原位聚合PPy/g-C<sub>3</sub>N<sub>4</sub>复合物增强可见光催化性能

引用本文: 韩红桔, 傅敏, 李亚林, 关伟, 卢鹏, 胡雪利. 原位聚合PPy/g-C₃N₄复合物增强可见光催化性能[J]. 催化学报, 2018, 39(4): 831-840. doi: 10.1016/S1872-2067(17)62997-8 shu

Citation: Hongju Han, Min Fu, Yalin Li, Wei Guan, Peng Lu, Xueli Hu. In-situ polymerization for PPy/g-C₃N₄ composites with enhanced visible light photocatalytic performance[J]. Chinese Journal of Catalysis, 2018, 39(4): 831-840. doi: 10.1016/S1872-2067(17)62997-8 shu

原位聚合PPy/g-C₃N₄复合物增强可见光催化性能

韩红桔 ^a, ,
傅敏 ^a, ,
李亚林 ^b, ,
关伟 ^c, ,
卢鹏 ^a, ,
胡雪利 ^a,

a 重庆工商大学环境与资源学院, 重庆市催化与环境新材料重点实验室, 重庆 400067;
b 重庆市沙坪坝区环境监测站, 重庆 400031;
c 重庆文理学院, 重庆市环境材料与修复技术重点实验室, 重庆 402160
基金项目:
重庆市社会民生科技创新专项（cstc2016shmszx20012）；重庆市高校优秀成果转化资助项目（KJZH17122）；国家自然科学基金（5160080705）；重庆工商大学重点实验室开放项目（1556036）；重庆市教委科学技术研究项目（KJ130704）；重庆工商大学创新型科研项目（yjscxx2016-060-34）.

摘要: 近年发展起来的低能耗、高效率的光催化技术为解决环境污染和能源短缺等问题提供了新途径.在众多光催化材料中，非金属石墨相氮化碳（g-C₃N₄）半导体材料因其化学稳定性和热稳定性优异、能带结构易调控、前驱体价格低廉等特点备受关注.然而，g-C₃N₄的光生电子-空穴对极易复合，比表面积较小，不能充分利用太阳光等，因而其光催化活性较低.目前，为了提高g-C₃N₄光催化性能，多采用金属或非金属元素掺杂、与其他物质形成异质结、与其他半导体材料进行共聚合等方式.其中，共聚合有利于调节g-C₃N₄内部电子结构，促进g-C₃N₄光生载流子的分离与迁移，而且具有高度离域π-π^*共轭结构的导电聚合物更适合与g-C₃N₄进行共聚合，从而进一步提高g-C₃N₄的光催化性能.
本文采用原位聚合法制备合成了导电聚吡咯（PPy）与g-C₃N₄的复合材料，并以10mgL^-1亚甲基蓝（MB）作为目标污染物评价其可见光催化性能.经X射线衍射、扫描电镜、透射电镜、比表面积、紫外-可见光谱等一系列表征分析可知，PPy/g-C₃N₄复合物（002）晶面衍射峰强度较g-C₃N₄减弱，表明PPy抑制了g-C₃N₄晶型生长，但未影响其晶型结构.不规则薄片状g-C₃N₄表面均匀地负载有非晶态PPy颗粒，复合物微观形貌发生变化.PPy与g-C₃N₄共轭芳香环层间堆积形成的介孔、大孔孔径和孔容积均增加，比表面积增大了7m²g^-1，使目标污染物能与光催化剂表面活性物质充分接触反应.同时，PPy具有较强吸光系数，对可见光能完全吸收；PPy/g-C₃N₄复合物的可见光吸收边带发生红移，呈现出较g-C₃N₄更强的可见光吸收能力，提高对可见光的利用效率.
光催化降解MB实验结果表明，在可见光（12 W LED灯）照射2h后，含有0.75 wt% PPy的复合样品0.75PPy/g-C₃N₄表现出最佳光催化活性，MB降解效率为99%；且污染物光催化降解过程符合准一级动力学，反应速率常数（0.03773min^-1）约为同条件下g-C₃N₄（0.01284min^-1）的3倍.自由基捕获测试实验表明，g-C₃N₄和0.75PPy/g-C₃N₄均产生了·O₂^-自由基，但后者的·O₂^-信号更强.这是因为PPy也可吸收可见光并激发出电子，该电子转移到g-C₃N₄导带，再与其本身的电子共同与O₂反应生成·O₂^-.然而只有0.75PPy/g-C₃N₄在光催化过程中产生了·OH自由基，是由于g-C₃N₄的价带（+1.4eV）较H₂O/·OH（+2.38eVvs.NHE）和OH^-/·OH（+1.99eVvs.NHE）小，此价带上的h⁺不能与H₂O和OH^-反应生成·OH，而是由生成的·O₂^-再与e^-和H⁺反应产生，即·O₂^-+2H+2e_CB^-→·OH+OH^-.本文最后分析了以·O₂^-和·OH作为主要活性物质的PPy/g-C₃N₄复合物光催化降解污染物的反应机理，PPy具有强导电性，可作为光生电子和空穴的传输通道，抑制其在g-C₃N₄表面的复合.

关键词:

English

In-situ polymerization for PPy/g-C₃N₄ composites with enhanced visible light photocatalytic performance

Hongju Han ^a, ,
Min Fu ^a, ,
Yalin Li ^b, ,
Wei Guan ^c, ,
Peng Lu ^a, ,
Xueli Hu ^a,

a Chongqing Key Laboratory of Catalysis and New Environmental Materials, College of Environment and Resources, Chongqing Technology and Business University, Chongqing 400067, China;
b Chongqing Shapingba Environmental Monitoring Station, Chongqing 400031, China;
c Chongqing Key Laboratory of Environmental Materials & Remediation Technologies, Chongqing University of Arts and Sciences, Chongqing 402160, China
Received Date: 08 November 2017
Revised Date: 11 December 2017
Fund Project:
This work was supported by the Specialized Innovation of Social and People's Livelihood in Chongqing (cstc2016shmszx20012), Converting Outstanding Achievements of University-funded Projects of Chongqing (KJZH17122), National Natural Science Foundation of China (5160080705), Key Laboratory Open Project from CTBU (1556036), Scientific and Technological Research Program of Chongqing Municipal Education Commission (KJ130704), and Innovative Research Project from CTBU (yjscxx2016-060-34).

Abstract: Polypyrrole-modified graphitic carbon nitride composites (PPy/g-C₃N₄) are fabricated using an in-situ polymerization method to improve the visible light photocatalytic activity of g-C₃N₄. The PPy/g-C₃N₄ is applied to the photocatalytic degradation of methylene blue (MB) under visible light irradiation. Various characterization techniques are employed to investigate the relationship between the structural properties and photoactivities of the as-prepared composites. Results show that the specific surface area of the PPy/g-C₃N₄ composites increases upon assembly of the amorphous PPy nanoparticles on the g-C₃N₄ surface. Owing to the strong conductivity, the PPy can be used as a transition channel for electrons to move onto the g-C₃N₄ surface, thus inhibiting the recombination of photogenerated carriers of g-C₃N₄ and improving the photocatalytic performance. The elevated light adsorption of PPy/g-C₃N₄ composites is attributed to the strong absorption coefficient of PPy. The composite containing 0.75 wt% PPy exhibits a photocatalytic efficiency that is 3 times higher than that of g-C₃N₄in 2 h. Moreover, the degradation kinetics follow a pseudo-first-order model. A detailed photocatalytic mechanism is proposed with·OH and·O₂^- radicals as the main reactive species. The present work provides new insights into the mechanistic understanding of PPy in PPy/g-C₃N₄ composites for environmental 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

原位聚合PPy/g-C₃N₄复合物增强可见光催化性能

English

In-situ polymerization for PPy/g-C₃N₄ composites with enhanced visible light photocatalytic performance

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原位聚合PPy/g-C3N4复合物增强可见光催化性能

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In-situ polymerization for PPy/g-C3N4 composites with enhanced visible light photocatalytic performance

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