TY - JOUR
T1 - CPO-27-M as heterogeneous catalysts for aldehyde cyanosilylation and styrene oxidation
AU - Yao, Hong Fei
AU - Yang, Yang
AU - Liu, Hui
AU - Xi, Fu Gui
AU - Gao, En Qing
PY - 2014/11/15
Y1 - 2014/11/15
N2 - A series of isostructural 3D metal-organic frameworks of 2,5-dihydroxyterephthalate with different metal ions, CPO-27-M (or MOF-74-M, M = Co, Mg, Mn, Ni and Zn), have been studied as catalysts for cyanosilylation of aldehydes with trimethylsilylcyanide and oxidation of styrene with tert-butylhydroperoxide, and two mixed-metal Co-Mn MOFs also studied for cyanosilylation. All these MOFs are active in promoting cyanosilylation, but for styrene oxidation, only the Co and Mn MOFs are active while the others behave as initiators rather than catalysts. For both reactions, CPO-27-Mn exhibits the highest activity, and the catalytic processes are heterogeneous. Radical mechanisms were proposed for the styrene oxidation over CPO-27-Mn, which yields styrene oxide, benzaldehyde and a minor amount of phenylacetaldehyde. The cyanosilylation over CPO-27-Mn shows size selectivity towards aldehyde substrates, and the catalyst can be recycled without losing its structural integrity and catalytic activity. It is also recyclable for styrene oxidation, though the structure changes after the catalytic reaction.
AB - A series of isostructural 3D metal-organic frameworks of 2,5-dihydroxyterephthalate with different metal ions, CPO-27-M (or MOF-74-M, M = Co, Mg, Mn, Ni and Zn), have been studied as catalysts for cyanosilylation of aldehydes with trimethylsilylcyanide and oxidation of styrene with tert-butylhydroperoxide, and two mixed-metal Co-Mn MOFs also studied for cyanosilylation. All these MOFs are active in promoting cyanosilylation, but for styrene oxidation, only the Co and Mn MOFs are active while the others behave as initiators rather than catalysts. For both reactions, CPO-27-Mn exhibits the highest activity, and the catalytic processes are heterogeneous. Radical mechanisms were proposed for the styrene oxidation over CPO-27-Mn, which yields styrene oxide, benzaldehyde and a minor amount of phenylacetaldehyde. The cyanosilylation over CPO-27-Mn shows size selectivity towards aldehyde substrates, and the catalyst can be recycled without losing its structural integrity and catalytic activity. It is also recyclable for styrene oxidation, though the structure changes after the catalytic reaction.
KW - Cyanosilylation
KW - Heterogeneous catalysis
KW - Manganese
KW - Metal-organic frameworks
KW - Styrene oxidation
UR - https://www.scopus.com/pages/publications/84904891912
U2 - 10.1016/j.molcata.2014.06.040
DO - 10.1016/j.molcata.2014.06.040
M3 - 文章
AN - SCOPUS:84904891912
SN - 1381-1169
VL - 394
SP - 57
EP - 65
JO - Journal of Molecular Catalysis A: Chemical
JF - Journal of Molecular Catalysis A: Chemical
ER -