Five inorganic-organic hybrid vanadates based on tetravanadate cores, transition metals and N-donor ligands have been designed and synthesized under hydrothermal conditions, namely, [Zn(elM)312V4O12 (1), [Zn(plM...Five inorganic-organic hybrid vanadates based on tetravanadate cores, transition metals and N-donor ligands have been designed and synthesized under hydrothermal conditions, namely, [Zn(elM)312V4O12 (1), [Zn(plM)3]2V4O12.H2O (2), [Zn(iplM)3]2V4O12 (3), [Co(eIM)3]2V4O12.H2o (4), [Cu(eIM)2(H20)]2V4O12 (5) (eIM = 1-ethylimidazole, plM = 1-propylimidazole, ipIM = isopropylimidazole). All compounds were fully characterized by single-crystal XRD, powder XRD, elemental analysis, TGA, and FT-IR spectroscopy. The hybrid zinc vanadates (1-3) and cobalt vanadate (4) exhibit interesting 2D folded structures and the hybrid copper vanadate (5) presents a 1D chain configuration. All compounds can catalyze olefin epoxidation reactions when using TBHP (TBHP = tert-butyl hydroperoxide) as an oxidant in acetonitrile. The introduction of transition metal ions into tetravanadate cores not only improved the catalytic activity but also fulfilled the heterogeneous catalytic behavior. 1-5 all exhibit extraordinary efficiency in converting olefins to the corresponding epoxides with high conversion and selectivity (particularly, cony. up to 97.1%, sele. up to 100% for 1 ). Leaching test was also carried out to prove the heterogeneous behavior.展开更多
基金financially supported by the National Natural Science Foundation of China (Nos. 21173021, 21231002, 21271025 and 21276026)973 Program (No. 2014CB932103)+1 种基金the 111 Project (No. B07012)Beijing Higher Education Youth Elite Teacher Project (No. 1209)
文摘Five inorganic-organic hybrid vanadates based on tetravanadate cores, transition metals and N-donor ligands have been designed and synthesized under hydrothermal conditions, namely, [Zn(elM)312V4O12 (1), [Zn(plM)3]2V4O12.H2O (2), [Zn(iplM)3]2V4O12 (3), [Co(eIM)3]2V4O12.H2o (4), [Cu(eIM)2(H20)]2V4O12 (5) (eIM = 1-ethylimidazole, plM = 1-propylimidazole, ipIM = isopropylimidazole). All compounds were fully characterized by single-crystal XRD, powder XRD, elemental analysis, TGA, and FT-IR spectroscopy. The hybrid zinc vanadates (1-3) and cobalt vanadate (4) exhibit interesting 2D folded structures and the hybrid copper vanadate (5) presents a 1D chain configuration. All compounds can catalyze olefin epoxidation reactions when using TBHP (TBHP = tert-butyl hydroperoxide) as an oxidant in acetonitrile. The introduction of transition metal ions into tetravanadate cores not only improved the catalytic activity but also fulfilled the heterogeneous catalytic behavior. 1-5 all exhibit extraordinary efficiency in converting olefins to the corresponding epoxides with high conversion and selectivity (particularly, cony. up to 97.1%, sele. up to 100% for 1 ). Leaching test was also carried out to prove the heterogeneous behavior.