A series of Mo-containing MFI zeolites with different Mo loadings(Mo-MFI-n,n represent the initial Si/Mo molar ratio)was hydrothermally synthesized by using tetrapropylammonium hydroxide as the template and Mo-EDTA co...A series of Mo-containing MFI zeolites with different Mo loadings(Mo-MFI-n,n represent the initial Si/Mo molar ratio)was hydrothermally synthesized by using tetrapropylammonium hydroxide as the template and Mo-EDTA complex as the Mo source.Various characterization results demonstrated that the use of the Mo-EDTA complex is beneficial for the incorporation of more Mo species into the MFI-type zeolites.The special complexing capability of EDTA^(2–)plays a critical role in adjusting the release rate of the Mo species to combine with the Si tetrahedron species during the zeolite growth process,thus leading to a uniform distribution of Mo in the MFI framework.In addition,a small portion of extra-framework Mo clusters may be distributed inside the channels or near the pore window of the zeolites.The catalytic properties of these Mo-containing MFI zeolites were evaluated for the epoxidation of cyclohexene with H_(2)O_(2)as the oxidant.The composition-optimized catalyst,Mo-MFI-50,efficiently converted cyclohexene to the corresponding epoxide with a relatively high conversion(93%)and epoxide selectivity(82%)at 75℃after 9 h of reaction.Moreover,the resultant Mo-containing MFI catalyst exhibited excellent structural stability and recoverability and was easily recycled by simple filtration without the need for calcination treatment.展开更多
Catalytic cracking of naphtha is now a process of huge development potential to produce light olefins, which are important basic raw materials used in various industries, but current industrial catalysts like ZSM-5 ze...Catalytic cracking of naphtha is now a process of huge development potential to produce light olefins, which are important basic raw materials used in various industries, but current industrial catalysts like ZSM-5 zeolites suffer from low selectivity and high energy consumption. Here, Ti/Al-containing nanosize MFI-structure zeolites in-situly synthesized through one-pot method were applied to the catalytic cracking using n-hexane as the model reactant. The maximum mass yield of combined light olefins reaches 49.2% with 99% conversion at 600<span style="color:#4F4F4F;font-family:-apple-system, "font-size:16px;white-space:normal;background-color:#FFFFFF;">°</span>C and 1 atm. Multiple characterizations are used to identify the Ti-related active species and their effect on the performance. It was found that a higher proportion of LAS caused by Ti was beneficial to the activation of reactant, and the slightly increased amount of BAS leaded to more alkanes converting into light olefins. This understanding may open new opportunities for design and modification of catalytic cracking catalysts.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
The co-aromatization of methane with higher hydrocarbons represents a promising route to valorize methane, an abundant but underexploited carbon resource. In this study, we elucidate a novel approach to enhance the ca...The co-aromatization of methane with higher hydrocarbons represents a promising route to valorize methane, an abundant but underexploited carbon resource. In this study, we elucidate a novel approach to enhance the catalytic co-aromatization of hexane and methane by confining Pt within zeolite catalysts and modulating its electron density. Our findings show that encapsulating Pt within MFI structure is pivotal for activating the feedstock and fostering the formation of aromatic products. Interaction between K atoms and the silanol nest forms siloxy groups which are critical for the stabilization of Pt species. Tuning the K content in PtSn@MFI catalysts adeptly alters the electronic configuration of Pt clusters. This modification is corroborated by infrared and X-ray photoelectron spectroscopy analysis, and density functional theory calculations. Remarkably, the catalyst with 0.8 wt% K exhibits an optimal Pt electron density, driving its superior efficacy in the co-aromatization reaction, converting 0.78 mol of methane for each mole of hexane processed. By employing ~(13)C isotopic labeling and solid-state NMR studies, we demonstrate the participation of methane in the adsorbed species inside the zeolite channel and its incorporation to the benzyl site of the substitute group and phenyl rings in aromatic compounds, underscoring the importance of Pt encapsulation.展开更多
Tin dioxide （SnO2） nano-particles were prepared on high silica TON, MFI and FAU type zeolites by impregnation of SnC12 solution and subsequent calcination at 873 K. XRD and SAED were used to characterize the crystal...Tin dioxide （SnO2） nano-particles were prepared on high silica TON, MFI and FAU type zeolites by impregnation of SnC12 solution and subsequent calcination at 873 K. XRD and SAED were used to characterize the crystalline phase, and TEM was used to characterize the morphology, the particle size and the agglomerative state of the formed nano-materials. The nano-particles, which possess 8 nm, 10-80 nm and 6 nm in size, were found to form on the outer surface of TON, MFI and FAU zeolites, respectively. SnO2 microcapsules and SnOz netlike nanostructure were obtained by decomposition of SnO2-TON and SnO2-MFI in 40% hydrofluoric acid at room temperature. Compared with the nano-particles formed on NaY zeolite, the special morphology and the agglomerative state of SnO2 nanostructures on TON and MFI type zeolites with one and two dimension channel system indicate that the heterogeneous framework, surface structure and property perform important function for forming and growing SnO2 nanostructure on the outer surface of the zeolites.展开更多
Engineering of crystal morphology affects the catalytic and adsorption properties of zeolitic materials.Considering the anisotropic diffusion of molecules derived from its topological features,MFI zeolite nanosheets w...Engineering of crystal morphology affects the catalytic and adsorption properties of zeolitic materials.Considering the anisotropic diffusion of molecules derived from its topological features,MFI zeolite nanosheets with short b-axis thickness are highly desired materials to reduce diffusion resistance.However,the design and development of eco-friendly synthesis protocols with reasonable cost and high efficiency remain elusive.Herein,we reported a systematic study on the synthesis of MFI nanosheets using urea as an additive.Both silicalite-1 and ZSM-5 zeolites(MFI type framework structure)with controllable b-thicknesses ranging from 50–200 nm were achieved by optimizing the synthetic parameters including water content,urea and SDA concentrations.The concentration of hydroxide anions was found to dominate the crystallization kinetics compared with the counterpart tetrapropylammonium cations(TPA^(+)).To facilitate the crystal growth of MFI zeolites in the presence of urea,the ratio OH−/SiO_(2)has to be higher than 0.2,independent of the TPA+concentration.The role of urea in the assistance of plate-like crystal formation through the inhibition of(010)facet growth was revealed by electron microscopy and infrared(IR)spectroscopy analyses.The developed strategy for morphological engineering is not limited to the MFI-type zeolite and can be applied to other frameworks depending on the intrinsic properties of additive molecules and the interactions between them.展开更多
Core-shell structured ZSM-5@Silicalite-1 zeolite could effectively hinder the deactivation of catalyst surface. Currently, organic structure directing agents(OSDAs) are necessary in the conventional route for the synt...Core-shell structured ZSM-5@Silicalite-1 zeolite could effectively hinder the deactivation of catalyst surface. Currently, organic structure directing agents(OSDAs) are necessary in the conventional route for the synthesis of this core-shell zeolite under hydrothermal conditions, which is costly and environmental-unfriendly. In this research, a synthesis of the core-shell structured ZSM-5@Silicalite-1 zeolite with a strategy of alcohol filling and zeolite seeding without any organic template or solvent is exhibited. The obtained products are well characterized by X-ray powder diffractometer(XRD), scanning electron microscopy(SEM), transmission electron microscopy(TEM), N2 sorption isotherms, solid magic angle spinning(MAS) NMR, temperature-programmed-desorption of ammonia(NH3-TPD), and X-ray photoelectron spectroscopy(XPS) techniques, in order to confirm the core-shell structure. More importantly, the core-shell structured ZSM-5@Silicalite-1 zeolite exhibits a long lifetime and a high p-xylene selectivity in the alkylation of toluene with methanol, compared with the conventional ZSM-5 catalyst.展开更多
文摘A series of Mo-containing MFI zeolites with different Mo loadings(Mo-MFI-n,n represent the initial Si/Mo molar ratio)was hydrothermally synthesized by using tetrapropylammonium hydroxide as the template and Mo-EDTA complex as the Mo source.Various characterization results demonstrated that the use of the Mo-EDTA complex is beneficial for the incorporation of more Mo species into the MFI-type zeolites.The special complexing capability of EDTA^(2–)plays a critical role in adjusting the release rate of the Mo species to combine with the Si tetrahedron species during the zeolite growth process,thus leading to a uniform distribution of Mo in the MFI framework.In addition,a small portion of extra-framework Mo clusters may be distributed inside the channels or near the pore window of the zeolites.The catalytic properties of these Mo-containing MFI zeolites were evaluated for the epoxidation of cyclohexene with H_(2)O_(2)as the oxidant.The composition-optimized catalyst,Mo-MFI-50,efficiently converted cyclohexene to the corresponding epoxide with a relatively high conversion(93%)and epoxide selectivity(82%)at 75℃after 9 h of reaction.Moreover,the resultant Mo-containing MFI catalyst exhibited excellent structural stability and recoverability and was easily recycled by simple filtration without the need for calcination treatment.
文摘Catalytic cracking of naphtha is now a process of huge development potential to produce light olefins, which are important basic raw materials used in various industries, but current industrial catalysts like ZSM-5 zeolites suffer from low selectivity and high energy consumption. Here, Ti/Al-containing nanosize MFI-structure zeolites in-situly synthesized through one-pot method were applied to the catalytic cracking using n-hexane as the model reactant. The maximum mass yield of combined light olefins reaches 49.2% with 99% conversion at 600<span style="color:#4F4F4F;font-family:-apple-system, "font-size:16px;white-space:normal;background-color:#FFFFFF;">°</span>C and 1 atm. Multiple characterizations are used to identify the Ti-related active species and their effect on the performance. It was found that a higher proportion of LAS caused by Ti was beneficial to the activation of reactant, and the slightly increased amount of BAS leaded to more alkanes converting into light olefins. This understanding may open new opportunities for design and modification of catalytic cracking catalysts.
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.
基金supported by the National Natural Science Foundation of China(22002179)the Shanxi Provincial Science and Technology Department(YDZJSX2022A074)。
文摘The co-aromatization of methane with higher hydrocarbons represents a promising route to valorize methane, an abundant but underexploited carbon resource. In this study, we elucidate a novel approach to enhance the catalytic co-aromatization of hexane and methane by confining Pt within zeolite catalysts and modulating its electron density. Our findings show that encapsulating Pt within MFI structure is pivotal for activating the feedstock and fostering the formation of aromatic products. Interaction between K atoms and the silanol nest forms siloxy groups which are critical for the stabilization of Pt species. Tuning the K content in PtSn@MFI catalysts adeptly alters the electronic configuration of Pt clusters. This modification is corroborated by infrared and X-ray photoelectron spectroscopy analysis, and density functional theory calculations. Remarkably, the catalyst with 0.8 wt% K exhibits an optimal Pt electron density, driving its superior efficacy in the co-aromatization reaction, converting 0.78 mol of methane for each mole of hexane processed. By employing ~(13)C isotopic labeling and solid-state NMR studies, we demonstrate the participation of methane in the adsorbed species inside the zeolite channel and its incorporation to the benzyl site of the substitute group and phenyl rings in aromatic compounds, underscoring the importance of Pt encapsulation.
基金Project supported by the National Natural Science Foundation of China （No. 2073010）, the National Basic Research Program of China （No. 2003CB615801）, the Nano-Materials Foundation of Shanghai （No. 0213NM042） and the Science and Technology Foundation of Ministry of Construction （No. 05-k2-33）.
文摘Tin dioxide （SnO2） nano-particles were prepared on high silica TON, MFI and FAU type zeolites by impregnation of SnC12 solution and subsequent calcination at 873 K. XRD and SAED were used to characterize the crystalline phase, and TEM was used to characterize the morphology, the particle size and the agglomerative state of the formed nano-materials. The nano-particles, which possess 8 nm, 10-80 nm and 6 nm in size, were found to form on the outer surface of TON, MFI and FAU zeolites, respectively. SnO2 microcapsules and SnOz netlike nanostructure were obtained by decomposition of SnO2-TON and SnO2-MFI in 40% hydrofluoric acid at room temperature. Compared with the nano-particles formed on NaY zeolite, the special morphology and the agglomerative state of SnO2 nanostructures on TON and MFI type zeolites with one and two dimension channel system indicate that the heterogeneous framework, surface structure and property perform important function for forming and growing SnO2 nanostructure on the outer surface of the zeolites.
基金the National Natural Science Foundation of China(NSFC)(No.22178389)S.M.acknowledges the support from NSFC(No.21975285)Z.X.Q.and S.M.acknowledge the support from PetroChina(Nos.PRIKY21084 and KYWX-21-021).
文摘Engineering of crystal morphology affects the catalytic and adsorption properties of zeolitic materials.Considering the anisotropic diffusion of molecules derived from its topological features,MFI zeolite nanosheets with short b-axis thickness are highly desired materials to reduce diffusion resistance.However,the design and development of eco-friendly synthesis protocols with reasonable cost and high efficiency remain elusive.Herein,we reported a systematic study on the synthesis of MFI nanosheets using urea as an additive.Both silicalite-1 and ZSM-5 zeolites(MFI type framework structure)with controllable b-thicknesses ranging from 50–200 nm were achieved by optimizing the synthetic parameters including water content,urea and SDA concentrations.The concentration of hydroxide anions was found to dominate the crystallization kinetics compared with the counterpart tetrapropylammonium cations(TPA^(+)).To facilitate the crystal growth of MFI zeolites in the presence of urea,the ratio OH−/SiO_(2)has to be higher than 0.2,independent of the TPA+concentration.The role of urea in the assistance of plate-like crystal formation through the inhibition of(010)facet growth was revealed by electron microscopy and infrared(IR)spectroscopy analyses.The developed strategy for morphological engineering is not limited to the MFI-type zeolite and can be applied to other frameworks depending on the intrinsic properties of additive molecules and the interactions between them.
基金This work was supported by the National Key Research and Development Program of China(No.2017YFB0702803)the Fundamental Research Funds for the Central Universities,China(No.2021QNA4028)the National Natural Science Foundation of China(Nos.21802121,2217020097,21720102001).
文摘Core-shell structured ZSM-5@Silicalite-1 zeolite could effectively hinder the deactivation of catalyst surface. Currently, organic structure directing agents(OSDAs) are necessary in the conventional route for the synthesis of this core-shell zeolite under hydrothermal conditions, which is costly and environmental-unfriendly. In this research, a synthesis of the core-shell structured ZSM-5@Silicalite-1 zeolite with a strategy of alcohol filling and zeolite seeding without any organic template or solvent is exhibited. The obtained products are well characterized by X-ray powder diffractometer(XRD), scanning electron microscopy(SEM), transmission electron microscopy(TEM), N2 sorption isotherms, solid magic angle spinning(MAS) NMR, temperature-programmed-desorption of ammonia(NH3-TPD), and X-ray photoelectron spectroscopy(XPS) techniques, in order to confirm the core-shell structure. More importantly, the core-shell structured ZSM-5@Silicalite-1 zeolite exhibits a long lifetime and a high p-xylene selectivity in the alkylation of toluene with methanol, compared with the conventional ZSM-5 catalyst.
