多钒氧簇基晶态材料的制备及催化氧化性能研究

催化氧化反应在合成化学中发挥着关键作用，尤其是以双氧水(H₂O₂)和氧气为氧化剂的催化氧化体系能将原料以更为环保与经济的方式转化为具有高附加值的氧化产物。多酸凭借其优异的Lewis酸/碱性和氧化还原活性等优势，在催化氧化领域中脱颖而出。然而，相较于已被系统研究的含钼和钨的多酸化学，同样作为多酸化学重要分支的多钒氧簇(POVs)化学，其相关研究成果和应用案例相对较少，尤其是合成仍具有一定挑战。更重要的是，尽管目前已被报道的分立型POVs或由有机配体修饰的分立型POVs的催化氧化活性较高，其在极性溶剂中易溶解、非极性溶剂中易团聚以及在反应过程中结构易分解等问题严重限制了其催化应用。因此，上述问题的解决对POVs催化剂的应用研究具有重要的理论与实际意义。

本论文采取金属-有机框架(MOFs)载体固定POVs的策略，实现了POVs分子的均匀分散并解决了其作为催化剂易溶解难回收的问题。我们以含氮类有机配体通过一步水热法，合成了五例集所有理想特性的多钒氧簇基晶态材料：[Zn₂(BPB)₂][V₄O₁₂]·0.5BPB·H₂O (1)，[Ni(BPB)(H₂O)][V₂O₆]·2H₂O (2)，[Co(HBPB)₂][V₄O₁₂] (3), 以及{[M^II(bibp)_1.5][V^V₂O₆]}·H₂O (M=Ni 4，Co 5) (BPB=1,4-双(吡啶-4-基)苯；bibp=4,4’-双(咪唑基-1-甲基)联苯)。以双氧水为氧化剂，化合物1-3在硫醚氧化中均展现良好的催化活性和高的亚砜选择性，而化合物4和5利用氧气为氧化剂成功催化各种部分饱和N-杂环化合物的氧化脱氢，生成相应的N-杂芳烃化合物。化合物1-5在这些催化氧化反应中均表现非均相催化属性，尤其是1与4经过五或六次循环后没有观察到催化活性的明显降低。根据化合物1和4的结构信息与实验结果，我们推测在1在催化氧化硫醚化合物时，不饱和Zn^II与V^V位点与H₂O₂形成金属过氧化中间体进而与起到协同催化作用，最后氧原子转移到底物上形成对应的亚砜产物；而4在催化氧化N-杂环芳烃化合物脱氢时，底物N原子的电子先转移到预催化剂4的V^V位点，随后V^V还原为V^IV进而引发催化进程。

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