Bi2S3@ MOFs核-壳结构构筑、界面调控及光催化协同机理研究

The photocatalysis is considered as a low-cost and high effective technology for solving the current environmental problems with utilization of solar energy. Among them, the visible-light photocatalysis is paid more attention on. The crystalline bismuth sulfide (Bi2S3) has been extensively studied because of its narrow band because of its high absorption efficiency as well as its optimal band gap. However, the single Bi2S3 photocatalyst is unlikely to improve photogenerated electron-hole separation and migration, which limit the potential application. In this project, to overcome their individual shortages mentioned above, we report on a novel Bi2S3@MOFs core-shell heterostructure, where the matched MOFs are selected to according to the theoretical calculation, and the Bi2S3 MOFs is modified by the topochemical reaction and post-functionalized method. It is expected that the mutual charge transfer and the covalent bonding interface is facile to improve charge separation and migration in the Bi2S3@MOFs core-shell structure. The influence of microstructure, band structure and interface structure on photocatalytic properties will be investigated in details. In the end, the synergistic photocatalytic model of Bi2S3@MOFs composites is proposed. The achievements of this project will provide a new platform for the design and synthesis of the visible light driven photocatalysis.

利用光催化技术降解污染物是一种低成本、高效率的环境净化方案，其中高效可见光催化材料的设计是光催化技术的关键。Bi2S3光催化材料因其具有高吸光系数和窄带隙而受到了广泛关注，但其存在光生电子-空穴容易复合以及界面传输效率低的问题。本项目利用理论计算筛选能级匹配的MOFs，并通过局部规整反应和后修饰策略对Bi2S3、MOFs进行缺陷设计和巯基化处理，构筑新型Bi2S3@MOFs核-壳结构。以期通过材料间的电荷相互转移、有机共价链特性界面提高载流子的分离效率和传导速率，提高可见光催化效率，并应用于降解空气、水中污染物。本项目将着重研究Bi2S3@MOFs核-壳结构材料的微观结构、能带结构和界面结构对光催化性能的影响，揭示Bi2S3@MOFs核-壳结构光催化协同作用机理，指导高活性可见光催化材料的设计与制备。

利用光催化技术降解污染物是一种低成本、高效率的环境净化方案，其中高效可见光催化材料的设计时光催化技术的关键。Bi2S3因其具有高吸光系数和窄带隙而收到广泛关注，但Bi2S3光催化剂存在的光生电子-空穴复合率高、界面传输效率低的问题。本项目针对Bi2S3存在问题，研制开发了具有高催化活性的Bi2S3@MOFs核壳复合材料。通过对Bi2S3的改性以及MOFs的巯基化后修饰策略，实现有机偶联界面的调控，提高界面的结合力，提高电荷传导速率；另外，通过溶剂热反应构筑一类与Bi2S3能带匹配的新型MOFs，通过在界面上的电荷相互转移，提高光生载流子的分离效率和氧化能力，提高可见光催化效率。本项目中，（1）能带结构匹配的新颖的金属CoII/NiII/CdII的MOFs构筑，相关研究结果发表在Micro. Meso. Mater., CrystEngComm等SCI期刊上，此类MOFs在催化有机反应、金属离子等检测方面表现出较好的普适性；（2）半导体/MOFs复合材料构筑及催化性能研究，以Bi2S3纳米棒为为核，ZIF-8为壳的核壳催化剂显著降低光生电子-空穴的复合，加快其转移速率进而提高催化效率发表在Dalton Trans. 2018, 47, 684-692, 同时文章被邀请作为封面文章；（3）构筑了Bi2S3 NP@SH-UiO-66复合材料，CdS NR/ NH2-MIL-125(Ti), In2S3@UiO-66，Ag/Ag3PO4/UiO-66, rGO@In2S3@UiO-66等复合材料并详细研究其光催化效果，发表在Dalton Trans, J Photochem. Photobio. A: Chem等期刊上;（4）积极探索此类材料的实用价值，实现了一类Fe-MOFs 的宏量制备并应用在“厕所革命”中；开发了一种热催化材料，并与新风系统并网联用，应用在室内空气净化领域，获得中国产学研合作创新成果奖一等奖、上海市产学研合作优秀项目奖二等奖等科技奖8项，助推4家公司成为高新技术企业，2家企业上市。目前，已发表相关论文15篇，申请中国发明专利10项，培养硕士研究生3名。