单层ZIF67纳米颗粒修饰的C<sub>3</sub>N<sub>4</sub>在可见光下光催化降解有机污染物

引用本文: 苏佩东, 张俊珂, 肖轲, 赵燊, Ridha Djellabi, 李学伟, 杨波, 赵旭. 单层ZIF67纳米颗粒修饰的C₃N₄在可见光下光催化降解有机污染物[J]. 催化学报, 2020, 41(12): 1894-1905. doi: 10.1016/S1872-2067(20)63620-8 shu

Citation: Peidong Su, Junke Zhang, Ke Xiao, Shen Zhao, Ridha Djellabi, Xuewei Li, Bo Yang, Xu Zhao. C₃N₄ modified with single layer ZIF67 nanoparticles for efficient photocatalytic degradation of organic pollutants under visible light[J]. Chinese Journal of Catalysis, 2020, 41(12): 1894-1905. doi: 10.1016/S1872-2067(20)63620-8 shu

单层ZIF67纳米颗粒修饰的C₃N₄在可见光下光催化降解有机污染物

苏佩东 ^a,b, ,
张俊珂 ^a, ,
肖轲 ^c, ,
赵燊 ^b, ,
Ridha Djellabi ^a, ,
李学伟 ^a,b, ,
杨波 ^a, ,
赵旭 ^b,

a 深圳大学化学与环境工程学院, 广东深圳 518060, 中国;
b 中国科学院生态环境研究中心, 中国科学院饮用水科学与技术重点实验室, 北京 100085, 中国;
c 杰克逊州立大学土木与环境工程学院, 杰克逊 39217, 美国
基金项目:
国家自然科学基金（21707154）；国家重大水污染控制科学技术计划（2017ZX07202）.

摘要: 随着全球工业化水平的提高，有机污染物引起的水环境问题也日益严重.针对有机污染物表现出的持久性和难降解性等问题，全球科研工作者提出了不同的方法去治理相关环境问题.其中利用光催化降解有机污染物作为一种新兴技术，因处理成本低、污染物降解效率高、光催化剂可回收利用等优点受到越来越多的关注.在诸多的光催化剂中，氮化碳（C₃N₄）拥有2.7eV的能带宽度，且其合成简单，价格低廉，环境友好，以及在可见光下即可催化降解污染物等特点而被广泛研究.但是，比表面积小和易与光激发电荷载流子结合等缺点也制约C₃N₄的广泛应用.针对上述问题，本文将具有巨大比表面积的金属骨架材料ZIF67引入到C₃N₄之中，合成了均匀分布的单层ZIF67衍生的C₃N₄（ZIF67-C₃N₄），并将其应用于可见光下的亚甲基蓝（MB）光催化降解.结果表明，所制得的ZIF67-C₃N₄的最大比表面积可达541.392m²/g，远高于未加工的C₃N₄的97.291m²/g.ZIF67-C₃N₄光催化活性结果表明，2.57g ZIF67和0.3g C₃N₄即ZIF67-C₃N₄（0.3）表现出优异的光催化活性.加入0.01g的ZIF67-C₃N₄（0.3）可以在70min内降解90%以上的浓度为10mg/L的亚甲基蓝，而原C₃N₄在同等条件下处理相同浓度的亚甲基蓝所需的时间超过140min.同时，本文还考察了溶液的pH值，亚甲基蓝的初始浓度和ZIF67-C₃N₄复合材料中C₃N₄的含量等因素对亚甲基蓝光催化降解的影响.结果显示，ZIF67-C₃N₄（0.3）在碱性条件下降解亚甲基蓝的效率高于中性条件.在pH=12的情况下，ZIF67-C₃N₄（0.3）可以在10min内完全降解100mL的浓度为10mg/L的亚甲基蓝.此外，在酸性条件下亚甲基蓝的降解效果很差，说明ZIF67-C₃N₄（0.3）在酸性条件下容易失活.通过对亚甲基蓝初始浓度对光催化反应的研究显示，当亚甲基蓝的初始浓度为20mg/L时，经140min反应后，亚甲基蓝的去除率小于90%；当亚甲基蓝的浓度降至15 mg/L时，其在120min的降解效率超过92%；而10mg/L的亚甲基蓝可在120min内完全降解.对制备的五种催化剂对亚甲基蓝的降解效果分析得出ZIF67-C₃N₄（0.3）比其他四种催化剂的效果更好.为了揭示ZIF67-C₃N₄（0.3）在可见光条件下催化降解亚甲基蓝的反应机理，本文利用叔丁醇、甲酸以及对苯醌进行淬灭实验.结果表明，光致空穴（h⁺）和超氧自由基（O₂^-·）是降解亚甲基蓝的主要活性物质.

关键词:

English

C₃N₄ modified with single layer ZIF67 nanoparticles for efficient photocatalytic degradation of organic pollutants under visible light

a College of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen 518060, Guangdong, China;
b Key Laboratory of Drinking Water Science and Technology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, China;
c Department of Civil and Environmental Engineering, Jackson State University, Jackson, MS 39217, USA
Received Date: 05 March 2020
Revised Date: 17 April 2020
Fund Project:
This work was jointly funded by the National Natural Science Foundation of China (21707154) and the National Major Science & Technology Program for Water Pollution Control & Treatment (2017ZX07202).

Abstract: Uniformly distributed single layer of ZIF67-derived C₃N₄ (ZIF67-C₃N₄) was synthesized and applied to the photocatalytic degradation of methylene blue (MB) under visible light. Results indicated that the obtained ZIF67-C₃N₄has a maximum specific surface area of 541.392 m²/g, which is much larger than that of raw C₃N₄ of 97.291 m²/g. The investigation of C₃N₄ amount involved in ZIF67-C₃N₄on the photoactivity revealed that 2.57 g ZIF67 with 0.3 g C₃N₄, which named ZIF67-C₃N₄(0.3) exhibited superior photocatalytic activities. More than 90% of MB at 10 mg/L was degraded within 70 min with the addition of 0.01 g ZIF67-C₃N₄(0.3), while this time required for raw C₃N₄ was over 140 min. The effects of pH of solution, initial concentration of MB and dosage of C₃N₄ in ZIF67-C₃N₄composites on the photocatalytic efficiency for MB degradation were also evaluated. Quenching experiments indicated that the photo-induced holes (h⁺) and superoxide radicals (O^2-·) were mainly responsible for MB degradation. It is anticipated that the insertion of ZIF67 nanoparticles not only increases the adsorption capacity of C₃N₄ but also promotes the generation and migration of the photo-induced active species.

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

单层ZIF67纳米颗粒修饰的C₃N₄在可见光下光催化降解有机污染物

English

C₃N₄ modified with single layer ZIF67 nanoparticles for efficient photocatalytic degradation of organic pollutants under visible light

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CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

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中国化学会秘书处

单层ZIF67纳米颗粒修饰的C3N4在可见光下光催化降解有机污染物

English

C3N4 modified with single layer ZIF67 nanoparticles for efficient photocatalytic degradation of organic pollutants under visible light

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

单层ZIF67纳米颗粒修饰的C₃N₄在可见光下光催化降解有机污染物

C₃N₄ modified with single layer ZIF67 nanoparticles for efficient photocatalytic degradation of organic pollutants under visible light

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