炭载钯硫化物催化剂的原位合成机制及其构效关系研究

Catalytic hydrogenation of the sulfur-containing organic compounds is difficult as sulfur is a poison to metal catalysts. We found a new and efficient method of hydrogenating thio aromatic nitro compounds to thio aromatic amines over carbon supported palladium sulphide catalyst which is in situ synthesized from Pd/C. However, there still is a lack of the studies on in situ synthetic mechanism and catalytic mechanism of carbon supported palladium sulphide catalysts. In this project, three basic problems will be resolved: 1) what are the law and mechanism of in situ synthesis of different carbon supported palladium sulphides from Pd/C during the hydrogenation of sulfur-containing organic compounds; 2) there are several crystalline phases for palladium sulphide, such as Pd4S、Pd3S、Pd16S7、PdS、PdS2, and what is the catalytic mechanism of each different carbon supported palladium sulphide catalysts; 3) what is the general law of the catalytic performance of carbon supported palladium sulphide catalysts during the hydrogenation of different thio aromatic nitro compounds. Through this project, we can establish an important theoretical foundation for in situ synthesis of carbon supported palladium sulphide catalysts with high activity and stability, and also provide a new method of green and economic synthesis of thio aromatic amines for industries.

硫是金属催化剂的毒物，催化含硫有机化合物加氢反应是一个难题。申请者发现了Pd/C原位硫化合成炭载钯硫化物催化剂并高效催化硫代芳香硝基化合物加氢合成硫代芳胺的新路线。但目前对钯硫化物的原位合成机制及其催化加氢机理尚缺乏深入研究。本项目拟解决以下三个基础问题：1）在含硫化合物的加氢反应中，Pd/C原位硫化合成不同炭载钯硫化物的规律与机理；2）钯的硫化物分别有Pd4S、Pd3S、Pd16S7、PdS、PdS2等晶相，不同晶相的钯硫化物催化剂在含硫化合物加氢反应中的催化性能与催化机理；3）钯硫化物催化剂对不同硫代芳香硝基化合物催化加氢性能的一般规律。本项目的开展并顺利完成，为原位硫化合成高活性、高稳定性的炭载钯硫化物催化剂奠定理论基础；亦可为工业上提供一种绿色、经济的合成硫代芳胺化合物的新方法。

硫是金属催化剂的毒物，催化含硫有机化合物加氢反应是一个难题。申请者发现了Pd/C原位硫化合成炭载钯硫化物催化剂并高效催化硫代芳香硝基化合物加氢合成硫代芳胺的新路线。但目前对钯硫化物的原位合成机制及其催化加氢机理尚缺乏深入研究。本项目解决以下三个基础问题：1）在含硫化合物的加氢反应中，Pd/C原位硫化合成不同炭载钯硫化物的规律与机理；2）钯的硫化物分别有Pd4S、Pd3S、Pd16S7、PdS、PdS2等晶相，不同晶相的钯硫化物催化剂在含硫化合物加氢反应中的催化性能与催化机理；3）钯硫化物催化剂对不同硫代芳香硝基化合物催化加氢性能的一般规律。本项目的开展并顺利完成，为原位硫化合成高活性、高稳定性的炭载钯硫化物催化剂奠定理论基础；亦可为工业上提供一种绿色、经济的合成硫代芳胺化合物的新方法。