Lin-Fan Dai, Yi-Qi Tian, Wen-Lei Mu, Xiao-Yi Yi, Chao Liu*, Auxiliary Carboxylate-Induced Assembly of Calix[6]arene-Polyoxotitanate Hybrid Systems with Photocatalytic Activity in the Oxidation of Sulfides, Inorganic Chemistry, 2023, doi.org/10.1021/acs.inorgchem.2c04528.
发布时间:2022-12-28
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摘要:我们采用单羧酸诱导组装策略,采用叔丁基杯[6]芳烃为主配体,有机羧酸为辅助配体,通过溶剂热条件下有机酸与乙醇溶剂之间的酯化反应原位产生并缓慢释放Ti4+离子水解所需要的水分子,进而通过调节有机酸的种类、用量和反应温度等控制反应体系中含水量,实现了钛氧簇簇核结构从{Ti-TBC[6]-Ti},到{Ti2-TBC[6]-Ti2},到{Ti3-TBC[6]-Ti3},最后到3.0nm {Ti3-TBC[6]-Ti2-TBC[6]-Ti3}的演变。我们以所得簇为光催化剂,双氧水为绿色氧化剂,研究了团簇对硫醚选择性氧化成亚砜的能力,并结合中间物质谱表征及电子顺磁共振波谱证实了反应催化路径。研究表明TBC[6]-Tix体系催化效率与团簇结构密切相关,当TBC[6]配体采用双锥构型时候,钛氧核可以保留在团簇表面,簇表面Ti(IV)活性位点的暴露使得团簇与双氧水结合形成过氧化物中间体,光照下释放的超氧自由基氧化底物。
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上一条: Wen-Lei Mu, Linlin Wu, Wei-Dong Yu, Jun Yan, Xiao-Yi Yi, and Chao Liu*, Atomically Accurate Structural Tailoring of Thiacalix[4]arene-Protected Cu(II)-Based Metallamacrocycles, Dalton Transactions, 2023,52, 5438-5442.
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