MOR zeolite has been effectively utilized for dimethyl ether(DME)carbonylation reaction due to its unique pore structure and acidity.During industrial production,the transformation of ammonium type MOR zeolite(NH_(4)-...MOR zeolite has been effectively utilized for dimethyl ether(DME)carbonylation reaction due to its unique pore structure and acidity.During industrial production,the transformation of ammonium type MOR zeolite(NH_(4)-MOR)into proton type MOR zeolite(H-MOR)causes inevitable dealumination.Therefore,understanding the influencing factors and dynamic evolution mechanism of zeolite dealumination is crucial.In this work,the stability of framework aluminum was studied by X-ray diffraction(XRD),Fourier transform infrared(FT-IR)spectroscopy,^(29)Si,^(27)Al,^(1)H magic angle spinning nuclear magnetic resonance(MAS NMR),and DME carbonylation performance evaluation.These results indicate that extra-framework cation Na^(+)and NH_(4)^(+)could better preserve the aluminum structure of the MOR zeolite framework compared to H^(+),primarily due to the different'attraction'of the framework to water.Furthermore,the impact of water on the zeolite framework aluminum at high temperature was studied by manipulating the humidity of the calcination atmosphere,revealing the formation of extra-framework six-coordinated aluminum(Al(Ⅵ)-EF)and the mechanism of water influence on the zeolite framework aluminum.展开更多
制备了不同Al含量的Al-MCM-41试样,其中Si/Al比值最小为3,即最高含铝量xAl=0.303.X射线粉末衍射（XPD）分析表明样品具有MCM-41的特征结构,氮气吸附研究表明,样品呈现Ⅳ型吸附等温线,具有孔径分布均一的中孔结构.文中还利用27Al MAS NM...制备了不同Al含量的Al-MCM-41试样,其中Si/Al比值最小为3,即最高含铝量xAl=0.303.X射线粉末衍射（XPD）分析表明样品具有MCM-41的特征结构,氮气吸附研究表明,样品呈现Ⅳ型吸附等温线,具有孔径分布均一的中孔结构.文中还利用27Al MAS NMR研究了试样中Al的化学环境,结果表明,即使在高铝含量的情况下,样品中的铝原子仍以四配位结合在MCM-41的硅骨架上,未能检测出骨架外六配位铝的存在.文中还就Al含量对孔结构的影响以及Al-MCM-41形成机理作了讨论.展开更多
采用27Al MAS NMR、N2吸附-脱附、IR等表征技术及XRD Rietveld结构精修的方法,通过清除和交换引入非骨架铝,探讨了USY沸石中非骨架铝的形态。结果表明,27Al MAS NMR化学位移为0的非骨架铝以游离在超笼中的非骨架铝为主,化学位移为30-50...采用27Al MAS NMR、N2吸附-脱附、IR等表征技术及XRD Rietveld结构精修的方法,通过清除和交换引入非骨架铝,探讨了USY沸石中非骨架铝的形态。结果表明,27Al MAS NMR化学位移为0的非骨架铝以游离在超笼中的非骨架铝为主,化学位移为30-50的非骨架铝与沸石骨架存在键合作用;晶体学可识别的离子态非骨架铝存在于方钠石笼的SⅠ′和SⅡ′位置,其中,SⅠ′位置的非骨架铝与沸石骨架3个O3原子及与其配位的三重轴的O形成不稳定的四配位结构,SⅡ′位置的Al不与沸石骨架O形成配位。超笼中未发现可识别的离子态非骨架铝。聚合态非骨架铝的存在将堵塞沸石孔道,影响微孔吸附性能,并掩盖B酸中心。清除非骨架铝后,可以使沸石孔道畅通,使B酸中心得到恢复。展开更多
以吸附等温线、动力学和热力学等方法研究了金属-有机骨架对苯二甲酸酯-铝[MIL-53(Al),MIL:Materials of Institut Lavoisier]对水中邻硝基苯酚、苯酚和邻苯二酚的吸附行为。MIL-53(Al)对上述酚类化合物的吸附符合准二级吸附动力学模型...以吸附等温线、动力学和热力学等方法研究了金属-有机骨架对苯二甲酸酯-铝[MIL-53(Al),MIL:Materials of Institut Lavoisier]对水中邻硝基苯酚、苯酚和邻苯二酚的吸附行为。MIL-53(Al)对上述酚类化合物的吸附符合准二级吸附动力学模型,且包含表面吸附和孔内扩散两个过程。吸附热力学结果表明,MIL-53(Al)对酚类化合物的吸附是自发的,且为吸热和熵增加过程。在40℃条件下,MIL-53(Al)对邻硝基苯酚、苯酚和邻苯二酚的吸附量分别为78.6、30.5和16.5 mg/g。展开更多
基金support provided by the National Key Research and Development Program of China(No.2022YFE0116000)the National Natural Science Foundation of China(22241801,22022202,22032005,22288101,21972142,21991090,21991092,21991093)Dalian Outstanding Young Scientist Foundation(2021RJ01).
文摘MOR zeolite has been effectively utilized for dimethyl ether(DME)carbonylation reaction due to its unique pore structure and acidity.During industrial production,the transformation of ammonium type MOR zeolite(NH_(4)-MOR)into proton type MOR zeolite(H-MOR)causes inevitable dealumination.Therefore,understanding the influencing factors and dynamic evolution mechanism of zeolite dealumination is crucial.In this work,the stability of framework aluminum was studied by X-ray diffraction(XRD),Fourier transform infrared(FT-IR)spectroscopy,^(29)Si,^(27)Al,^(1)H magic angle spinning nuclear magnetic resonance(MAS NMR),and DME carbonylation performance evaluation.These results indicate that extra-framework cation Na^(+)and NH_(4)^(+)could better preserve the aluminum structure of the MOR zeolite framework compared to H^(+),primarily due to the different'attraction'of the framework to water.Furthermore,the impact of water on the zeolite framework aluminum at high temperature was studied by manipulating the humidity of the calcination atmosphere,revealing the formation of extra-framework six-coordinated aluminum(Al(Ⅵ)-EF)and the mechanism of water influence on the zeolite framework aluminum.
文摘制备了不同Al含量的Al-MCM-41试样,其中Si/Al比值最小为3,即最高含铝量xAl=0.303.X射线粉末衍射（XPD）分析表明样品具有MCM-41的特征结构,氮气吸附研究表明,样品呈现Ⅳ型吸附等温线,具有孔径分布均一的中孔结构.文中还利用27Al MAS NMR研究了试样中Al的化学环境,结果表明,即使在高铝含量的情况下,样品中的铝原子仍以四配位结合在MCM-41的硅骨架上,未能检测出骨架外六配位铝的存在.文中还就Al含量对孔结构的影响以及Al-MCM-41形成机理作了讨论.
文摘采用27Al MAS NMR、N2吸附-脱附、IR等表征技术及XRD Rietveld结构精修的方法,通过清除和交换引入非骨架铝,探讨了USY沸石中非骨架铝的形态。结果表明,27Al MAS NMR化学位移为0的非骨架铝以游离在超笼中的非骨架铝为主,化学位移为30-50的非骨架铝与沸石骨架存在键合作用;晶体学可识别的离子态非骨架铝存在于方钠石笼的SⅠ′和SⅡ′位置,其中,SⅠ′位置的非骨架铝与沸石骨架3个O3原子及与其配位的三重轴的O形成不稳定的四配位结构,SⅡ′位置的Al不与沸石骨架O形成配位。超笼中未发现可识别的离子态非骨架铝。聚合态非骨架铝的存在将堵塞沸石孔道,影响微孔吸附性能,并掩盖B酸中心。清除非骨架铝后,可以使沸石孔道畅通,使B酸中心得到恢复。
文摘以吸附等温线、动力学和热力学等方法研究了金属-有机骨架对苯二甲酸酯-铝[MIL-53(Al),MIL:Materials of Institut Lavoisier]对水中邻硝基苯酚、苯酚和邻苯二酚的吸附行为。MIL-53(Al)对上述酚类化合物的吸附符合准二级吸附动力学模型,且包含表面吸附和孔内扩散两个过程。吸附热力学结果表明,MIL-53(Al)对酚类化合物的吸附是自发的,且为吸热和熵增加过程。在40℃条件下,MIL-53(Al)对邻硝基苯酚、苯酚和邻苯二酚的吸附量分别为78.6、30.5和16.5 mg/g。
