二维g-C3N4表面Au粒子尺寸调节的界面电子传输行为及光催化性能

doi:10.1016/S1872-2067(19)63347-4

催化学报 ›› 2019, Vol. 40 ›› Issue (6): 928-939.DOI: 10.1016/S1872-2067(19)63347-4

二维g-C₃N₄表面Au粒子尺寸调节的界面电子传输行为及光催化性能

李鑫^a, 刘重阳^a, 吴东遥^a, 李金择^a, 霍鹏伟^a, 王会琴^b

a 江苏大学化学化工学院绿色化学与化工技术研究院, 江苏镇江 212013;
b 江苏大学能源与动力工程学院, 江苏镇江 212013

收稿日期:2018-12-09 修回日期:2019-03-01 出版日期:2019-06-18 发布日期:2019-04-26
通讯作者: 霍鹏伟, 王会琴
基金资助:
国家自然科学基金（21776117，21576125）；中国博士后科研基金（2017M611716，2017M611734）；江苏省六大人才高峰工程（XCL-014）；镇江科技计划（SH2016012）.

Improved charge transfer by size-dependent plasmonic Au on C₃N₄ for efficient photocatalytic oxidation of RhB and CO₂ reduction

Xin Li^a, Chongyang Liu^a, Dongyao Wu^a, JinZe Li^a, Pengwei Huo^a, Huiqin Wang^b

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:2018-12-09 Revised:2019-03-01 Online:2019-06-18 Published:2019-04-26
Contact: S1872-2067(19)63347-4
Supported by:
This work was supported by the National Natural Science Foundation of China (21776117 and 21576125), China Postdoctoral Science Foundation (2017M611716 and 2017M611734), Six Talent Peaks Project in Jiangsu Province (XCL-014), and Zhenjiang Science and Technology Program (SH2016012).

摘要/Abstract

摘要：

目前，环境污染与能源危机是直接影响着人类生存与发展的两大难题.以半导体材料作为催化剂、太阳能作为驱动力的光催化技术由于具有成本低廉、清洁环保、反应条件温和等优点被认为是解决上述问题最具开发价值的理想方法，并得到科研工作者的广泛研究与关注.近几十年的研究表明，该技术在有机污水处理及光催化还原CO₂转化成高能燃料领域均有良好表现.本文采用高温热聚合及酸处理剥离技术，以尿素作为原料，成功制备出薄层二维g-C₃N₄（CN）纳米片材料，并以该材料作为载体及催化主体，通过恒温水浴还原技术在其表面负载不同尺寸的Au纳米粒子，成功制备出一系列Au/CN复合光催化材料.
运用系统的表征及测试手段，对所制备的二维光催化材料的晶相结构、化学组分、形貌和表面特征及光电化学特性进行了详细表征与研究，并针对该二维材料表面Au纳米粒子的尺寸效应、表面效应和等离子体共振效应（LSPR）等特性研究了复合材料界面间电子的传输效率与迁移机制.尺寸较小的Au纳米粒子的费米能级到CN导带底端的距离较短，其表面原子比例及缺陷含量较高，有利于Au纳米粒子对光生电子的捕获并抑制电子空穴对的复合.由于LSPR效应，可见光下Au表面可产生大量高能热电子并注入到CN表面，从而抑制光生电子从CN导带到Au表面的传输.三维时域有限差分法（FDTD）模拟结果显示，Au纳米颗粒的尺寸越大，拥有的LSPR效应越强，其表面热电子含量越高，光电子传输抑制现象越强烈.光电化学性能分析（PEC）结果显示，在颗粒分布密度合理的情况下，具有较小尺寸Au纳米颗粒的复合材料内部光生电子空穴对的分离效率越高.
光催化实验表明，在Au纳米粒子分布合理的情况下，拥有最小Au纳米颗粒尺寸的3-Au/CN样品表现出最好的光催化活性.在可见光条件下照射30min，该样品对罗丹明B水溶液（RhB，10mg/L）的光降解效率高达92.66%；紫外光条件下照射8h，该样品光催化还原CO₂转化成CO和CH₄的产率分别为77.5和38.5μmol/g，约是纯CN还原性能的6倍和10倍.结合文献报道及上述实验结果，我们提出了一个尺寸影响的光催化作用机制.

关键词: Au/g-C₃N₄, 纳米片, 尺寸影响, 光催化还原CO₂, 光催化剂

Abstract:

A series of Au/g-C₃N₄ (Au/CN) nanocomposites were successfully prepared, where g-C₃N₄ nanosheets (CN NSs) served as a substrate for the growth of different sized Au nanoparticles (Au NPs) using the constant temperature bath-reduction method. The effect of Au NP size on electron transfer efficiency between the interfaces of the nanocomposite was studied. The three-dimensional finite-difference time-domain results revealed that larger Au NPs showed increased strength of the localized surface plasmon resonance effect. An increased number of high-energy electrons were available for transfer from Au NPs to CN under the visible light irradiation, inhibiting electron transfer from CN to Au NPs. Photoelectrochemical performance analysis showed that smaller Au NPs exhibited higher separation efficiency of the electron-hole pairs photo-generated with reasonable distribution density. These results are favorable for the improvement of photocatalytic performance. Compared to other nanocomposites, the 3-Au/CN sample (prepared using 3 mL HAuCl₄ solution) with reasonable distribution density and small Au NPs exhibited the best photodegradation activity (92.66%) of RhB in 30 min under the visible light irradiation and photoreduction performance of CO₂ to CO and CH₄ with yields of 77.5 and 38.5 μmol/g, respectively, in 8 h under UV light irradiation. Considering the experimental results in the context of the literature, a corresponding size-dependent photocatalytic mechanism was proposed.

Key words: Au/g-C₃N₄, Nanosheet, Size dependence, CO₂ photoreduction, Photocatalyst

李鑫, 刘重阳, 吴东遥, 李金择, 霍鹏伟, 王会琴. 二维g-C₃N₄表面Au粒子尺寸调节的界面电子传输行为及光催化性能[J]. 催化学报, 2019, 40(6): 928-939.

Xin Li, Chongyang Liu, Dongyao Wu, JinZe Li, Pengwei Huo, Huiqin Wang. Improved charge transfer by size-dependent plasmonic Au on C₃N₄ for efficient photocatalytic oxidation of RhB and CO₂ reduction[J]. Chinese Journal of Catalysis, 2019, 40(6): 928-939.

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二维g-C₃N₄表面Au粒子尺寸调节的界面电子传输行为及光催化性能

Improved charge transfer by size-dependent plasmonic Au on C₃N₄ for efficient photocatalytic oxidation of RhB and CO₂ reduction

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