摘要
It is extremely important for photocatalysts to exhibit intelligent responsiveness to their environment. Herein, a poly N-isopropyl acrylamide(PNIPAM)-modified Ag/Ag3PO4-20/CN hybrid material with excellent convertible photocatalytic activity is prepared. PNIPAM has good hydrophilicity below the lower critical solution temperature(LCST);this increases the capacity of the photocatalyst for adsorbing tetracycline(TC) molecules. In addition, the PNIPAM-modified Ag/Ag3PO4-20/CN can prevent the loss of Ag3PO4. The dispersity is improved by loading g-C3N4 nanosheets(CN) for enhancing the efficiency of photocatalytic activity. Furthermore, a Z-scheme heterostructure is formed between CN and Ag3PO4, accelerating the separation efficiency of the holes and electrons. Ag nanoparticles can be used as electron-shuttle mediators, and electrons receiving more energy are transferred via the localized surface plasmon resonance(LSPR) effect. Furthermore, the PNIPAM@Ag/Ag3PO4-20/CN photocatalyst exhibits an excellent degradation rate for the degradation of TC when the temperature is lower than the LCST. The photoluminescence spectra and photocurrent curves prove that the carrier-separation efficiency of PNIPAM@Ag/Ag3PO4-20/CN is higher than those of Ag/Ag3PO4/CN and CN. The main active species of ·O2-and h+ are detected to reveal the plausible mechanism of the PNIPAM@Ag/Ag3PO4-20/CN hybrid material system. This work provides a way to develop intelligent materials for switchable photocatalytic applications.
近年来,在银盐半导体光催化剂的研究过程中, Ag3PO4由于具有各向同性分布、强氧化性和优异的可见光吸收能力等优点,引起了人们的广泛关注.Ag3PO4在反应过程中生成的Ag纳米颗粒会产生等离子体共振效应,对可见光驱动的光催化过程起积极作用.但是,在催化剂制备过程中Ag3PO4颗粒容易发生团聚,这限制了光催化降解过程中催化剂的反应活性.片状g-C3N4具有较大的比表面积,可对Ag3PO4颗粒起到良好的分散作用,并为反应提供更多活性位点.此外, g-C3N4与Ag3PO4能够形成Z-型异质结,提高电子与空穴的分离效率.在光催化降解污染物过程中,周围环境对催化剂性能具有显著影响,构建对环境具有响应性的光催化剂,实现环境调控光解过程对于理解光催化降解机理具有重要意义.聚N-异丙基丙烯酰胺(PNIPAM)是一种温度响应型聚合物,在LCST(32℃)附近具有可逆的亲水性至疏水性转化.随着温度降低, PNIPAM亲水性增加,显示出从收缩团聚到拉伸溶胀状态的变化.PNIPAM还可以用作保护层包裹在Ag3PO4颗粒表面,防止Ag3PO4颗粒在反应过程的损失.本文采用沉淀法和乳液聚合法合成了热响应型PNIPAM@Ag/Ag3PO4/CN复合光催化剂,并以20 mg·L-1四环素(TC)作为目标污染物探究其对温度可逆转换的光催化性能.通过X射线衍射(XRD)、X射线光电子能谱(XPS)、扫描电镜(SEM)、透射电镜(TEM)、荧光(PL)、接触角测试等一系列表征对该催化剂的结构特征、微观形貌、光学性能和亲疏水性进行了分析.由XRD可知, Ag/Ag3PO4/CN复合物和PNIPAM@Ag/Ag3PO4/CN具有相同的衍射峰强度和位置,表明PNIPAM未影响Ag/Ag3PO4/CN复合物的晶型结构.XPS结果表明,复合材料含有Ag, P, O, C和N.由SEM和TEM可知, PNIPAM已将Ag/Ag3PO4/CN复合物成功包裹.接触角测试表明, PNIPAM@Ag/Ag3PO4/CN在25℃表现出亲水性,在45℃呈现疏水性.光催化性能测试结果进一步表明, PNIPAM@Ag/Ag3PO4/CN实现了在不同温度下的光催化可逆转换性能:25℃时照射120min, TC降解效率可达88.96%;45℃时照射120 min, TC降解效率是56.73%.此外,对催化剂进行了循环实验,经过4次循环后催化剂仍具有优异的光催化降解性能,表明所制备的催化剂具有良好的稳定性.为了进一步研究PNIPAM@Ag/Ag3PO4/CN光催化剂的光催化机理,用抗坏血酸、乙二胺四乙酸和异丙醇进行了自由基捕获实验.结果表明,超氧自由基和羟基自由基在降解TC过程中起主要作用.通过价带谱测试和带隙计算出材料的价导带位置,计算出的导带位置与莫特肖基曲线测试结果一致.最后,对可能的机理进行了分析.总之,PNIPAM@Ag/Ag3PO4/CN光催化剂不仅实现了对降解过程不同温度的响应性,还可防止Ag3PO4颗粒团聚和光腐蚀,提高了电子-空穴对的传输速率.这为环境响应型复合光催化剂的制备提供了一种策略.
基金
国家自然科学基金(21576125,21776117)
中国博士后科学基金(2017M611734)
江苏省六大人才高峰项目(XCL-014).
