用粉末XRD,FT—IR,^(29)Si MAS NMR,对高硅HZSM—5沸石及疏水硅沸石Silicalite-Ⅰ进行结构性质表征.在室温下,疏水硅沸石具有ZSM—5的单斜对称性.它的红外骨架振动谱及高分辨^(29)Si固体核磁共振谱均显示出高的分辨率.在红外光谱中,3700...用粉末XRD,FT—IR,^(29)Si MAS NMR,对高硅HZSM—5沸石及疏水硅沸石Silicalite-Ⅰ进行结构性质表征.在室温下,疏水硅沸石具有ZSM—5的单斜对称性.它的红外骨架振动谱及高分辨^(29)Si固体核磁共振谱均显示出高的分辨率.在红外光谱中,3700和3500^(-1)左右的表面Si-OH基振动消失.表明疏水硅沸石晶格中的[SiO_4]四面体排列完美.由—Si—O—Si—构成的微孔表面,具有优良的疏水性.展开更多
How the silkworm spins out such an excellent silk fiber has been a hot topic. The issue here is to know how the coil chains in the gland of silkworm transform to β sheet in silk fiber. We used the regenerated silk fi...How the silkworm spins out such an excellent silk fiber has been a hot topic. The issue here is to know how the coil chains in the gland of silkworm transform to β sheet in silk fiber. We used the regenerated silk fibroin to imitate the silk fibroin of the gland to investigate the effect of metal ion(Ca 2+ . Cu 2+ ) on the silk spinning process of Bombyx mori silkworm. The solutions or gel obtained from hte mixture of regenerated silk fibroin and metal ions were dried for mimicking the gradual loss of water in the spinning process. The 13 C NMR spectrum simulation for C β nucleus of alanine quantitatively demonstrated that the conformation of the regenerated silk fibroin is dominantly of silk Ⅰ, whereas the fibroin with metal ions has more silk Ⅱ conformation. Raman spectroscopies show the consistent results with that of NMR. The binding of metal ion with carbonyl and amide in protein backbone allows the protein chain to array regularly, therefore leading to the β sheet formation.展开更多
用三甲基氯硅烷、二甲基二氯硅烷、甲基三氯硅烷、四氯化硅与甲基碘改性高硅MCM-41中孔分子筛.XRD,^(29)Si MAS NMR,^(13)C CP MAS NMR,以及N_2、水与环己烷吸附的表征,显示改性不同程度地改变了分子筛的表面组成与结构,减小孔径,增加...用三甲基氯硅烷、二甲基二氯硅烷、甲基三氯硅烷、四氯化硅与甲基碘改性高硅MCM-41中孔分子筛.XRD,^(29)Si MAS NMR,^(13)C CP MAS NMR,以及N_2、水与环己烷吸附的表征,显示改性不同程度地改变了分子筛的表面组成与结构,减小孔径,增加孔壁厚度,因而影响吸附行为,减小吸附容量.硅烷化减少了MCM-41的表面硅羟基含量,增加其疏水性.用CH_3I改性使孔径减小1.4nm,而硅羟基含量并未显著减少.硅烷化以及用CH_3I改性可提高MCM-41分子筛的热稳定性.SiCl_4的改性作用相对不明显.样品的水及环己烷吸附容量与其表面硅羟基含量呈现不同的线性关系,揭示高硅MCM-41分子筛表面吸附中心的本性.展开更多
The interaction between the adsorbed methylamine(MA) and siliceous FAU zeolite with a perfect framework is investigated with XRD, 29 Si and 13 C MAS NMR and FTIR. As methylamine is loaded into the zeolite, the crystal...The interaction between the adsorbed methylamine(MA) and siliceous FAU zeolite with a perfect framework is investigated with XRD, 29 Si and 13 C MAS NMR and FTIR. As methylamine is loaded into the zeolite, the crystal structure of the zeolite changes. One peak splits to four peaks for the 29 Si MAS NMR spectrum, and the IR vibration of framework with a high resolution become simpler. The fact indicates that there is a strong interaction between adsorbed methylamine and Si—O framework of FAU zeolite, leading to high A T value of affinity index for methylamine on the zeolite. The order structure of MA/FAU associate is discussed as well.展开更多
在TMEDA(四甲基乙基二胺)-Na_2O-SiO_2-Al_2O_3-H_2O体系(Ⅰ),Na_2O-K_2O-Al_2O_3-SiO_2-H_2-HCO_3^-CO_3^(2-) (Ⅱ)及Py(吡啶)-PrNH_2(正丙胺)-HF-SiO_2-H_2O体系(Ⅲ)中,分别合成了纯相FER沸石及FER硅沸石.用粉末XRD,FT-IR,^(29)Si MAS...在TMEDA(四甲基乙基二胺)-Na_2O-SiO_2-Al_2O_3-H_2O体系(Ⅰ),Na_2O-K_2O-Al_2O_3-SiO_2-H_2-HCO_3^-CO_3^(2-) (Ⅱ)及Py(吡啶)-PrNH_2(正丙胺)-HF-SiO_2-H_2O体系(Ⅲ)中,分别合成了纯相FER沸石及FER硅沸石.用粉末XRD,FT-IR,^(29)Si MAS NMR及TG/DTA等表征其结构性质,并用超微量电子真空吸附天平测定这些沸石样品对正己烷,甲醇和水的吸附等温线.结果表明:各体系合成的样品虽然结晶度高,呈现出FER沸石的典型结构特征,但由于它们的组成和晶格微结构不同,热稳定性与吸附性质有明显的差异.在(Ⅰ)体系中合成的FER沸石层错缺陷少,晶格完美,正己烷与甲醇的吸附量可达到理论值,结构破坏温度为1190℃.红外精细谱及^(29)Si MAS NMR高分辨谱证明FER硅沸石具有十分完美的骨架结构.由于晶胞收缩,它对正己烷与甲醇吸附量略低于理论值,并呈现出高度的疏水性.它的结构破坏温度高于1300℃.在(Ⅱ)体系中合成的FER型沸石结构缺陷多,沸石孔中的钾离子不易被质子完全交换.它的正己烷与甲醇吸附量均较低,而水的吸附量相对较高.吸附现象表明,正己烷和甲醇都被吸附于FER沸石的十元环主孔道中,分压较高时,甲醇可通过八元环进入小笼,而水的吸附性质则主要与各样品的Si-OH缺陷及骨架中的阳离子含量有关.展开更多
The structures of silicalite-1 and H、 Na form of ZSM-5 with various SiO2/Al2O3 ratios were characterized by powder XRD, 29Si MAS NMR, and the desorption process of р-xylene (p-x) on the zeolites was investigated by ...The structures of silicalite-1 and H、 Na form of ZSM-5 with various SiO2/Al2O3 ratios were characterized by powder XRD, 29Si MAS NMR, and the desorption process of р-xylene (p-x) on the zeolites was investigated by using TG/DTG/DTA. SiOH defects of ZSM-5 have no relation with the content of structural Al. Silicalite-1 possesses perfect framwork structure without SiOH defects and structural Al. On a curve of TG/DTG/DTA, p-x adsorbed by silicalite completely desorbs in the range of 57-174℃by two steps, accompaned with endothermal effect. While on the TG/DTG/DTA curves of H, Na-ZSM-5, there is a third desorption step of p-x in the range of 180-600℃ with exothermic effect. Below 180℃ the number of desorbed p-x molecules is related to pore space, but over 180℃，it is related to SiOH and positive ion linking with the structural Al.展开更多
对OFF沸石进行离子交换,制备出NH4-OFF沸石,然后通过Li2CO3/NH4-OFF体系的固态反应制备了不同锂离子交换度的Li-OFF沸石.对吸附氮气和氧气的Li-OFF样品进行了7Li MAS NMR表征,结果表明,所有吸附氧气样品的部分7Li MAS NMR共振峰均发生...对OFF沸石进行离子交换,制备出NH4-OFF沸石,然后通过Li2CO3/NH4-OFF体系的固态反应制备了不同锂离子交换度的Li-OFF沸石.对吸附氮气和氧气的Li-OFF样品进行了7Li MAS NMR表征,结果表明,所有吸附氧气样品的部分7Li MAS NMR共振峰均发生了顺磁位移.通过对实验谱的拟合,得知Li-OFF沸石中的锂离子可分布在3类阳离子位置(A,B和C)上,对应于3个不同位移的谱峰.Li+离子并非等比例地进入3类可交换的位置,而是优先占据主孔道中的A位置,随着交换度的升高,位能较高的C和B位置上的Li离子占有率逐渐增加.在100%固态交换度样品中,Li+离子在不同离子位的占有率分别为17%(位置B),29%(位置C)和54%(位置A).其中,位置B是O2分子不可接近的,所以Li-OFF沸石中有83%的阳离子是可以接近的.展开更多
采用离子交换和焙烧等方法,对我国CXN天然沸石(STI型)进行改性.应用化学分析,粉末XRD,TG/DTA,^(27)Al MAS NMR,^(29)Si MAS NMR,低温N_2吸附等方法表征相关的结构、离子交换等性质.CXN沸石的晶胞组成Na_(0.2)Mg_(0.1)Ca_(8.4)[Al_(17.2)...采用离子交换和焙烧等方法,对我国CXN天然沸石(STI型)进行改性.应用化学分析,粉末XRD,TG/DTA,^(27)Al MAS NMR,^(29)Si MAS NMR,低温N_2吸附等方法表征相关的结构、离子交换等性质.CXN沸石的晶胞组成Na_(0.2)Mg_(0.1)Ca_(8.4)[Al_(17.2)Si_(54.8)O_(144)]·65H_2O,属富钙型.经离子交换脱出Ca^(2+)后的沸石在焙烧过程中伴随有骨架脱铝,骨架的热稳定性已由原样的500℃以下提高到700℃以上.交换改性后的沸石,呈现反映该沸石微孔特性的Ⅰ型氮吸附等温线.展开更多
文摘用粉末XRD,FT—IR,^(29)Si MAS NMR,对高硅HZSM—5沸石及疏水硅沸石Silicalite-Ⅰ进行结构性质表征.在室温下,疏水硅沸石具有ZSM—5的单斜对称性.它的红外骨架振动谱及高分辨^(29)Si固体核磁共振谱均显示出高的分辨率.在红外光谱中,3700和3500^(-1)左右的表面Si-OH基振动消失.表明疏水硅沸石晶格中的[SiO_4]四面体排列完美.由—Si—O—Si—构成的微孔表面,具有优良的疏水性.
文摘How the silkworm spins out such an excellent silk fiber has been a hot topic. The issue here is to know how the coil chains in the gland of silkworm transform to β sheet in silk fiber. We used the regenerated silk fibroin to imitate the silk fibroin of the gland to investigate the effect of metal ion(Ca 2+ . Cu 2+ ) on the silk spinning process of Bombyx mori silkworm. The solutions or gel obtained from hte mixture of regenerated silk fibroin and metal ions were dried for mimicking the gradual loss of water in the spinning process. The 13 C NMR spectrum simulation for C β nucleus of alanine quantitatively demonstrated that the conformation of the regenerated silk fibroin is dominantly of silk Ⅰ, whereas the fibroin with metal ions has more silk Ⅱ conformation. Raman spectroscopies show the consistent results with that of NMR. The binding of metal ion with carbonyl and amide in protein backbone allows the protein chain to array regularly, therefore leading to the β sheet formation.
文摘用三甲基氯硅烷、二甲基二氯硅烷、甲基三氯硅烷、四氯化硅与甲基碘改性高硅MCM-41中孔分子筛.XRD,^(29)Si MAS NMR,^(13)C CP MAS NMR,以及N_2、水与环己烷吸附的表征,显示改性不同程度地改变了分子筛的表面组成与结构,减小孔径,增加孔壁厚度,因而影响吸附行为,减小吸附容量.硅烷化减少了MCM-41的表面硅羟基含量,增加其疏水性.用CH_3I改性使孔径减小1.4nm,而硅羟基含量并未显著减少.硅烷化以及用CH_3I改性可提高MCM-41分子筛的热稳定性.SiCl_4的改性作用相对不明显.样品的水及环己烷吸附容量与其表面硅羟基含量呈现不同的线性关系,揭示高硅MCM-41分子筛表面吸附中心的本性.
文摘The interaction between the adsorbed methylamine(MA) and siliceous FAU zeolite with a perfect framework is investigated with XRD, 29 Si and 13 C MAS NMR and FTIR. As methylamine is loaded into the zeolite, the crystal structure of the zeolite changes. One peak splits to four peaks for the 29 Si MAS NMR spectrum, and the IR vibration of framework with a high resolution become simpler. The fact indicates that there is a strong interaction between adsorbed methylamine and Si—O framework of FAU zeolite, leading to high A T value of affinity index for methylamine on the zeolite. The order structure of MA/FAU associate is discussed as well.
基金Project supported by The National Natural Science Foundation of China(Grant CH29236120)-03)Gansu Longhai FuelChemical Company
文摘在TMEDA(四甲基乙基二胺)-Na_2O-SiO_2-Al_2O_3-H_2O体系(Ⅰ),Na_2O-K_2O-Al_2O_3-SiO_2-H_2-HCO_3^-CO_3^(2-) (Ⅱ)及Py(吡啶)-PrNH_2(正丙胺)-HF-SiO_2-H_2O体系(Ⅲ)中,分别合成了纯相FER沸石及FER硅沸石.用粉末XRD,FT-IR,^(29)Si MAS NMR及TG/DTA等表征其结构性质,并用超微量电子真空吸附天平测定这些沸石样品对正己烷,甲醇和水的吸附等温线.结果表明:各体系合成的样品虽然结晶度高,呈现出FER沸石的典型结构特征,但由于它们的组成和晶格微结构不同,热稳定性与吸附性质有明显的差异.在(Ⅰ)体系中合成的FER沸石层错缺陷少,晶格完美,正己烷与甲醇的吸附量可达到理论值,结构破坏温度为1190℃.红外精细谱及^(29)Si MAS NMR高分辨谱证明FER硅沸石具有十分完美的骨架结构.由于晶胞收缩,它对正己烷与甲醇吸附量略低于理论值,并呈现出高度的疏水性.它的结构破坏温度高于1300℃.在(Ⅱ)体系中合成的FER型沸石结构缺陷多,沸石孔中的钾离子不易被质子完全交换.它的正己烷与甲醇吸附量均较低,而水的吸附量相对较高.吸附现象表明,正己烷和甲醇都被吸附于FER沸石的十元环主孔道中,分压较高时,甲醇可通过八元环进入小笼,而水的吸附性质则主要与各样品的Si-OH缺陷及骨架中的阳离子含量有关.
文摘The structures of silicalite-1 and H、 Na form of ZSM-5 with various SiO2/Al2O3 ratios were characterized by powder XRD, 29Si MAS NMR, and the desorption process of р-xylene (p-x) on the zeolites was investigated by using TG/DTG/DTA. SiOH defects of ZSM-5 have no relation with the content of structural Al. Silicalite-1 possesses perfect framwork structure without SiOH defects and structural Al. On a curve of TG/DTG/DTA, p-x adsorbed by silicalite completely desorbs in the range of 57-174℃by two steps, accompaned with endothermal effect. While on the TG/DTG/DTA curves of H, Na-ZSM-5, there is a third desorption step of p-x in the range of 180-600℃ with exothermic effect. Below 180℃ the number of desorbed p-x molecules is related to pore space, but over 180℃，it is related to SiOH and positive ion linking with the structural Al.
文摘对OFF沸石进行离子交换,制备出NH4-OFF沸石,然后通过Li2CO3/NH4-OFF体系的固态反应制备了不同锂离子交换度的Li-OFF沸石.对吸附氮气和氧气的Li-OFF样品进行了7Li MAS NMR表征,结果表明,所有吸附氧气样品的部分7Li MAS NMR共振峰均发生了顺磁位移.通过对实验谱的拟合,得知Li-OFF沸石中的锂离子可分布在3类阳离子位置(A,B和C)上,对应于3个不同位移的谱峰.Li+离子并非等比例地进入3类可交换的位置,而是优先占据主孔道中的A位置,随着交换度的升高,位能较高的C和B位置上的Li离子占有率逐渐增加.在100%固态交换度样品中,Li+离子在不同离子位的占有率分别为17%(位置B),29%(位置C)和54%(位置A).其中,位置B是O2分子不可接近的,所以Li-OFF沸石中有83%的阳离子是可以接近的.
文摘采用离子交换和焙烧等方法,对我国CXN天然沸石(STI型)进行改性.应用化学分析,粉末XRD,TG/DTA,^(27)Al MAS NMR,^(29)Si MAS NMR,低温N_2吸附等方法表征相关的结构、离子交换等性质.CXN沸石的晶胞组成Na_(0.2)Mg_(0.1)Ca_(8.4)[Al_(17.2)Si_(54.8)O_(144)]·65H_2O,属富钙型.经离子交换脱出Ca^(2+)后的沸石在焙烧过程中伴随有骨架脱铝,骨架的热稳定性已由原样的500℃以下提高到700℃以上.交换改性后的沸石,呈现反映该沸石微孔特性的Ⅰ型氮吸附等温线.
