The modification of pillared MFI zeolites was performed by nitridation of silica pillared MFI zeolite nanosheets under NH3 atmosphere with different time. The resultant zeolites were characterized by a complementary c...The modification of pillared MFI zeolites was performed by nitridation of silica pillared MFI zeolite nanosheets under NH3 atmosphere with different time. The resultant zeolites were characterized by a complementary combination of X-ray power diffraction(XRD), scanning electron microscopy(SEM),transmission electron microscopy(TEM), pyridine-IR spectroscopy and N2 adsorption–desorption isotherms. The analyses showed that the nitridation didn’t destroy the crystallinity and specific surface area of zeolites, and the acidity of zeolites can be tailored by tuning the time of nitridation, resulting in the different concentration ratios of Br?nsted-to-Lewis(B/L) acid sites. Moreover, the nitrided zeolites exhibited high selectivity to 2-benzyl-1,3,5-trimethylbenzene than parent silica pillared MFI zeolite nanosheets in benzylation of mesitylene with benzyl alcohol. A balance between Br?nsted acid sites and Lewis acid sites can inhibit the self-etherification of benzyl alcohol and enhance the selectivity of alkylated product. These experimental data implied that nitridation was an effective method to modulate the acidity of zeolites and the synergy between Br?nsted acid sites and Lewis acid sites was a decisive factor to determine the selectivity.展开更多
Titanosilicate pillared MFI zeolite nanosheets were successfully synthesized by infiltrating the mixed tetraethyl orthosilicate(TEOS)/tetrabutyl orthotitanate(TBOT)solvent into the gallery space between adjacent MFI z...Titanosilicate pillared MFI zeolite nanosheets were successfully synthesized by infiltrating the mixed tetraethyl orthosilicate(TEOS)/tetrabutyl orthotitanate(TBOT)solvent into the gallery space between adjacent MFI zeolite layers.The obtained zeolite catalysts were characterized using powder X-ray diffraction,N2 adsorption/desorption isotherms,scanning electron microscopy,transmission electron microscopy,ultraviolet-visible spectroscopy,X-ray photoelectron spectroscopy,and Fouriertransform infrared spectroscopy techniques.The H2〇2 oxidation of dibenzothiophene(DBT)was used to evaluate the catalytic performance of the obtained titanosilicate pillared MFI zeolites.The conversion of DBT and selectivity of dibenzothiophene sulfone(DBTS)were most affected by the textural properties of the zeolites.This was attributed to the DBT and DBTS molecules being larger than micropores of the MFI zeolites.The conversion of DBT and yield of DBTS could be systematically tailored by tuning the molar ratio of the TEOS/TBOT solvent.These results implied that a balance between the meso-and microporosity of zeolites and tetrahedrally coordinated Ti(IV)active sites of titanosilicate pillars can be achieved for the preparation of desired catalysts during the oxidation of bulk S compounds.展开更多
基金Supported by the Science and Technology Program of Guangzhou,China(201804010172)National Natural Science Foundation of China(21808040,21706031,21276052,21776049)Science and Technology Planning Project of Guangdong Province,China(2012A090300006)
文摘The modification of pillared MFI zeolites was performed by nitridation of silica pillared MFI zeolite nanosheets under NH3 atmosphere with different time. The resultant zeolites were characterized by a complementary combination of X-ray power diffraction(XRD), scanning electron microscopy(SEM),transmission electron microscopy(TEM), pyridine-IR spectroscopy and N2 adsorption–desorption isotherms. The analyses showed that the nitridation didn’t destroy the crystallinity and specific surface area of zeolites, and the acidity of zeolites can be tailored by tuning the time of nitridation, resulting in the different concentration ratios of Br?nsted-to-Lewis(B/L) acid sites. Moreover, the nitrided zeolites exhibited high selectivity to 2-benzyl-1,3,5-trimethylbenzene than parent silica pillared MFI zeolite nanosheets in benzylation of mesitylene with benzyl alcohol. A balance between Br?nsted acid sites and Lewis acid sites can inhibit the self-etherification of benzyl alcohol and enhance the selectivity of alkylated product. These experimental data implied that nitridation was an effective method to modulate the acidity of zeolites and the synergy between Br?nsted acid sites and Lewis acid sites was a decisive factor to determine the selectivity.
基金This work was funded by the National Natural Science Foundation of China(Grant Nos.21808040,51476176,and 21776049)The support of the Science and Technology Program of Guangzhou,China(Grant No.201804010172)is also gratefully acknowledged.
文摘Titanosilicate pillared MFI zeolite nanosheets were successfully synthesized by infiltrating the mixed tetraethyl orthosilicate(TEOS)/tetrabutyl orthotitanate(TBOT)solvent into the gallery space between adjacent MFI zeolite layers.The obtained zeolite catalysts were characterized using powder X-ray diffraction,N2 adsorption/desorption isotherms,scanning electron microscopy,transmission electron microscopy,ultraviolet-visible spectroscopy,X-ray photoelectron spectroscopy,and Fouriertransform infrared spectroscopy techniques.The H2〇2 oxidation of dibenzothiophene(DBT)was used to evaluate the catalytic performance of the obtained titanosilicate pillared MFI zeolites.The conversion of DBT and selectivity of dibenzothiophene sulfone(DBTS)were most affected by the textural properties of the zeolites.This was attributed to the DBT and DBTS molecules being larger than micropores of the MFI zeolites.The conversion of DBT and yield of DBTS could be systematically tailored by tuning the molar ratio of the TEOS/TBOT solvent.These results implied that a balance between the meso-and microporosity of zeolites and tetrahedrally coordinated Ti(IV)active sites of titanosilicate pillars can be achieved for the preparation of desired catalysts during the oxidation of bulk S compounds.