三元磁性氮化碳复合光催化剂的制备和表征及其在可见光下去除四环素的应用

doi:10.1016/S1872-2067(16)62591-3

摘要/Abstract

摘要：

g-C₃N₄作为一种新型有机半导体材料，由于其良好的化学稳定性和可直接利用可见光等优点已经引起了人们的广泛关注，近年来已逐渐将其应用于光催化氧化环境污染物等方面.同时在实际应用中因其光能利用率低、难回收、电子-空穴易复合等缺点也受到了限制.研究发现将四氧化三铁与氮化碳相结合，可以有效提高复合催化剂的光催化活性，而且可回收再利用很大程度上降低成本.采用光催化氧化技术处理实际环境污染物废水时，将光催化剂投入到废水中后，环境及水体的温度往往会对催化剂的催化活性产生一定的影响，导致无法实现最佳的光催化处理效果.制备一种催化活性不受外界温度影响的智能光催化材料是当今面临的一项挑战.我们研究制备了一种具有温度响应的磁性复合光催化剂PNIPAM/Fe₃O₄/g-C₃N₄，其可根据外界温度的不同而表现出不同的光催化活性.温敏型聚合物PNIPAM是一类结构、性能和形态随温度变化而做出响应的功能材料，将光催化材料与温敏型PNIPAM智能高分子材料相结合，实现了智能催化的效果.PNIPAM温敏聚合物在水溶液中存在一个低临界溶解温度，其可以作为开关，通过改变温度实现对光催化过程的控制，达到过程智能化的效果.随着温度的改变，温敏聚合物的溶解状态在临界点附近会发生变化.不同温度对催化速率影响很大，当温度升高到临界值以上，催化反应速率降低很多；当温度降低到临界值以下，催化活性随之升高.这样不仅随时控制反应的进行，还可以通过改变温度控制反应速率.同时，温敏聚合层又相当于一个保护层，可以增强其抗腐蚀能力，提高对内部光催化材料的保护，进而提高其稳定性. 众所周知四环素等抗生素类药物生产废水，属于高浓度有机废水，具有一定的毒性，一般较难处理. 我们将制备的PNIPAM/Fe₃O₄/g-C₃N₄复合光催化材料用于四环素废水的处理取得了很好的效果.
XRD，FT-IR、Raman等表征手段充分证明了我们所制备的三元复合材料PNIPAM/Fe₃O₄/g-C₃N₄的组成及各个组分的存在.并对PNIPAM/Fe₃O₄/g-C₃N₄复合光催化剂在不同温度（20和45℃）条件下处理四环素废水进行了系统的研究，从20和45℃的吸附曲线结果可以看出，低温时PNIPAM/Fe₃O₄/g-C₃N₄的吸附性较强，高温时吸附较差.同时PNIPAM/Fe₃O₄/g-C₃N₄低温时具有较高的催化活性，高温时催化活性较低.经过分析可知这种对温度响应的特殊性能与PNIPAM的亲水及疏水性密切相关.另外，通过对PNIPAM/Fe₃O₄/g-C₃N₄复合材料的VSM测试及5次循环实验测试可以看出，PNIPAM/Fe₃O₄/g-C₃N₄复合材料由于Fe₃O₄的引入而表现出较好的磁性，且在外加磁铁的作用下很容易实现分离回收.另外，PNIPAM/Fe₃O₄/g-C₃N₄在经过5次重复利用后其催化活性几乎没有减退，说明催化剂具有很好的稳定性.另一方面，说明我们的复合光催化剂在工业废水等污染治理方面有一定的潜在应用价值.

关键词: 四氧化三铁/氮化碳, 四环素, 磁性, 中间产物, 光催化剂

Abstract:

A stable PNIPAM/Fe₃O₄/g-C₃N₄ composite photocatalyst was designed and prepared by a thermal photoinitiation technology. The structure and properties of the materials were characterized and the composite photocatalyst was found to show good stability for tetracycline degradation. The sample not only retained the magnetic properties of Fe₃O₄, allowing it to be recycled, but its photocatalytic properties could also be changed by controlling the temperature of the reaction system. The degradation intermediate products of tetracycline were further investigated by MS. This work provides a new facile strategy for the development of intelligent and recyclable photocatalytic materials.

Key words: Fe₃O₄/g-C₃N₄, Tetracycline, Magnetism, Intermediate products, Photocatalyst

唐旭, 倪良, 韩娟, 王赟. 三元磁性氮化碳复合光催化剂的制备和表征及其在可见光下去除四环素的应用[J]. 催化学报, 2017, 38(3): 447-457.

Xu Tang, Liang Ni, Juan Han, Yun Wang. Preparation and characterization of ternary magnetic g-C₃N₄ composite photocatalysts for removal of tetracycline under visible light[J]. Chinese Journal of Catalysis, 2017, 38(3): 447-457.

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https://www.cjcatal.com/CN/Y2017/V38/I3/447

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