梯型多孔g-C3N4/Zn0.2Cd0.8S-DETA复合材料的合成及其高效稳定光催化产氢性能

doi:10.1016/S1872-2067(19)63389-9

催化学报 ›› 2020, Vol. 41 ›› Issue (1): 41-49.DOI: 10.1016/S1872-2067(19)63389-9

梯型多孔g-C₃N₄/Zn_0.2Cd_0.8S-DETA复合材料的合成及其高效稳定光催化产氢性能

梅飞飞^a, 李真^a, 代凯^a, 张金锋^a, 梁长浩^b

a 淮北师范大学物理与电子信息学院, 安徽含能材料重点实验室, 安徽淮北 235000;
b 中国科学院固体物理研究所, 材料物理重点实验室和安徽纳米材料和纳米技术重点实验室, 安徽合肥 230031

收稿日期:2019-04-08 修回日期:2019-05-01 出版日期:2020-01-18 发布日期:2019-10-22
通讯作者: 代凯, 张金锋, 梁长浩
基金资助:
国家自然科学基金（51572103，51502106）；安徽省杰出青年基金（1808085J14）；安徽省高等学校省级优秀青年人才基金（gxyqZD201751）；安徽省教育厅重点项目（KJ2016SD53）；安徽省创新团队（KJ2015TD003）.

Step-scheme porous g-C₃N₄/Zn_0.2Cd_0.8S-DETA composites for efficient and stable photocatalytic H₂ production

Feifei Mei^a, Zhen Li^a, Kai Dai^a, Jinfeng Zhang^a, Changhao Liang^b

a College of Physics and Electronic Information, Anhui Key Laboratory of Energetic Materials, Huaibei Normal University, Huaibei 235000, Anhui, China;
b Key Laboratory of Materials Physics and Anhui Key Laboratory of Nanomaterials and Nanotechnology, Institute of Solid State Physics, Hefei Institutes of Physical Science, Chinese Academy of Sciences, Hefei 230031, Anhui, China

Received:2019-04-08 Revised:2019-05-01 Online:2020-01-18 Published:2019-10-22
Supported by:
This work was supported by the National Natural Science Foundation of China (51572103, 51502106), the Distinguished Young Scholar of Anhui Province (1808085J14), the Foundation for Young Talents in College of Anhui Province (gxyqZD2017051), the Key Foundation of Educational Commission of Anhui Province (KJ2016SD53) and Innovation Team of Design and Application of Advanced Energetic Materials (KJ2015TD003).

摘要/Abstract

摘要： 近年来，化石燃料燃烧导致的环境污染问题和能源危机越来越严重.在众多解决方案中，光催化产氢由于其可持续性以及无污染等特点而受到广泛关注.然而，由于许多半导体光催化剂性能不理想，光催化水分解研究进程缓慢.本研究采用水热法成功制备了梯型Pg-C₃N₄/Zn_0.2Cd_0.8S-DETA复合材料用于光催化产氢.DETA（二亚乙基三胺）作为一种有机分子插入在Zn_0.2Cd_0.8S的层中构成有机-无机杂化材料.采用X射线衍射（XRD）、扫描电子显微镜（SEM）、透射电子显微镜（TEM）、X射线光电子能谱（XPS）、紫外-可见光漫反射光谱（UV-vis）以及光电流研究了所制备样品的结构、形貌、元素组成以及光电特征，并提出了可能的光催化机制.
XRD和XPS结果表明Pg-C₃N₄和Zn_0.2Cd_0.8S-DETA复合在一起而不是机械混合.通过TEM可以看出Pg-C₃N₄是一种带有很多孔洞的纳米片，而Zn_0.2Cd_0.8S-DETA类似于纳米花瓣，在Pg-C₃N₄/Zn_0.2Cd_0.8S-DETA复合材料中Pg-C₃N₄表面充满了Zn_0.2Cd_0.8S-DETA纳米花瓣.经过元素分析得知所合成的复合材料没有杂质元素.UV-vis表明Pg-C₃N₄和Zn_0.2Cd_0.8S-DETA具有良好的吸收带边以及带隙，分别为2.83 eV和2.48 eV.光电流和PL显示15% Pg-C₃N₄/Zn_0.2Cd_0.8S-DETA具有很高的载流子分离及传输效率.光催化性能测试显示15% Pg-C₃N₄/Zn_0.2Cd_0.8S-DETA具有很好的产氢活性，为6.69 mmol g^-1 h^-1，分别是Pg-C₃N₄和Zn_0.2Cd_0.8S-DETA的16.73和1.44倍.在经过七次循环实验后15% Pg-C₃N₄/Zn_0.2Cd_0.8S-DETA仍保持很优异的活性，说明它具有很好的稳定性.
通过高分辨XPS中各元素结合能的变化可以看出构成异质结之后电子的流向，从而看出光催化可能的机制为梯形.光照射之后，Pg-C₃N₄和Zn_0.2Cd_0.8S-DETA中产生电子-空穴对，电子迁移到导带并在价带留下空穴.当Pg-C₃N₄与Zn_0.2Cd_0.8S-DETA复合之后，在它们的接触处会形成内部电场，Zn_0.2Cd_0.8S-DETA导带上的电子和Pg-C₃N₄价带上的空穴会在内部电场作用下复合.Zn_0.2Cd_0.8S-DETA价带上的空穴和Pg-C₃N₄上的电子分别参与氧化还原反应.梯形机制促使电子和空穴在空间上分离，从而具有强氧化还原性.梯形异质结的形成加快了15% Pg-C₃N₄/Zn_0.2Cd_0.8S-DETA复合材料中电子-空穴对的分离效率，并减少了电子-空穴对的复合，从而使其具有很优异的光催化性能和稳定性.

关键词: Pg-C₃N₄, Zn_0.2Cd_0.8S, 二亚乙基三胺, 光催化, 梯形多孔复合物

Abstract: In recent years, environmental pollution and energy crisis have become increasingly serious issues owing to the burning of fossil fuels. Among the many technologies, decomposition of water to produce hydrogen has attracted much attention because of its sustainability and non-polluting characteristic. However, highly efficient decomposition of water that is driven by visible light is still a challenge. Herein, we report the large-scale preparation of step-scheme porous graphite carbon nitride/Zn_0.2Cd_0.8S-diethylenetriamine (Pg-C₃N₄/Zn_0.2Cd_0.8S-DETA) composite by a facile solvothermal method. It was found by UV-vis spectroscopy that 15%Pg-C₃N₄/Zn_0.2Cd_0.8S-DETA exhibited suitable visible absorption edge and band gap for water decomposition. The hydrogen production rate of 15%Pg-C₃N₄/Zn_0.2Cd_0.8S-DETA composite was 6.69 mmol g^-1 h^-1, which was 16.73, 1.61, and 1.44 times greater than those of Pg-C₃N₄, CdS-DETA, and Zn_0.2Cd_0.8S-DETA, respectively. In addition, 15%Pg-C₃N₄/Zn_0.2Cd_0.8S-DETA composite displayed excellent photocatalytic stability, which was maintained for seven cycles of photocatalytic water splitting test. We believe that 15%Pg-C₃N₄/Zn_0.2Cd_0.8S-DETA composite can be a valuable guide for the development of solar hydrogen production applications in the near future.

Key words: Pg-C₃N_4, Zn_0.2Cd_0.8S, Diethylenetriamine, Photocatalysis, Step-scheme porous composite

梅飞飞, 李真, 代凯, 张金锋, 梁长浩. 梯型多孔g-C₃N₄/Zn_0.2Cd_0.8S-DETA复合材料的合成及其高效稳定光催化产氢性能[J]. 催化学报, 2020, 41(1): 41-49.

Feifei Mei, Zhen Li, Kai Dai, Jinfeng Zhang, Changhao Liang. Step-scheme porous g-C₃N₄/Zn_0.2Cd_0.8S-DETA composites for efficient and stable photocatalytic H₂ production[J]. Chinese Journal of Catalysis, 2020, 41(1): 41-49.

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梯型多孔g-C₃N₄/Zn_0.2Cd_0.8S-DETA复合材料的合成及其高效稳定光催化产氢性能

Step-scheme porous g-C₃N₄/Zn_0.2Cd_0.8S-DETA composites for efficient and stable photocatalytic H₂ production

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