镍盐和氧化镍在NaY沸石中存在状态研究

用ＸＲＤ、ＥＸＡＦＳ和ＴＰＲ方法研究了Ｎｉ（ＮＯ３）２／ＮａＹ和ＮｉＯ／ＮａＹ分散体系。在沸石上，Ｎｉ（ＮＯ３）２的分散比ＮｉＯ容易得多。ＸＲＤ相定量方法测定的ＮｉＯ在ＮａＹ沸石上的分散阈值很低，仅为密置单层容量的２％左右。在分散阈值关ＮｉＯ在沸石上处于分散相和笼外小晶粒两种状态。分散相ＮｉＯ比笼外ＮｉＯ小晶粒难还原。样品中ＮｉＯ含量超过阈值时，笼外小晶粒长大成ＸＲＤ可检测的较大晶粒。     

ZnO在NaY沸石表面的分散研究

利用ＸＲＤ、Ｒａｍａｎ光谱分析了影响ＺｎＯ在ＮａＹ表面分散的各种因素，发现延长干燥时间和多次浸渍能促进ＺｎＯ的分散，测量ＺｎＯ的最大分散量为０．４６ｇ／ｇＮａＹ，已远大于文献结果。与模型估算值进行了比较分析，探讨了ＺｎＯ在分子筛内表面的排布状态。     

一氧化碳高效吸附剂CuCl／分子筛

利用自发单层分散原理，将ＣｕＣｌ分散在载体表面制备高效的ＣＯ吸附剂，将ＣｕＣｌ与γ－Ａｌ２Ｏ３，４Ａ，１３Ｘ，ＮａＹ，ＣｕＹ分子筛等高比表在载体混合，在３５０℃焙烧数小时，ＸＲＤ和ＥＸＡＦＳ研究证明ＣｕＣｌ可在载体表面达到原子水平的分散由于Ｃｕ＾＋可与ＣＯ生成配位键。由此可制得对ＣＯ有高吸附容量和选择性的吸附剂，其中ＣｕＣｌ／ＮａＹ和ＣｕＣｌ／Ｃｕ＾＋Ｙ吸附剂的吸附容量在２０℃，ＣＯ分压为６０ｋＰ     

担载的含氮,氧配体的Ni（Ⅱ）配合物对苯乙烯的催化环氧化研究

合成了３种含氮、氧配体的Ｎｉ（Ⅱ）配合物，并把它们担载于不同的载体上。在无有机溶剂及无相转移剂存在时，考察了在用ＮａＯＣｌ作为氧源时它们对苯乙烯环氧化的催化活性；用共沉淀法将微水溶性的Ｎｉ（ＰＡ）２（Ｈ２Ｏ）２固载于硅溶胶上；利用两种水溶性的新催化剂（Ｎｉ（Ｃ１２Ｈ１２Ｎ２Ｏ２）Ｃｌ２和Ｎｉ（Ｃ１６Ｈ１２Ｎ２Ｏ２）Ｃｌ２）离子型的特性，可以顺利的将它们固载于ＮａＹ型分子筛、Ｎａ基蒙脱土和离子交换树     

NiO在USY分子筛、γ-Al2O3及其混合载体上的NO吸附行为和分布规律

运用红外技术和高斯函数对红外谱图进行分峰拟合,研究了对ＮｉＯ在ＵＳＹ分子筛、γ－Ａｌ２Ｏ３和混合载体上的对ＮＯ吸附规律,并推断出不同ＮｉＯ含量时,Ｎｉ２＋在这些载体上的分布．结果表明：位于γ－Ａｌ２Ｏ３表面、ＵＳＹ分子筛ＳⅡ、ＳⅠ位和ＳⅡ位的Ｎｉ２＋离子吸附ＮＯ时,它们的吸附频率分别为１８５５～１８７５、１９００和１９０５ｃｍ－１．ＮｉＯ在γ－Ａｌ２Ｏ３的体相和表面间存在分布平衡,约有７５％ＮｉＯ存在于γ－Ａｌ２Ｏ３体相中．在ＵＳＹ分子筛上,Ｎｉ２＋分布于分子筛ＳⅠ位的趋势远大于ＳⅡ和ＳⅡ、ＳⅠ位．增加ＮｉＯ含量将增强这种趋势．在混合载体上,Ｎｉ２＋分布于Ａｌ２Ｏ３表面的能力大于分布于分子筛的ＳⅡ和ＳⅡ、ＳⅠ位,增加ＮｉＯ量,分布于γ－Ａｌ２Ｏ３表面及ＵＳＹ分子筛ＳⅡ位的Ｎｉ２＋量显著增加,而分布于分子筛ＳⅡ、ＳⅠ位的Ｎｉ２＋量受其影响较小     

以水热法于ZSM-5分子筛中分散MoO3的研究

热扩散法的ＭｏＯ３最高分散量为每克ＺＳＭ－５上０．０８克ＭｏＯ３．而本文采用水热分散法可使ＭｏＯ３在ＺＳＭ－５分子筛中的分散量大大提高．当分散量高达每克ＺＳＭ－５上０．３克ＭｏＯ３时，通过ＸＲＤ，ＩＲ，ＤＴＡ谱测试和吸附测定，都证实了ＭｏＯ３在ＺＳＭ－５中仍然是以非晶相分散态存在．此时，样品有吸附自重６％的水的吸附能力和相应的孔道．     

双组分体系分散阈值的测定及应用

双组分体系分散阈值的测定及应用陈宜,郭士岭,程爱珠（郑州工学院化工系郑州,４５０００２）关键词分散阈值,分散量,ＣｕＯ,ＮｉＯ,ＨＺＳＭ－５分散阈值与活性组分及载体相互作用有关,是催化研究中的重要参数。对分散阈值的研究大都仅涉及了单组分活性物质在载体...     

利用SHIP－IN－BOTTLE技术在NaY分子筛中合成Ru_8（CO）_（12）原子簇

利用ＳＨＩＰ－ＩＮ－ＢＯＴＴＬＥ技术在ＮａＹ分子筛中合成Ｒｕ_８（ＣＯ）_（１２）原子簇肖丰收，徐如人，何亚男，丁红，张艳秋（吉林大学化学系，长春，１３００２３）关键词原子簇，Ｒｕ_３（ＣＯ）_１２，ＮａＹ分子筛，钌，羰基在多相催化研究中，金属羰基簇合物...     

分子筛笼内铂羰基簇合物在CO＋NO反应中的催化研究

研究了ＮａＹ分子筛超笼内包容的Ｐｔ羰基簇合物催化剂在ＣＯ＋ＮＯ反应中的催化性能。「Ｐｔ１２（ＣＯ）２４」＾２－／ＮａＹ和「Ｐｔ９（ＣＯ）１３」＾２－／ＮａＹ在此反应中表现出比较高的活性。Ｎ２Ｏ被认为是ＣＯ＋ＮＯ反应的中间产物，同时笼内羰基簇合物还表现了比ＳｉＯ２负载的簇合物好的热稳定性，动力学研究表明，在「Ｐｔ１２（ＣＯ）２４」＾２－／ＮａＹ上，ＮＯ被还原和Ｎ２Ｏ生成的反应级数，相对于ＣＯ分压为小     

微波法制备Al2O3/NaY新型复合多孔催化材料

微波法制备Ａｌ２Ｏ３／ＮａＹ新型复合多孔催化材料孙德坤朱建华时吉须沁华（南京大学化学化工学院化学系，南京２１００９３）关键词微波辐射，氧化铝，ＮａＹ沸石，表面分散，多孔复合材料分类号ＴＱ４２６收稿日期：１９９７０２１７．孙德坤：女，１９４１年生，...     

CuCl2/NaY体系表面分散态研究

铜负载分子筛作为催化剂或吸附剂，在石油化工、环境保护等方面有许多用途[1，2]．已有研究发现，铜交换的Y型分子筛对NO分解等反应具有较高活性及稳定性［3-5］．因此研究铜负载Y型分子筛对有关吸附剂和催化剂的制备有重要意义．我们实验室在研究活性组分在载体表面分散现象时     

Zeolites modified by CuCl for separating CO from gas mixtures containing CO2

Although zeolites such as NaY and 13X adsorb CO₂ much more than CO, the adsorption amount of CO₂ and CO can be reversed if the zeolites are modified with CuCl. When zeolite NaY or 13X is mixed with CuCl and heated, high CO adsorption selectivity and capacity can be obtained. Isotherms show the adsorbents have CO capacity much higher than CO₂. This is because CuCl has dispersed onto the surface of the zeolites to form a monolayer after the heat treatment and the monolayer dispersed CuCl can provide tremendous Cu(I) to selective adsorb CO and inhibit the CO₂ adsorption. The monolayer dispersion of CuCl is confirmed by XRD and EXAFS studies. The loading of CuCl on the zeolites has a threshold below which the CuCl forms monolayer after heating and crystalline phase of CuCl can not be detected by XRD. An adsorbent of CuCl/NaY with CuCl content closed to the monolayer capacity shows very high CO selective adsorbability for CO₂, N₂, H₂ and CH₄. At temperature higher than room temperature, the adsorbent has even better CO selectivity for CO₂. Using the adsorbent, a single-stage 4 beds PSA process, working at 70°C and 0.4 MPa to 0.013 MPa, can obtain CO product with purity >99.5% and yield >85%.     

Dehydrogenation activities of highly dispersed transition metal oxides on NaY zeolite

Highly dispersed α-Fe_2O_3/NaY,NiO/NaY,and CuO/NaY catalyst systems were pre-pared by impregnation method.Dispersion thresholds of the transition metal oxides on NaY" zeolitewere determined by XRD phase analysis.The dispersion capacities of the transition metal oxides on NaYzeolite are much lower than that estimated on the basis of a closed packed monolayer in the micropores.The catalytic activity and selectivity of the highly dispersed oxide catalyst systems for ethylben-zene and cyclohexane dehydrogenation reactions were reported.     

用EXAFS方法研究双功能催化剂NiO-MoO3/γ-A2O3的表面分散那

The surface dispersion of bifunctional NiO-MoO_3/γ-alumina catalysts prepared by different procedures was studied with Ni-K EXAFS spectroscopy. The contents of NiO(13.6%) and MoO_3(16.5%) were the same in the three samples, which were a little higher than the monolayer dispersion capacity of each component on γ-Al_2O_3. The dispersion temperature was 450 ℃. The sample impregnated with NiO first shows that the NiO is monolayer-dispersed on γ-Al_2O_3 surface and the outer layer is MoO_3. The sample impregnated with MoO_3 and the outer layer is NiO. There is strong interaction between MoO_3 and γ-Al_2O_3 which affects the dispersion of NiO on the surface. The sample impregnated with NiO and MoO_3 simultaneously shows that the Ni is not dispersed in the form of NiO but another compound on the surface.     

Highly dispersed Cu supported on mesoporous Al-KIT-6 for oxidative carbonylation of methanol to dimethyl carbonate

Microporous NaY zeolite is a common support of Cu catalysts for oxidative carbonylation of methanol, but the dispersion of Cu species on NaY is usually subjected to its micropore size. Here, ordered mesoporous KIT-6 was employed as the support for Cu catalyst and Al was incorporated into its framework to increase the surface acidity, which eventually improves the surface exchange capacity and Cu dispersion. The evolution of the state of Cu species on KIT-6 was analyzed combined with control of Cu loading. The physicochemical properties of the supports and corresponding catalysts were characterized by N₂ adsorption–desorption, X-ray diffraction, ammonia temperature programmed desorption, Fourier transform infrared spectra, transmission electron microscopy, hydrogen temperature programmed reduction, and X-ray photoelectron spectroscopy. It was found that mesoporous KIT-6 showed better Cu dispersion than microporous NaY zeolite. Agglomerated CuO, dispersed CuO, and Cu²⁺ are the major Cu species observed on the catalyst surface. The increased surface acidic sites of KIT-6 by Al incorporation promoted the formation of Cu²⁺ and dispersion of CuO. With the increase in Cu loading, the Cu²⁺ content in the catalyst was decreased gradually along with increase in the bulk CuO. It was speculated that some exchanged Cu²⁺ could be transformed into highly dispersed CuO and even bulk CuO after calcination at a high Cu loading. Combined with the catalyst evaluation results, it was deduced that highly dispersed Cu²⁺ and CuO particles play significant roles in catalytic activity. The catalyst Cu/Al-K-10 achieved the highest space time yield of dimethyl carbonate of 135.4 mg/(g·h), which is 2.7 times the Cu/K-10 owing to its more dispersed Cu species. This laid the basis for preparing highly dispersed Cu species on mesoporous silica supports.     

NiO在γ-Al_2O_3及 TiO_2/γ-Al_2O_3载体上的表面存在状态

本文采用 LRS, XRD, UV-DRS, TPR考查了γ-Al2O3上 TiO2的分散容量,分散态 Ti4＋离子的配位环境; NiO在经 TiO2改性后的γ-Al2O3载体上的分散容量。结果表明：（ 1） TiO2在γ-Al2O3表面的分散容量约为 0.62 mmol/100m2γ-Al2O3,当 TiO2含量低于该分散容量时 Ti4＋在γ-Al2O3载体表面以嵌入形式呈离子态分布;而含量高于分散容量时还有结晶态的 TiO2出现。（ 2） NiO在 TiO2/γ-Al2O3载体表面的分散容量约为 1.1 mmol/100m2γ-Al2O3,比之在γ-Al2O3载体表面的分散容量 (1.5mmol/100m2γ-Al2O3)要低,这是由于γ-Al2O3表面上部分空位被 Ti4＋离子占据。用表面相互作用的“嵌入模型” (Incorporation Model）讨论了这些结果。     

三组分(NiO、La2O3、SiO2)负载型加氢催化剂中La2O3的作用

用X射线衍射分析、FT-IR、小角X光散射等方法研究了浸渍法制备的NiO/SiO_2和NiO/(La_2O_3+SiO_2)样品中组分之间的相互作用。La_2O_3在SiO_2上可形成近乎密置单层的分散。在负载了La_2O_3的SiO_2上,NiO的分散程度比在SiO_2上有明显提高,也更容易被还原,而且还原后所得金属镍粒子的平均粒度降低,小粒子所占百分比提高。这些结果表明,NiO/(La_2O_3+SiO_2)比NiO/SiO_2样品具有更高的加氢还原硝基普鲁卡因为胺基普鲁卡因的活性,与Ni/(La_2O_3+SiO_2)比Ni/SiO_2活性高的情形相一致。