g-C3N4修饰β-ZnMoO4光催化降解磺胺二甲嘧啶:合成方法的影响、降解动力学及机理

doi:10.1016/S1872-2067(17)62935-8

催化学报 ›› 2017, Vol. 38 ›› Issue (12): 2009-2020.DOI: 10.1016/S1872-2067(17)62935-8

g-C₃N₄修饰β-ZnMoO₄光催化降解磺胺二甲嘧啶:合成方法的影响、降解动力学及机理

张婧^a, 毛旭辉^a, 肖巍^a, 庄艳峰^b

a 武汉大学资源与环境科学学院, 湖北省资源与能源可持续利用技术示范型国际科技合作基地, 湖北武汉 430079;
b 武汉大学土木建筑工程学院, 湖北武汉 430072

收稿日期:2017-09-11 修回日期:2017-10-19 出版日期:2017-12-18 发布日期:2017-12-29
通讯作者: 毛旭辉, 庄艳峰
基金资助:
国家自然科学基金（51778505）；湖北省技术创新重大专项（2016ACA162）；湖北省自然科学基金创新团队项目（2015CFA017）.

Photocatalytic degradation of sulfamethazine by graphitic carbon nitride-modified zinc molybdate: Effects of synthesis method on performance, degradation kinetics, and mechanism

Jing Zhang^a, Xuhui Mao^a, Wei Xiao^a, Yanfeng Zhuang^b

a School of Resources and Environmental Science, Hubei International Scientific and Technological Cooperation Base of Sustainable Resource and Energy, Wuhan University, Wuhan 430079, Hubei, China;
b School of Civil Engineering, Wuhan University, Wuhan 430072, Hubei, China

Received:2017-09-11 Revised:2017-10-19 Online:2017-12-18 Published:2017-12-29
Supported by:
This work was supported by the National Natural Science Foundation of China (51778505) and the grants from Hubei Province of China (Special Grant for Technological Innovation (2016ACA162), and the Natural Science Foundation, 2015CFA017).

摘要/Abstract

摘要：

在过去几十年中，钼酸盐在功能材料领域的应用备受关注.例如，半导体材料二价金属钼酸盐MMoO₄（M=Ca，Mg，Zn）在发光、催化、电容器、闪烁探测器等方面已有良好的应用.研究表明，钼酸锌在紫外或可见光照射下能够有效降解甲基橙、维多利亚蓝、苯酚等污染物.中国拥有丰富的钼资源，目前钼主要用于生产高强度钢.制备钼基高效除污除材料可作为钼资源的另一种高附加值利用模式.氮化碳（g-C₃N₄）作为一种低成本的光活性改性剂，可提高半导体材料的光催化性能.迄今为止，基于氮化碳复合材料的制备方法包括：原位水热合成、超声波复合、一步升温合成和沉淀法等.然而，很少讨论合成方法对复合材料性能的影响.本文以β-ZnMoO₄为主体材料，g-C₃N₄为修饰材料，首次制备了两者复合的新型光催化剂.采用不同的方法和条件制备了β-ZnMoO₄和β-ZnMoO₄/C₃N₄复合材料，探讨了合成方法对复合材料光催化性能的影响，并进一步研究了材料光催化降解磺胺二甲嘧啶的动力学和降解途径.
以钼酸钠和硝酸锌为原料，在不同温度和时间条件下，采用水热法合成得到了两种不同形貌的β-ZnMoO₄材料.光催化降解实验结果显示，水热合成条件对催化剂的光催化活性影响很大，280 ℃水热条件下维持24 h，得到表面光滑的不规则微米颗粒（β-ZnMoO₄-280），其光催化活性高于180 ℃条件下获得的片状形貌的钼酸锌材料（β-ZnMoO₄-180）.β-ZnMoO₄/C₃N₄复合材料通过原位水热法和超声法合成，结果显示，原位水热合成条件下获得的β-ZnMoO₄-180/C₃N₄光催化剂对磺胺二甲嘧啶表现出显著增强的降解能力.相比之下，在280 ℃水热条件下，C₃N₄颗粒发生逐步分解，且反应开始时C₃N₄颗粒会扰乱β-ZnMoO₄-280晶体生长的连续性，使复合材料性能下降.对于超声法合成的β-ZnMoO₄/C₃N₄材料，两种β-ZnMoO₄/C₃N₄复合材料的光催化活性均提高，但提高程度不及水热法180 ℃条件下制备的材料.结果表明，对于光催化复合材料的制备，要选择适当的合成方法，才能得到高性能复合光催化材料，本文采用180 ℃的水热合成条件，添加3% g-C₃N₄，可得到性能最佳的β-ZnMoO₄-180/C₃N₄复合光催化剂.
添加自由基抑制剂的光催化降解实验结果表明，超氧负离子（·O₂^-）和空穴（h⁺）在降解中起主导作用.β-ZnMoO₄/C₃N₄复合材料光催化活性的增强归因于C₃N₄与β-ZnMoO₄之间形成异质结，该异质结提高了光生电子-空穴对的分离效率.通过液相-质谱联用手段，测定了磺胺二甲嘧啶降解的中间产物，结果表明，污染物的光催化降解途径主要包括脱氨基和脱甲基过程.

关键词: 钼酸锌, 石墨相氮化碳, 光催化, 磺胺二甲嘧啶, 水处理

Abstract:

In the present study, zinc molybdate (β-ZnMoO₄) and graphitic carbon nitride (g-C₃N₄)-modified β-ZnMoO₄ (β-ZnMoO₄/g-C₃N₄) were prepared to decontaminate aqueous solutions from the antibiotic sulfamethazine (SMZ). Our results revealed that the hydrothermal synthesis method greatly influenced the photocatalytic activity of the resultant catalysts. The pristine β-ZnMoO₄ samples obtained under more intensive synthesis conditions (24 h at 280℃) showed higher photocatalytic activity than that prepared for 12 h at 180℃ (denoted β-ZnMoO₄-180). In the case of in situ hydrothermal synthesis of β-ZnMoO₄/g-C₃N₄, a surface-modified sample was only obtained under the reaction conditions of 180℃ for 12 h. Compared with the sheet-like β-ZnMoO₄-180 sample, the β-ZnMoO₄-180/g-C₃N₄ composite showed enhanced photocatalytic activity for the degradation of SMZ. By contrast, the hydrothermal reaction at 280℃ caused the gradual decomposition of g-C₃N₄. It is believed that the structural incorporation of g-C₃N₄ into β-ZnMoO₄ at 280℃ might disrupt the crystal growth, thereby deteriorating the performance of the composite catalysts formed at this temperature. For the composite catalysts prepared by the ultrasonic method, a remarkable increase in the degradation rate of SMZ was only observed at a high g-C₃N₄ content of 8 mol%. The photocatalytic degradation of SMZ by β-ZnMoO₄-180/g-C₃N₄ composite catalysts followed pseudo-first-order kinetics. Further study of the photocatalytic mechanism revealed that holes and superoxide radicals were the dominant oxidative species in the photodegradation process. The enhanced photocatalytic performance of the composites was attributed to the higher separation efficiency of the photogenerated electron-hole pairs at heterogeneous junctions. The degradation intermediates of SMZ were detected by liquid chromatography-mass spectrometry, from which plausible reaction pathways for the photodegradation of SMZ were proposed. Our results indicated that the synthesis method for g-C₃N₄ composites should be care-fully selected to achieve superior photocatalytic performance.

Key words: Zinc molybdate, Graphitic carbon nitride, Photocatalysis, Sulfamethazine, Water treatment

张婧, 毛旭辉, 肖巍, 庄艳峰. g-C₃N₄修饰β-ZnMoO₄光催化降解磺胺二甲嘧啶:合成方法的影响、降解动力学及机理[J]. 催化学报, 2017, 38(12): 2009-2020.

Jing Zhang, Xuhui Mao, Wei Xiao, Yanfeng Zhuang. Photocatalytic degradation of sulfamethazine by graphitic carbon nitride-modified zinc molybdate: Effects of synthesis method on performance, degradation kinetics, and mechanism[J]. Chinese Journal of Catalysis, 2017, 38(12): 2009-2020.

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g-C₃N₄修饰β-ZnMoO₄光催化降解磺胺二甲嘧啶:合成方法的影响、降解动力学及机理

Photocatalytic degradation of sulfamethazine by graphitic carbon nitride-modified zinc molybdate: Effects of synthesis method on performance, degradation kinetics, and mechanism

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