主要是由于Bi₂S₃/BiVO₄异质结结构的形成提高了其对可见光的吸收能力和电子空穴对的分离效率.此外，Bi₂S₃/BiVO₄具有相对稳定性和可重复使用性.该方法简单，可制备用于光催化降解有机污染、光催化裂解水和光催化还原二氧化碳等不同领域的高活性复合光催化剂.

关键词:

English

One-pot synthesis of peony-like Bi₂S₃/BiVO₄(040) with high photocatalytic activity for glyphosate degradation under visible light irradiation

College of Materials and Energy, South China Agricultural University, Guangzhou 510642, Guangdong, China
Received Date: 14 November 2018
Revised Date: 07 January 2019

Abstract: In this work, samples consisting of BiVO₄ with exposed (040) facets coupled with Bi₂S₃ (Bi₂S₃/BiVO₄) were prepared through a one-pot hydrothermal method, using ethylenediaminetetraacetic acid as directing agent and L-cysteine as sulfur source and soft template. X-ray diffraction, field emission scanning electron microscopy, and high-resolution transmission electron microscopy measurements indicated that the Bi₂S₃ content had a significant influence on the growth of (040) and (121) facets as well as on the morphology of the Bi₂S₃/BiVO₄ samples. When the Bi₂S₃ content reached 1 mmol, the Bi₂S₃/BiVO₄ samples exhibited a peony-like morphology. The results of transient photocurrent tests and electrochemical impedance spectroscopy measurements confirmed that a more effective charge separation and a faster interfacial charge transfer occurred in Bi₂S₃/BiVO₄ than BiVO₄. The enhanced photocatalytic activity of the Bi₂S₃/BiVO₄ samples could be attributed to the improved absorption capability in the visible light region and the enhanced electron-hole pair separation efficiency due to the formation of the Bi₂S₃/BiVO₄ heterostructure. In addition, the Bi₂S₃/BiVO₄ samples showed relative stability and reusability. The simple method presented in this work could be used to fabricate composite photocatalysts with high activity for different applications, such as photocatalytic degradation of organic pollutants, photocatalytic splitting of water, and photocatalytic reduction of carbon dioxide.

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

一锅法合成在可见光下具有高效降解草甘膦的牡丹状Bi₂S₃/BiVO₄(040)复合光催化剂

English

One-pot synthesis of peony-like Bi₂S₃/BiVO₄(040) with high photocatalytic activity for glyphosate degradation under visible light irradiation

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