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Polyoxometalate-Incorporated Metal-Organic Network as a Heterogeneous Catalyst for Selective Oxidation of Aryl Alkenes
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2022-06-14 , DOI: 10.1021/acs.inorgchem.2c00036
Wen-Jing Cui 1 , Si-Meng Zhang 1 , Yuan-Yuan Ma 1 , Yue Wang 1 , Ruo-Xuan Miao 1 , Zhan-Gang Han 1
Affiliation  

Selective oxidation of aryl alkenes is important for chemical synthesis reactions, in which the key lies in the rational design of efficient catalysts. Herein, four polyoxometalate (POM)-incorporated metal-organic networks, with the formulas of [Co(ttb)(H2O)3]2[SiMo12O40]·2H2O (1), [Co(ttb)(H2O)2]2[SiW12O40]·8H2O (2), [Zn(Httb)(H2ttb)][BW12O40]·9H2O (3) and {[Zn(H2O)3(ttb)]4[Zn3(H2O)6]}[H3SiW10.5Zn1.5O40]2·24H2O (4) (ttb = 1,3,5-tri(1,2,4-triazol-1-ylmethyl)-2,4,6-trimethylbenzene), were hydrothermally synthesized and structurally characterized. Structural analysis showed that compound 1 consists of a POM-encapsulated three-dimensional (3-D) supramolecular framework; compound 2 is composed of a POM-supported 3-D coordination network; and compounds 3–4 show POM-incorporated 3-D supramolecular networks. Using selective catalytic oxidation of styrene as the model reaction, compounds 1–4 as heterogeneous catalysts display excellent performance with the double advantages of high styrene conversion and benzaldehyde selectivity owing to the synergistic effect among POM anions and transition metal (TM) centers. Among them, compound 1 exhibits the highest performance with ca. 96% styrene conversion and ca. 99% benzaldehyde selectivity in 3 h. In addition, compound 1 also displays excellent substrate compatibility, good reusability, and structural stability. Thus, a plausible reaction pathway for the selective oxidation of styrene is proposed. This study on the structure–function relationship paves a way for the rational design of POM-based heterogeneous catalysts for important catalysis applications.

中文翻译:

多金属氧酸盐结合金属有机网络作为多相催化剂用于芳基烯烃的选择性氧化

芳基烯烃的选择性氧化对化学合成反应具有重要意义,其中关键在于合理设计高效催化剂。在此,四种多金属氧酸盐(POM)结合的金属有机网络,其分子式为[Co(ttb)(H 2 O) 3 ] 2 [SiMo 12 O 40 ]·2H 2 O ( 1 ), [Co(ttb) (H 2 O) 2 ] 2 [SiW 12 O 40 ]·8H 2 O ( 2 ), [Zn(Httb)(H 2 ttb)][BW 12 O 40 ]·9H 2 O ( 3) 和 {[Zn(H 2 O) 3 (ttb)] 4 [Zn 3 (H 2 O) 6 ]}[H 3 SiW 10.5 Zn 1.5 O 40 ] 2 ·24H 2 O ( 4 ) (ttb = 1, 3,5-三(1,2,4-三唑-1-基甲基)-2,4,6-三甲基苯)是水热合成和结构表征。结构分析表明,化合物1由 POM 封装的三维 (3-D) 超分子骨架组成;化合物2由 POM 支持的 3-D 协调网络组成;和化合物3-4显示 POM 结合的 3-D 超分子网络。以苯乙烯的选择性催化氧化为模型反应,由于 POM 阴离子和过渡金属 (TM) 中心之间的协同作用,化合物1-4作为非均相催化剂表现出优异的性能,具有高苯乙烯转化率和苯甲醛选择性的双重优势。其中,化合物1表现出最高的性能,大约 96% 的苯乙烯转化率和ca. 3 小时内苯甲醛选择性达到 99%。此外,化合物1还表现出优异的基材相容性、良好的可重复使用性和结构稳定性。因此,提出了一种合理的苯乙烯选择性氧化反应途径。这项关于结构-功能关系的研究为合理设计用于重要催化应用的 POM 基多相催化剂铺平了道路。
更新日期:2022-06-14
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