Selective oxidation of aryl alkenes to aldehydes is an important approach to produce industrial raw materials,in which the exploration of an efficient heterogeneous catalyst is significant but challenging.In this work...Selective oxidation of aryl alkenes to aldehydes is an important approach to produce industrial raw materials,in which the exploration of an efficient heterogeneous catalyst is significant but challenging.In this work,three hydrogen bond-mediated polyoxometalate(POM)-contained metal–organic networks with the formulas of[Ni(BTD)2(H2O)2]2[SiW12O40]·12H2O(1),[Ni(BTD)2(H2O)]2[SiW12O40]·6H2O(2)and[Zn(BTD)2(H2O)]2[SiW12O40]·6H2O(3)(BTD=4H,4ʹH-[3,3ʹ-bi(1,2,4-triazole)]-5,5ʹ-diamine)were hydrothermally synthesized,in which the metal–organic fragments interact with POM clusters via abundant hydrogen bonding to extend the structure into three-dimensional supramolecular networks.To be explored as heterogenous catalysts,compounds 1–3 showed high catalytic activity and selectivity for the selective oxidation of styrene to benzaldehyde.Among them,compound 1 exhibits the highest performance with ca.99%styrene conversion and ca.99%selectivity of benzaldehyde in 5 h.Moreover,compound 1 displays rich substrate compatibility,recyclability and good structural stability.A series of experiments demonstrated that the high performance of compound 1 should be attributed to the synergistic effect among polyoxoanion and coordination-unsaturated metal centers in metal–organic fragments,which facilitates the activation of H2O2 and styrene substrates,thus enhancing the catalytic performance.展开更多
基金financially supported by National Natural Science Foundation of China (Grants 21901060, 21871076)Natural Science Foundation of Hebei Province (Grants B2019205074, B2020205008 and B2016205051)+3 种基金Science and Technology Project of Hebei Education Department (Grant BJ2020037)Project funded by China Postdoctoral Science Foundation (No. 2021TQ0095)Science Foundation of Hebei Normal University (L2019B15)Graduate Student Innovation Funding Project of Hebei Normal University (CXZZSS2021056)
文摘Selective oxidation of aryl alkenes to aldehydes is an important approach to produce industrial raw materials,in which the exploration of an efficient heterogeneous catalyst is significant but challenging.In this work,three hydrogen bond-mediated polyoxometalate(POM)-contained metal–organic networks with the formulas of[Ni(BTD)2(H2O)2]2[SiW12O40]·12H2O(1),[Ni(BTD)2(H2O)]2[SiW12O40]·6H2O(2)and[Zn(BTD)2(H2O)]2[SiW12O40]·6H2O(3)(BTD=4H,4ʹH-[3,3ʹ-bi(1,2,4-triazole)]-5,5ʹ-diamine)were hydrothermally synthesized,in which the metal–organic fragments interact with POM clusters via abundant hydrogen bonding to extend the structure into three-dimensional supramolecular networks.To be explored as heterogenous catalysts,compounds 1–3 showed high catalytic activity and selectivity for the selective oxidation of styrene to benzaldehyde.Among them,compound 1 exhibits the highest performance with ca.99%styrene conversion and ca.99%selectivity of benzaldehyde in 5 h.Moreover,compound 1 displays rich substrate compatibility,recyclability and good structural stability.A series of experiments demonstrated that the high performance of compound 1 should be attributed to the synergistic effect among polyoxoanion and coordination-unsaturated metal centers in metal–organic fragments,which facilitates the activation of H2O2 and styrene substrates,thus enhancing the catalytic performance.
