三维二硫化钼/还原氧化石墨烯气凝胶用作宏观可见光催化剂

引用本文: 张瑞阳, 万文超, 李大为, 董帆, 周莹. 三维二硫化钼/还原氧化石墨烯气凝胶用作宏观可见光催化剂[J]. 催化学报, 2017, 38(2): 313-320. doi: 10.1016/S1872-2067(16)62568-8 shu

Citation: Ruiyang Zhang, Wenchao Wan, Dawei Li, Fan Dong, Ying Zhou. Three-dimensional MoS₂/reduced graphene oxide aerogel as a macroscopic visible-light photocatalyst[J]. Chinese Journal of Catalysis, 2017, 38(2): 313-320. doi: 10.1016/S1872-2067(16)62568-8 shu

三维二硫化钼/还原氧化石墨烯气凝胶用作宏观可见光催化剂

张瑞阳 ^a, ,
万文超 ^a, ,
李大为 ^a, ,
董帆 ^b, ,
周莹 ^a,

a 西南石油大学油气藏地质及开发工程国家重点实验室, 四川成都 610500;
b 重庆工商大学催化与功能有机分子重庆市重点实验室, 重庆 400067
基金项目:
国家自然科学基金（U1232119，21403172）；四川杰出青年科技基金（2013JQ0034，2014JQ0017）；四川省青年科技创新研究团队（2016TD0011）.

摘要: 近年来，光催化技术在解决环境污染和能源短缺方面展现出巨大潜力.二硫化钼（MoS₂）作为一种二维层状光催化材料受到广泛关注.MoS₂具有可调的带隙（1.2-1.9 eV）、低的成本和高的存储量，是一种可替代铂的理想助催化剂.然而，MoS₂本身光催化活性较低.理论和实验已经证明，MoS₂只有暴露的边缘具有催化活性，并且MoS₂的光生电子-空穴对容易复合，导致其光催化效率低.增加暴露的活性边缘以及有效分离电子-空穴对是提高MoS₂光催化活性的关键.而石墨烯气凝胶是一种理想的催化剂载体，其高比表面积和高空隙率可以有效提高催化剂利用率.同时，其高导电性可以促进光生电子-空穴对分离.因此，将MoS₂负载到石墨烯气凝胶上制备宏观可回收光催化材料具有广阔的应用前景.然而，目前尚未见到有关MoS₂/石墨烯气凝胶光催化产氢以及还原Cr（VI）的报道.
本文以钼酸铵为钼源，硫脲为硫源和还原剂，同时加入氧化石墨烯及其还原剂氨水，通过一步水热法制备出二硫化钼/还原氧化石墨烯（MoS₂/RGO）水凝胶.最后通过冷冻干燥得到MoS₂/RGO气凝胶.经光催化测试发现其产氢达到38.9 μmol/g，光还原Cr（VI）达到92%，明显高于MoS₂粉体.采用X射线衍射（XRD）、扫描电镜（SEM）、透射电镜（TEM）、X射线光电子能谱（XPS）、紫外-可见-近红外吸收光谱（UV-Vis-NIR）及红外光谱（FTIR）等手段研究了其光催化性能提高的原因.
XRD测试显示，过量的NH₄⁺离子插入到MoS₂层与层之间增加了（002）面的晶面间距；SEM观察到在形成气凝胶后，MoS₂从粉末的片状转变成花状，这是因为氧化石墨烯上的含氧官能团促进MoS₂成核同时限制其生长导致的；TEM观察到MoS₂上存在大量的脱节和扭曲，这是由于过量硫脲阻碍了MoS₂晶体的取向生长而产生缺陷；XPS发现，除了形成MoS₂之外，还形成了MoO₂，同时大量的暴露边缘导致不饱和硫产生；FTIR表明MoS₂与RGO之间通过氢键链接在一起；UV-Vis-NIR吸收光谱显示，MoS₂/RGO气凝胶在可见光区具有很强的吸收，这是黑色的RGO以及光在花状结构的不断反射共同作用导致的.
综合以上结果，我们提出了MoS₂/RGO光催化性能增强的机理.首先，三维的气凝胶网状结构以及花状结构的MoS₂所带来的高比表面积（599.7 m²/g）使得材料对H⁺和Cr（VI）吸附量增加；其次，黑色的RGO以及入射光在花状结构层片间的不断反射增加了MoS₂/RGO气凝胶对可见光的吸收；最后，RGO本身的高导电性促进了光生电子-空穴有效分离，电子通过RGO快速转移到材料表面参与光催化反应.因此，将MoS₂负载在RGO上可提高光催化效率.另外，低密度的MoS₂/RGO气凝胶（56.1 mg/cm³）可以有效吸附有机溶剂且容易回收.综上所述，本文制备的MoS₂/RGO气凝胶光催化材料在环境与能源方面表现出潜在的应用前景.

关键词:

English

Three-dimensional MoS₂/reduced graphene oxide aerogel as a macroscopic visible-light photocatalyst

a State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation, School of Materials Science and Engineering, Southwest Petroleum University, Chengdu 610500, Sichuan, China;
b Chongqing Key Laboratory of Catalysis and Functional Organic Molecules, College of Environmental and Biological Engineering, Chongqing Technology and Business University, Chongqing 400067, China
Received Date: 29 August 2016
Revised Date: 26 September 2016
Available Online: 02 March 2017
Fund Project:
This work was supported by the National Natural Science Foundation of China (U1232119, 21403172), the Sichuan Youth Science and Technology Foundation (2013JQ0034, 2014JQ0017), and the Innovative Research Team of Sichuan Province (2016TD0011).

Abstract: Photocatalysis is regarded as an ideal technology for solving the urgent environmental and energy issues that we face today. Among the reported photocatalysts, molybdenum disulfide (MoS₂) is very promising for applications in hydrogen production and pollutant photodegradation. However, its lack of active sites and the difficulty of recovering catalysts in powder form have hindered its wide application. Here, we report the successful preparation of a macroscopic visible-light responsive MoS₂/reduced graphene oxide (MoS₂/RGO) aerogel. The obtained MoS₂/RGO aerogel exhibits enhanced photocatalytic activity towards hydrogen production and photoreduction of Cr(VI) in comparison with the MoS₂ powder. In addition, the low density (56.1 mg/cm³) of the MoS₂/RGO aerogel enables it to be used as an efficient adsorption material for organic pollutants. Our results demonstrate that this very promising multifunctional aerogel has potential applications in environmental remediation and clean energy production.

Key words:

Molybdenum disulfide/reduced graphene oxide aerogel
/ Composite
/ Photocatalysis
/ Visible light
/ Adsorption

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沈阳化工大学材料科学与工程学院沈阳 110142

三维二硫化钼/还原氧化石墨烯气凝胶用作宏观可见光催化剂

English

Three-dimensional MoS₂/reduced graphene oxide aerogel as a macroscopic visible-light photocatalyst

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三维二硫化钼/还原氧化石墨烯气凝胶用作宏观可见光催化剂

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