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/Zn0.2Cd0.8S-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Zn0.2Cd0.8S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Zn0.2Cd0.8S-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Zn0.2Cd0.8S-DETA类似于纳米花瓣,在Pg-C3N4/Zn0.2Cd0.8S-DETA复合材料中Pg-C3N4表面充满了Zn0.2Cd0.8S-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Zn0.2Cd0.8S-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/Zn0.2Cd0.8S-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/Zn0.2Cd0.8S-DETA具有很好的产氢活性,为6.69 mmol g^-1 h^-1,分别是Pg-C3N4和Zn0.2Cd0.8S-DETA的16.73和1.44倍.在经过七次循环实验后15%Pg-C3N4/Zn0.2Cd0.8S-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Zn0.2Cd0.8S-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Zn0.2Cd0.8S-DETA复合之后,在它们的接触处会形成内部电场,Zn0.2Cd0.8S-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.Zn0.2Cd0.8S-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/Zn0.2Cd0.8S-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.
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/Zn0.2Cd0.8S-diethylenetriamine(Pg-C3N4/Zn0.2Cd0.8S-DETA)composite by a facile solvothermal method.It was found by UV-vis spectroscopy that 15%Pg-C3N4/Zn0.2Cd0.8S-DETA exhibited suitable visible absorption edge and band gap for water decomposition.The hydrogen production rate of 15%Pg-C3N4/Zn0.2Cd0.8S-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 Zn0.2Cd0.8S-DETA,respectively.In addition,15%Pg-C3N4/Zn0.2Cd0.8S-DETA composite displayed excellent photocatalytic stability,which was maintained for seven cycles of photocatalytic water splitting test.We believe that 15%Pg-C3N4/Zn0.2Cd0.8S-DETA composite can be a valuable guide for the development of solar hydrogen production applications in the near future.
作者
梅飞飞
李真
代凯
张金锋
梁长浩
Feifei Mei;Zhen Li;Kai Dai;Jinfeng Zhang;Changhao Liang(College of Physics and Electronic Information,Anhui Key Laboratory of Energetic Materials,Huaibei Normal University,Huaibei 235000,Anhui,China;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)
基金
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)
Innovation Team of Design and Application of Advanced Energetic Materials(KJ2015TD003)~~
