热响应型PNIPAM@Ag/Ag<sub>3</sub>PO<sub>4</sub>/CN复合光催化剂的制备及性能

引用本文: 孙林林, 周亚举, 李鑫, 李金择, 沈东, 尹世康, 王会琴, 霍鹏伟, 闫永胜. 热响应型PNIPAM@Ag/Ag₃PO₄/CN复合光催化剂的制备及性能[J]. 催化学报, 2020, 41(10): 1573-1588. doi: 10.1016/S1872-2067(20)63554-9 shu

Citation: Linlin Sun, Yaju Zhou, Xin Li, Jinze Li, Dong Shen, Shikang Yin, Huiqin Wang, Pengwei Huo, Yongsheng Yan. Thermo-responsive functionalized PNIPAM@Ag/Ag₃PO₄/CN-heterostructure photocatalyst with switchable photocatalytic activity[J]. Chinese Journal of Catalysis, 2020, 41(10): 1573-1588. doi: 10.1016/S1872-2067(20)63554-9 shu

热响应型PNIPAM@Ag/Ag₃PO₄/CN复合光催化剂的制备及性能

孙林林 ^a, ,
周亚举 ^a, ,
李鑫 ^a, ,
李金择 ^a, ,
沈东 ^a, ,
尹世康 ^a, ,
王会琴 ^b, ,
霍鹏伟 ^a, ,
闫永胜 ^a,

a 江苏大学化学化工学院绿色化学与化学技术研究所, 江苏镇江 212013;
b 江苏大学能源与动力工程学院, 江苏镇江 212013
基金项目:
国家自然科学基金（21576125和21776117）；中国博士后科学基金（2017M611734）；江苏省六大人才高峰项目（XCL-014）.

摘要: 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20mg·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120min，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.

关键词:

English

Thermo-responsive functionalized PNIPAM@Ag/Ag₃PO₄/CN-heterostructure photocatalyst with switchable photocatalytic activity

a Institute of Green Chemistry and Chemical Technology, School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013, Jiangsu, China;
b School of Energy and Power Engineering, Jiangsu University, Zhenjiang 212013, Jiangsu, China
Received Date: 25 February 2020
Revised Date: 21 March 2020
Fund Project:
This work was supported by the National Natural Science Foundation of China (21576125 and 21776117), the China Postdoctoral Science Foundation (2017M611734), and the Six Talent Peaks Project in Jiangsu Province (XCL-014).

Abstract: 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.

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

热响应型PNIPAM@Ag/Ag₃PO₄/CN复合光催化剂的制备及性能

English

Thermo-responsive functionalized PNIPAM@Ag/Ag₃PO₄/CN-heterostructure photocatalyst with switchable photocatalytic activity

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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中国化学会秘书处

热响应型PNIPAM@Ag/Ag3PO4/CN复合光催化剂的制备及性能

English

Thermo-responsive functionalized PNIPAM@Ag/Ag3PO4/CN-heterostructure photocatalyst with switchable photocatalytic activity

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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热响应型PNIPAM@Ag/Ag₃PO₄/CN复合光催化剂的制备及性能

Thermo-responsive functionalized PNIPAM@Ag/Ag₃PO₄/CN-heterostructure photocatalyst with switchable photocatalytic activity

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