THF-FER沸石的系列研究—Ⅱ．模板剂分子THF的位置

用^13C HPDEC MAS NMR与热分析方法表征了在四氢呋喃（THF）-Na2O-SiO2- Al2O3-H2O体系中水热合成的高硅Na-THF-FER沸石、酸交换后的H-THF-FER沸石以及 吸附于Na-FER和H-FER沸石中的THF。结果证明，模板剂分子THF位于Na-THF-FER沸 石骨架的FER笼内，平衡骨架阳离子Na^+主要存在于十元环孔道；而吸附子FER沸石 中的THF仅处于十元环孔道中，合成样品中THF的化学位移与液态THF相比，向低场 移动，谱线明显变宽，表明THF分子与FER笼之间存在很强的相互作用。     

THF—FER沸石的系列研究—1．晶体结构稳定性

四氢呋喃（THF）-Na2O-SiO2-Al2O3-H2O体系水热合成的THF-FER沸石，经酸交 换-焙烧脱THF（Ⅰ）或焙烧脱THF-酸交换（Ⅱ）的不同方式处理，均可制得低钠H- FER沸石。经XRD，^27Al与^29Si MAS NMR,低温氮吸附等表征证明，通过1273K高温 的热处理和1073K饱和水蒸气下的水热处理，H-FER沸石骨架保持高度稳定。在高温 水蒸气作用下，Si(2Al）容易从骨架上脱离，而Si(1Al）则保持相对稳定，以（Ⅱ ）方法处理，制备的H-FER沸石在水热条件下易产生较多的硅差劲基缺陷。经高温 热和水热处理后，H-FER沸石孔道结构基本保持完美、开放。     

THF—FER沸石的系列研究—1．晶体结构稳定性

四氢呋喃（THF）-Na2O-SiO2-Al2O3-H2O体系水热合成的THF-FER沸石，经酸交 换-焙烧脱THF（Ⅰ）或焙烧脱THF-酸交换（Ⅱ）的不同方式处理，均可制得低钠H- FER沸石。经XRD，^27Al与^29Si MAS NMR,低温氮吸附等表征证明，通过1273K高温 的热处理和1073K饱和水蒸气下的水热处理，H-FER沸石骨架保持高度稳定。在高温 水蒸气作用下，Si(2Al）容易从骨架上脱离，而Si(1Al）则保持相对稳定，以（Ⅱ ）方法处理，制备的H-FER沸石在水热条件下易产生较多的硅差劲基缺陷。经高温 热和水热处理后，H-FER沸石孔道结构基本保持完美、开放。     

THF-FER沸石的系列研究Ⅰ.晶体结构稳定性

四氢呋喃(THF)-Na2O-SiO2-Al2O3-H2O体系水热合成的THF-FER沸石,经酸交换-焙烧脱THF(Ⅰ)或焙烧脱THF-酸交换(Ⅱ)的不同方式处理,均可制得低钠H-FER沸石.经XRD,27Al与29Si MAS NMR,低温氮吸附等表征证明,通过1273 K高温的热处理和1073 K饱和水蒸气下的水热处理,H-FER沸石骨架保持高度稳定.在高温水蒸气作用下,Si(2Al)容易从骨架上脱离,而Si(1Al)则保持相对稳定.以(Ⅱ)方式处理,制备的H-FER沸石在水热条件下易产生较多的硅羟基缺陷.经高温热和水热处理后,H-FER沸石孔道结构基本保持完美、开放.     

THF-FER沸石的系列研究Ⅲ.晶体结构

用SEM,HRTEM,SAED和XRD拟合等方法研究了在四氢呋喃(THF)-Na2O-SiO2-al2O3-H2O体系中水热合成的高硅Na-THF-FER沸石的晶体结构、孔道定向,以及不同因素对晶胞体积的影响.通过与全硅FER沸石和K-Na-FER沸石对比实验证明,片状的THF-FER沸石晶体与全硅FER沸石晶体骨架结构及晶体生长择优取向相同,其空间群为Pnnm.     

CXN天然沸石的研究Ⅰ.离子交换与结构性质表征

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.     

一种含锌MFI分子筛的合成与表征

本文首次报导了在0.3Na2O /0.08Zn(Ac)2 /SiO2 /0.15TPAOH /0.12柠檬酸 /100H2O的体系中水热合成含锌MFI沸石. 对合成产物用XRD, 29Si MAS NMR和EXAFS等一系列方法进行了表征. 结果表明,合成产物为含锌MFI沸石,锌原子进入到分子筛骨架.     

EU-1分子筛相邻酸性位的DFT计算和酸性表征

利用量子力学中的密度泛函理论(DFT),对EU-1分子筛中与T1、T2、T3、T6、T7、T8位相邻的骨架铝原子的落位稳定性及酸强度进行理论计算.通过计算得知,双Al原子在EU-1分子筛骨架中优先落位于Al7(Si6-Si7)Al8、Al1(Si2-Si2)Al1、Al2(Si1-Si2)Al2、Al1(Si2-Si2)Al3、Al1(Si2)Al3;根据(Al/Si,H)取代能确定了质子的落位,质子氢较易落位于(O12-H)Al1-(O12-H)Al1、(O12-H)Al1-Al1(O13-H)、(O12-H)Al1-Al1(O12-H)、(O14-H)Al2-(O14-H)Al2、Al2(O12-H)-(O14-H)Al2、Al1(O12-H)-(O15-H)Al3、(O26-H)Al7-Al8(O28-H);且根据质子亲和势分析知,EU-1分子筛骨架中质子氢落位于NNN位的Brnsted酸强度小于NNNN位.借助1H MAS NMR分析合成的不同硅铝比的样品,可知硅铝比低的EU-1分子筛Brnsted酸吸收峰的面积增加;由NH3-TPD可知硅铝比低的EU-1分子筛的强酸脱附峰温度降低,酸强度减小.硅铝比低的EU-1分子筛的强酸表现出酸量高、酸强度低的性质.     

天然CXN沸石分子筛水热稳定性研究 II. 水蒸汽处理温度对铵型沸石物化性质的影响

在前文研究天然Stilbite沸石(CXN沸石)水热稳定性影响因素的基础上, 以27Al与29Si MAS NMR, NH3-TPD和低温氮吸附等详细研究了铵型CXN沸石骨架铝配位状态和硅配位状态, 表面酸性与孔性质等与水蒸汽处理温度的关系. 随温度升高, 沸石骨架硅铝比逐渐提高, 并伴随硅羟基缺陷增多. 经750 ℃水蒸汽处理3 h后沸石骨架硅铝比可达到21.3. 沸石总酸量随水蒸汽处理温度的提高而降低, 沸石骨架铝脱除造成沸石孔道部分被堵塞, 但同时形成有利于分子扩散的介孔.     

CXN天然沸石的研究 V. 结构超稳化

以离子交换结合控制焙烧的方法分别制得结构超稳化高硅H-STI-I和H-STI-II沸石. EDX, ²⁹Si MAS NMR, ²⁷Al MAS NMR, FT-IR等表征证明, 其骨架硅铝原子比分别为4.43和10.62. 分段程序升温焙烧后的沸石样品经粉末XRD表征表明, 其结构热稳定性达到1000 ℃以上. 结构稳定化沸石呈现反映微孔特性的I型吸附等温线, 吸附孔道完美、开放. 经历过酸处理的H-STI-II沸石, 结构缺陷增多, 其热稳定性、比表面积及孔容积略低于H-STI-I.     

乙炔、丙烯在多种分子筛上的吸附和脱附性质

在80℃下研究了ZSM5、13X、Y、MOR、5A、SAPO34等多种分子筛和常见载体上乙炔和丙烯的吸附和脱附性能。结果表明，乙炔和丙烯在SiO2、γ-Al2O3上不吸附，而与分子筛存在较强的相互作用。对于同类型的分子筛，两者的饱和吸附量均随分子筛硅铝比的增大而减小。在同一种分子筛上，以摩尔计的丙烯吸附量均明显高于乙炔。在80℃改性β分子筛上乙炔和丙烯饱和吸附量可分别达到0.11mmol/g和4.89mmol/g，该结果明显高于文献报道的结果。     

The leading role of association in framework modification of highly siliceous zeolites with adsorbed methylamine.

Affinity index (AT value), adsorption heat, X-ray diffraction (XRD), and 13C and 29Si magic-angle spinning (MAS) NMR, FTIR, and Raman spectroscopies were used to study the interaction of highly siliceous MFI-, FAU-, and FER-type zeolites with adsorbed methylamine (MA). Compared with the data for methanol, the much higher AT values and adsorption heats, and significant changes in XRD patterns, 29Si MAS NMR spectra, and FTIR spectra for the zeolites after adsorption of MA, revealed a strong hydrogen-bonding interaction between the perfect framework of the zeolites and the adsorbed MAs. This interaction results from the fact that the H atom of the amine group attacks the [Si-O] framework to form a Si-OHN bond, which leads to the appearance of Si-N bonds in the zeolites at 323 K. Therefore, the zeolite framework can be modified with MA under mild conditions. The highly siliceous MFI zeolite and the H-ZSM-5 zeolite with SiO2/Al2O3=31:1 were modified with MA and investigated by temperature-programmed desorption of CO2. The modified zeolites exhibited greatly enhanced basic properties in comparison with those of the raw materials. The influence of defects in the zeolite on the adsorption and the interaction with MA is discussed.     

Structural and mechanistic investigation of a phosphate-modified HZSM-5 catalyst for methanol conversion

Phosphorus modification of a HZSM-5 (MFI) zeolite by wet impregnation has long been known to decrease aromatic formation in methanol conversion chemistry. We prepared and studied a catalyst modified by introducing trimethylphosphine under reaction conditions followed by oxidation. Magic-angle spinning (MAS) NMR shows that extensive dealumination occurs, resulting in a catalyst with a much higher framework SiO2/Al2O3 ratio, as well as extraframework aluminum and approximately 1.4 equiv of entrained phosphoric acid (under working conditions) per aluminum. Upon dehydration or regeneration, the phosphoric acid is converted, reversibly, to entrained P4O10. The aromatic selectivity of the modified catalyst is significantly lower than that of an unmodified zeolite with a similar, increased framework SiO2/Al2O3 ratio. By comparing the rates of H/D exchange in propene under conditions similar to those in methanol conversion chemistry, we determined that the acid site strength is indistinguishable on modified and unmodified zeolites, and this is consistent with theoretical modeling. On the phosphorus-modified zeolite, the rate of propene oligomerization is greatly suppressed, suggesting that entrained phosphate is an impediment to sterically demanding reactions.     

四氢呋喃/水体系中以蒸气相传输法合成高硅FER沸石

以X射线衍射(XRD), 红外光谱(FT-IR), 扫描电镜(SEM), 低温氮吸附, ²⁹Si固体核磁共振(MAS NMR)等研究了含FER晶种的Na₂O-SiO₂-Al₂O₃干胶(SDG)在四氢呋喃(THF)/水(H₂O)混合蒸气相中的结晶行为, 同时研究了体系中THF分子和[SiO₄], [AlO₄]基团在结晶前后状态的变化. 结果表明, 在THF/H₂O混合蒸气中以蒸气相传输法(VPT)可合成结晶度较高、结构完美且孔道开放的FER沸石. ¹³C交叉极化固体核磁共振(CPMASNMR)和差热分析(TG-DTG-DTA)等研究证明THF分子作为模板剂, 位于FER笼内. FER晶种和水能促进FER沸石的结晶.     

MFI沸石上对二甲苯的热脱附

MFI沸石（ZS－5型）的骨架结构内含十氧元环的二维孔道［‘］，孔容积0．18cm‘·g－‘，硅沸石（Silicallte－1）是骨架中不合铝的ZSM－5．’‘StMASNMR话可揭示沸石的结构对称性、硅铝比和局部缺陷［习．Nagy等人间提出St－OH缺陷在含铅量高时形成．Woolery等门则认为出OH完全是由于骨架内包藏的桂的存在而产生，并随铝合量降低而增大．ZSM－5、硅沸石的结构特征和对二甲苯（Px）的性质决定了Px在ZSM－5上的吸附特性·本文用’‘StMASNLDEL表征硅沸石及不同含铅量的H、Na型ZSM－5的结构，并用＊W＊＊G巾TA分析吸附于…     

Effects of ammonium exchange and Si/Al ratio on the conversion of methanol to propylene over a novel and large partical size ZSM-5

One type of ZSM-5 zeolite with large partical size was prepared and characterized by XRD, SEM, N2 adsorption-desorption, XRF, Py-IR and NH3-TPD techniques. Effects of ammonium exchange and SiO2/Al2O3 molar ratios on the reaction of methanol to propylene (MTP) over Na-ZSM-5 and H-ZSM-5 zeolites have been studied in a fixed-bed flow reactor under the operating conditions of T = 500 °C, P = 1 atm, and WHSV = 6 h-1. Ammonium exchange led to a rapid decrease in Na content for Na-ZSM-5 zeolite. The reaction results indicated that Na-ZSM-5 and H-ZSM-5 with different SiO2/Al2O3 molar ratios all exhibited high activity for methanol conversion. Ammonium exchange and the decreased SiO2/Al2O3 molar ratio of ZSM-5 zeolite led to an increase both in strong acid sites and weak acid sites. Na-ZSM-5 with high SiO2/Al2O3 molar ratio was favorable for the formation of propylene. The highest propylene selectivity (45.9%) was obtained over Na-ZSM-5 zeolite catalyst with SiO2/Al2O3 molar ratio of 220.     

CF-2沸石的表面酸性及催化性能

CF-2是一种新型的高硅沸石。1981年我们实验室首先在二乙醇胺-甘油-Na₂O-SiO₂-Al₂O₃-H₂O体系中制备成功^[1],以后才见到关于Theta-1^[2],ISI-1^[3],KZ-2^[4],NO-10^[5]和ZSM-22^[6]沸石的报道。     

Pd/Hβ-zeolite catalysts for catalytic combustion of toluene: Effect of SiO2/Al2O3 ratio

The effect of pure and high silica Hβ zeolites on the catalytic performance of toluene combustion over Pd/H/3 catalyst was evaluated.Pure and high silica β zeolites were prepared by direct synthesis procedures,then 0.1 wt% of palladium was impregnated on different Hβ zeolites via incipient wetness technique using palladium nitrate as the Pd source.The Pd/Hβ catalysts were characterized by XRD,N2 adsorption/desorption,H2O adsorption,NH3-TPD,H2-TPR and XPS techniques.With increasing the SIO2/Al2O3 ratio of β zeolite,the activity of the Pd/Hβ catalysts for toluene combustion increased clearly and the pure silica β zeolite supported Pd catalyst showed the best catalytic activity.The superior catalytic performance of Pd/β catalyst prepared from pure silica β zeolite was attributed to its high hydrophobicity and the preserving ability for PdO active species.