具有高电催化活性的g-C<sub>3</sub>N<sub>4</sub>-ZnS-DNA纳米复合材料的制备及应用

引用本文: 周鑫, 邹菁, 张胜, 潘敏, 龚晚芸. 具有高电催化活性的g-C₃N₄-ZnS-DNA纳米复合材料的制备及应用[J]. 催化学报, 2017, 38(2): 287-295. doi: 10.1016/S1872-2067(16)62582-2 shu

Citation: Xin Zhou, Jing Zou, Sheng Zhang, Ming Pan, Wanyun Gong. Preparation and application of g-C₃N₄-ZnS-DNA nanocomposite with enhanced electrocatalytic activity[J]. Chinese Journal of Catalysis, 2017, 38(2): 287-295. doi: 10.1016/S1872-2067(16)62582-2 shu

具有高电催化活性的g-C₃N₄-ZnS-DNA纳米复合材料的制备及应用

武汉工程大学化学与环境工程学院, 绿色化学过程教育部重点实验室, 湖北武汉 430205
基金项目:
国家自然科学基金（21471122），武汉工程大学研究生教育创新基金及校长基金（CX2015147，2016062）.

摘要: g-C₃N₄作为丰富的可见光光催化剂，具有独特的二维结构，优异的化学稳定性和可调的电子结构；但因其激子结合能高和结晶度较低，导致其光催化过程量子效率偏低，限制了光催化剂的推广应用.根据g-C₃N₄独特的可调电子结构，将其与半导体材料进行耦合，形成异质结构，通过调控半导体的能带结构，优化其光吸收能力，促进光生电子-空穴对的快速分离，从而抑制光生载流子的复合，提高其光催化效率.目前，人们已发展了许多g-C₃N₄与窄禁带和宽禁带半导体耦合形成的二元纳米复合材料，广泛应用于光催化降解污染物、光催化水解产氢和光催化还原将温室气体CO₂转换成有用的碳氢燃料等方面，但关于g-C₃N₄基的三元复合光催化剂，尤其与天然纳米材料DNA复合，研究其电催化性能的却鲜有报道.近年来，随着环境污染日益严重，被称为环境激素的五氯酚（PCP）、壬基酚（NP）等一系列环境激素在水体和土壤等环境介质中长期残留，难以降解，且容易聚集在生物体内，通过空气循环和食物链等方式进入人体，对环境和人体产生极大的危害，所以越来越多的人致力于环境激素的高效筛选和检测的研究.常规的分析方法已经很难满足人们对环境激素的高灵敏检测的要求，而电化学方法因其操作简单、成本低廉、选择性好、灵敏度高、样品前处理简单等特点而备受关注.
本文成功设计和制备了g-C₃N₄-ZnS-DNA三元纳米复合材料.首先，采用水热法制备了ZnS半导体纳米片，采用热解法制备了g-C₃N₄纳米片，接着将它们与DNA复合，成功制备了g-C₃N₄-ZnS-DNA纳米复合材料，通过苯胺聚合法修饰到玻碳电极表面，成功构建了NP和PCP环境激素新型的电化学传感器.通过透射电镜、X射线衍射、紫外-可见漫反射光谱和X射线光电子能谱等对其形貌、结构及组分进行了表征.采用CHI660C仪器对新型的电化学传感器的电催化性能进行了系统研究.通过循环伏安法（CV）和示差脉冲伏安法（DPV）研究了NP和PCP在g-C₃N₄-ZnS-DNA-GCE修饰电极的上的电化学行为.
电化学阻抗谱表明，g-C₃N₄-ZnS-DNA纳米复合材料大大促进了修饰电极的电子传递能力，与g-C₃N₄膜相比，ZnS和DNA共掺杂的g-C₃N₄膜对NP和PCP的电化学响应明显提高，峰电流是g-C₃N₄膜的2倍，电催化活性明显增强.在最优化条件下，NP和PCP检测的线性范围分别为2.0×10^-5-1.0×10^-8和1.0×10^-5-1.0×10^-8 mol L^-1，检出限均为3.3×10^-9 mol L^-1.将g-C₃N₄-ZnS-DNA-GCE修饰电极用于湖水中NP和PCP的测定，其回收率均高于90%，证明g-C₃N₄-ZnS-DNA纳米复合材料修饰电极可应用实际水样中痕量环境激素的测定.同时，我们分析了电催化活性增强的原因：（1）DNA分子通过C-O-C键连接到g-C₃N₄表面，导致ZnS纳米片组装成线性超结构，形成稳定的g-C₃N₄-ZnS-DNA纳米复合材料；（2）由于DNA和PCP或NP之间的相互作用使得电极表面上的PCP和NP的浓度增加；（3）纳米复合材料聚苯胺膜可促进电子转移和加速PCP或NP向电极表面的扩散；并提出了Z型g-C₃N₄-ZnS-DNA纳米复合材料的电子转移路径，以及PCP和NP的可能的电催化氧化机理.

关键词:

English

Preparation and application of g-C₃N₄-ZnS-DNA nanocomposite with enhanced electrocatalytic activity

School of Chemistry and Environmental Engineering, Key Laboratory for Green Chemical Process of Ministry of Education, Wuhan Institute of Technology, Wuhan 430205, Hubei, China
Received Date: 29 September 2016
Revised Date: 24 October 2016
Available Online: 02 March 2017
Fund Project:
This work was supported by the National Natural Science Foundation of China (21471122) and Graduate Student Education Innovation Fundation and President Foundation of Wuhan Institute of Technology (CX2015147, 2016062).

Abstract: We successfully designed and prepared a g-C₃N₄-ZnS-DNA nanocomposite by a simple method and systematically investigated its morphology, microstructure, and electrocatalytic properties. The as-prepared g-C₃N₄-ZnS-DNA nanocomposite possessed the electrocatalytic activity of g-C₃N₄-ZnS and the conductivity of DNA. The presence of DNA was found to enhance the electrocatalytic response of the nanocomposite towards environmental hormones, e.g. pentachlorophenol and nonylphenol, owing to the interaction between g-C₃N₄-ZnS and DNA, indicating that a stable nanocomposite was formed. The three components showed synergistic effects during electrocatalysis. Electrochemical impedance spectra indicated that the g-C₃N₄-ZnS-DNA nanocomposite dramatically facilitated the electron transfer of a modified electrode. The co-doping of g-C₃N₄ film with ZnS and DNA doubled the electrochemical response of the modified electrode in comparison with that of unmodified g-C₃N₄ film. The detection limits (3 S/N) of pentachlorophenol and nonylphenol were 3.3×10^-9 mol L^-1. Meanwhile, we propose a possible Z-scheme mechanism for electron transfer in the g-C₃N₄-ZnS-DNA nanocomposite and the possible pentachlorophenol and nonylphenol electrocatalytic oxidation mechanism. The g-C₃N₄-ZnS-DNA nanocomposite-modified electrode was demonstrated to be effective for electrochemical sensing of trace environmental hormones in water samples.

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

具有高电催化活性的g-C₃N₄-ZnS-DNA纳米复合材料的制备及应用

English

Preparation and application of g-C₃N₄-ZnS-DNA nanocomposite with enhanced electrocatalytic 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

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中国化学会秘书处

具有高电催化活性的g-C3N4-ZnS-DNA纳米复合材料的制备及应用

English

Preparation and application of g-C3N4-ZnS-DNA nanocomposite with enhanced electrocatalytic 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

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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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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

具有高电催化活性的g-C₃N₄-ZnS-DNA纳米复合材料的制备及应用

Preparation and application of g-C₃N₄-ZnS-DNA nanocomposite with enhanced electrocatalytic activity

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