结构原子组成对Keggin型杂多酸铯盐上丙烷选择氧化性能的影响

系统地研究了具有不同结构原子组成的Keggin型杂多酸铯盐上丙烷选择氧化性能,重点考察了H3+n-xCsxPMo12-nVnO40(n=0-4,x=0-3)系列化合物以及H0.5Cs2.5PW12O40,H1.5Cs2.5PW11VO40和H1.5Cs2.5SiMo12O40样品.应用BET,UV-Vis,FTIR,XRD,TPR和SEM等手段研究了催化剂的物化性质.V取代Mo增加了H3+nPMo12-nVnO40(n=0-4)系列杂多酸的酸量和氧化性能.Cs+对质子的取代调变了样品的表面酸性以及氧化还原性,同时催化剂的热稳定性也随着Cs+取代数的递增而增强,当Cs+的取代数达到2以上时催化剂的热稳定性较好.Cs+取代对H3+n-xCsxPMo12-nVnO40(n=0-4,x=0-3)催化剂上丙烷选择氧化性能有重要影响.随着一级结构中V5+取代数目的增多,可能的Cs+取代数目相应减少;而对丙烯酸的选择性则存在一适宜的Cs+取代数目.Keggin型杂多阴离子的结构原子组成及平衡离子的种类和数量决定了其酸性、氧化还原性和热稳定性,这是影响该类催化剂上丙烷选择氧化性能的首要因素.研究结果表明,以P为中心原子,以Mo和V为配位原子的杂多酸铯盐[x(Cs+)=2.5]具有较好的催化性能.

Ab initio Study on Crystal Orbital of One-dimensional Phthalocyaninato Polymers

The band structures and electronic properties of several phthalocyaninato polymers and their derivatives are calculated by using the ab initio self-consistent-field crystal orbital method based on density functional theory. The calculated results show that these polymers are semiconductors. The differences in polymeric manner and degree of conjugation not only affect the energy gaps but also the band structures. The substituents almost have no influence on the band patterns of the corresponding polymers, but its electronic characteristics influences the band levels.