摘要
Surface organometallic chemistry (SOMC) is a recently developing research field. It is of great significance for the quantitative modification, restoration of solid surface, identification of the physical and chemical nature of surface and the preparation of new catalyst. The production of R 3 Sn-O-MCM-41 (R 3 SnM) was obtained by heating tributyltin chloride and Al-MCM-41 mixture at 170 °C for 5 h under stirring in nitrogen atmosphere. The composition, structure and surface physical and chemical properties of the samples were characterized by inductively coupled plasma mass spectrometry (ICP-MS), 13 C, 119 Sn, 29 Si and 27 Al solid state NMR (nuclear magnetic resonance) spectra, in-situ pyridine infrared spectroscopy (Py-IR), N 2 adsorption-desorption, X-ray diffraction (XRD), transmission electron microscopy (TEM), etc. The results of ICP and organic elemental analysis shows that the grafting yield w Sn was 6.46% for R 3 SnM. H 0 (the negative logarithm of the acid concentration)and the number of acid sites for R 3 SnM respectively were 2.77-0.99 and 4.8 mmol·g-1 by the Hammett method. N 2 adsorption-desorption, XRD, TEM analysis showed that R 3 SnM with ordered hexagonal mesopore structure, resulted in the decease of surface areas and pore size as well as the increase of mesoporous volume and surface acidity, as compared to Al-MCM-41. R 3 SnM was used in the synthesis of isoamyl acetate. The yield of isoamyl acetate was 96% when n(isoamyl alcohol)︰n(acetic acid) 1.0︰1.0, 3 R SnM w 5%, 138 °C for 5 h. The catalyst can be reused and the yield of 86% can be attained when catalyst was reused five times at the same catalytic conditions.
Surface organometallic chemistry （SOMC） is a recently developing research field. It is of great significance for the quantitative modification, restoration of solid surface, identification of the physical and chemical nature of surface and the preparation of new catalyst. The production of R 3 Sn-O-MCM-41 （R 3 SnM） was obtained by heating tributyltin chloride and Al-MCM-41 mixture at 170 °C for 5 h under stirring in nitrogen atmosphere. The composition, structure and surface physical and chemical properties of the samples were characterized by inductively coupled plasma mass spectrometry （ICP-MS）, 13 C, 119 Sn, 29 Si and 27 Al solid state NMR （nuclear magnetic resonance） spectra, in-situ pyridine infrared spectroscopy （Py-IR）, N 2 adsorption-desorption, X-ray diffraction （XRD）, transmission electron microscopy （TEM）, etc. The results of ICP and organic elemental analysis shows that the grafting yield w Sn was 6.46% for R 3 SnM. H 0 （the negative logarithm of the acid concentration）and the number of acid sites for R 3 SnM respectively were 2.77-0.99 and 4.8 mmol·g-1 by the Hammett method. N 2 adsorption-desorption, XRD, TEM analysis showed that R 3 SnM with ordered hexagonal mesopore structure, resulted in the decease of surface areas and pore size as well as the increase of mesoporous volume and surface acidity, as compared to Al-MCM-41. R 3 SnM was used in the synthesis of isoamyl acetate. The yield of isoamyl acetate was 96% when n（isoamyl alcohol）︰n（acetic acid） 1.0︰1.0, 3 R SnM w 5%, 138 °C for 5 h. The catalyst can be reused and the yield of 86% can be attained when catalyst was reused five times at the same catalytic conditions.
基金
Supported by the National Science Foundation of Heilongjiang Province (B201010)
the Education Department of Heilongjiang Province (12511595)
