具有结构色的α-磷酸锆/有机溶剂分散体系

对α-磷酸锆（α-ZrP）/H₂O分散体系利用离心沉淀–再分散的方法,进行溶剂置换制备α-ZrP的有机溶剂分散体系.意外发现,使用这个方法可以容易地得到具有结构色的α-ZrP/有机溶剂分散体系.以丙酮为溶剂,当α-ZrP质量分数在0.76%～1.86%之间时,分散体系可以反射426～635 nm范围内的可见光,表现出相对应的结构色.增加体系中离子浓度,呈现红色结构色的α-ZrP/丙酮分散体系（α-ZrP质量分数0.87%）的紫外–可见光反射光谱曲线发生蓝移,表明体系中周期结构的形成主要依赖于α-ZrP纳米片层之间的静电排斥力.结构色的形成还存在一定的尺寸依赖性,大尺寸的α-ZrP纳米片相对于小尺寸样品（1.10 μm vs.0.48 μm）更容易形成表现出结构色的长程有序结构.利用此方法,还得到了以乙腈和丁腈为溶剂,具有明显结构色的分散体系.目前,研究中使用的许多片状无机粒子都具有与α-ZrP晶体相似的层间表面电荷结构,因此本工作所报道的方法对制备这类粒子的长程有序分散体系具有普遍借鉴意义.     

正丁胺对晶态层状苯乙烯基膦酸-磷酸氢锆的插层研究

合成了晶态层状有机-无机多功能材料苯乙烯基膦酸-磷酸氢锆(α-ZPPVPA),并研究了正丁胺(BA)对α-ZPPVPA的插层性能。用元素分析、XRD、IR、TG、SEM和TEM等分析方法对α-ZPPVPA及其插层化合物α-ZPPVPA-BA进行了结构表征和形貌分析。结果表明,正丁胺成功地插入了α-ZPPVPA层板之间,层间距为2.41 nm,正丁胺的插入使α-ZPPVPA的层间距(1.66 nm)增大了0.75 nm,插入的正丁胺在α-ZPPVPA中呈双分子层排列,且苯乙烯基侧链不饱和双键的存在不影响α-ZPPVPA与正丁胺的插层反应。     

磷酸锆类层柱催化剂的制备、表征及其催化甲醇氧化羰基化反应性能

以层状α－磷酸锆为插层主体,采用高温固相离子交换插层法制备Ｃｕ＾２＋,Ｋ柱撑的磷酸锆类层柱催化剂,并用ＸＲＤ,ＩＲ和ＴＧ等方法对其进行了表征。结果表明,金属离子柱撑的α－磷酸锆类层柱催化剂的层间距由原来的０．７６ｎｍ扩撑至０．８１ｎｍ,结晶度有所下降。     

三(2,2'-联吡啶)钌(II)在磷酸锆层状物中的组装及光物理性质

合成了两种层间距极其相近的层状材料Zr(HPO₄)₂•6H₂O(水合α-ZrP)和丁胺-磷酸锆的复合物(α-ZrP•BA), 将发光配合物 组装到层状物中使层间距从1.04 nm增大到1.52 nm. 与层状物相互作用后最大吸收峰均从452 nm (水溶液)红移到了462 nm. 在水合α-ZrP中, 最大发射峰位从610 nm蓝移到604 nm并且荧光强度是水溶液中的两倍多, 连续测定4 h以后, 的荧光强度仅仅下降了4%; 而与α-ZrP•BA相互作用后发射峰位从610 nm移动到了595 nm, 但荧光强度只是稍有增大, 4 h内强度下降了大约29%; 组装到水合α-ZrP中以后, 的激发态寿命从415 ns(水溶液)增大到787 ns (～95%), 在α-ZrP•BA中只增大到了747 ns (～89%). 这些结果表明层状物水合α-ZrP能够为 光物理性能的改善提供更加优良的微观环境.     

三(2,2'-联吡啶)钌(II)在磷酸锆层状物中的组装及光物理性质

合成了两种层间距极其相近的层状材料Zr(HPO₄)₂•6H₂O(水合α-ZrP)和丁胺-磷酸锆的复合物(α-ZrP•BA), 将发光配合物 组装到层状物中使层间距从1.04 nm增大到1.52 nm. 与层状物相互作用后最大吸收峰均从452 nm (水溶液)红移到了462 nm. 在水合α-ZrP中, 最大发射峰位从610 nm蓝移到604 nm并且荧光强度是水溶液中的两倍多, 连续测定4 h以后, 的荧光强度仅仅下降了4%; 而与α-ZrP•BA相互作用后发射峰位从610 nm移动到了595 nm, 但荧光强度只是稍有增大, 4 h内强度下降了大约29%; 组装到水合α-ZrP中以后, 的激发态寿命从415 ns(水溶液)增大到787 ns (～95%), 在α-ZrP•BA中只增大到了747 ns (～89%). 这些结果表明层状物水合α-ZrP能够为 光物理性能的改善提供更加优良的微观环境.     

混合金属氧化物柱撑α-磷酸锆的研究

制备、表征了混合铝/铬金属氧化物柱撑α-磷酸锆(Al/Cr-ZrP),并对胶体化使用有机胺的种类、柱化液金属离子浓度以及金属离子用量等因素进行了研究。研究表明以乙醇胺为胶体化有机胺比使用正丙胺为胶体化有机胺所得到的产物的层间距更大;采用较低金属离子浓度、较高金属离子用量有利于Al/Cr-ZrP的合成。在Al/Cr比为1、以正丙胺为胶体化有机胺、金属离子浓度为0.067mol·L^-1、金属离子用量为6.67CEC的条件下,制备出了混合金属氧化物柱撑α-磷酸锆,其层间距可达3.60nm,     

氧化硅柱撑磺化磷酸-苯膦酸锆的合成及性能

以磷酸-苯膦酸锆为层板,合成并表征了硅柱撑的层柱磷酸-苯膦酸锆,并磺化了其中的苯环.磺化后的产物具有较高的酸量,在酯化反应中催化活性与硫酸相当.     

层状(脯氨酸-N-甲基膦酸-磷酸氢)锆的合成及插层性能研究

以高结晶度制备了层状(脯氨酸-N-甲基膦酸-磷酸氢)锆(α-ZPMPP)晶体(层间距为1.52nm),并研究了其常温下对正丁胺的插层性能,用元素分析、IR、XRD和TG-DSC热分析对α-ZPMPP及其插层复合物进行了表征.结果表明,层状α-ZPMPP具有形成超分子主-客体化合物的插层性能,正丁胺客体分子在主体底物中形成单分子层,并插入α-ZPMPP中,使层间距增大0.45nm,插入的正丁胺可在150～250℃被脱除.     

晶态层状(甘氨酸-N，N-双亚甲基膦酸-磷酸氢)锆的制备和插层

晶态层状(甘氨酸-N;N-双亚甲基膦酸-磷酸氢)锆的制备和插层;（甘氨酸-N;N-双亚甲基膦酸-磷酸氢）锆; 正丁胺; 插层     

氧化铬层柱磷酸锆的制备及催化性能

详细研究了有机胺品种、层板预撑态、水解度以及Ｃｒ加入量等制备因对氧化铬层柱磷酸铬结构和性能的影响，用乙胺胶体化法制备的氧化铬层柱磷酸锆比表面积可高达４８２ｍ＾２／ｇ，而孔径集中在２．６ｎｍ附近，层板胶体化时表面磷酸根的知度水有利于提高支柱产品的比表面和形成规整的平板型层间孔，用ＴＧ，ＩＲ，ＸＲＤ和Ｎ２吸附等温线方法研究了氧化铬柱了的形成过程和热稳定性，异丙醇脱水和异丙苯裂解反应结果表明，氧化铬层柱     

Study on the Intercalation and Interlayer State of Porphyrins into <Emphasis Type="Italic">α</Emphasis>-Zirconium Phosphate

In this work, a new approach for TMPyP [5,10,15,20-tetrakis (1-methylpyridinium-4-yl) porphyrin] and TMAPP [5,10,15,20-tetrakis (N,N,N-trimethyl-anilinium-4-yl) porphyrin] intercalation into α-phase of zirconium hydrogen phosphate (α-ZrP) was described: porphyrins were inserted through exchanging pre-intercalated alkylamine. Pre-intercalated n-butylamine (BA) could form either a mobile monolayer or a stable bilayer in α-ZrP. The exchange speed between porphyrins and BA in mobile monolayer is obviously faster than that in stable bilayer. Therefore mobility of spacers is one important intercalation factor. In addition, we investigated the interlayer state of TMPyP by XRD, visible spectrum, fluorescence spectrum and molecular modeling. The results collectively revealed that the porphyrin was orderly arranged with their planes inclined to the host lamella and was presented as monomer instead of aggregation in the gallery of α-ZrP.This revised version was published online in July 2005 with a corrected issue number.     

Study on the Intercalation and Interlayer State of Porphyrins into α-Zirconium Phosphate

In this work, a new approach for TMPyP [5,10,15,20-tetrakis (1-methylpyridinium-4-yl) porphyrin] and TMAPP [5,10,15,20-tetrakis (N,N,N-trimethyl-anilinium-4-yl) porphyrin] intercalation into α-phase of zirconium hydrogen phosphate (α-ZrP) was described: porphyrins were inserted through exchanging pre-intercalated alkylamine. Pre-intercalated n-butylamine (BA) could form either a mobile monolayer or a stable bilayer in α-ZrP. The exchange speed between porphyrins and BA in mobile monolayer is obviously faster than that in stable bilayer. Therefore mobility of spacers is one important intercalation factor. In addition, we investigated the interlayer state of TMPyP by XRD, visible spectrum, fluorescence spectrum and molecular modeling. The results collectively revealed that the porphyrin was orderly arranged with their planes inclined to the host lamella and was presented as monomer instead of aggregation in the gallery of α-ZrP.     

Unique protonation behavior of cationic free-base porphyrins in the interlayer space of transparent solid films comprising layered α-zirconium phosphate

The protonation behavior of α,β,γ,δ-tetrakis(1-methylpyridinium-4-yl)porphyrin (H₂TMPyP) in the interlayer space of transparent solid films comprising layered α-zirconium phosphate was investigated. It was found that the exposure of H₂TMPyP-impregnated films to aqueous HCl resulted in pyrrole group protonation and induced a color change from yellow to greenish yellow. The two pK_a values of H₂TMPyP, determined as 2.4 and 2.6, exceeded those determined in aqueous solution (0.80 and 2.06), which was attributed to the condensation of H⁺ in the interlayer space caused by the cation exchange reaction between H⁺ in the aqueous solution and n-butylamine intercalated in the interlayer space.     

Surfactant-assisted intercalation of crystal violet in layered γ-zirconium phosphate. Dye uptake from aqueous solutions

Batch intercalation experiments have carried out using γ-zirconium phosphate (γ-ZrP) and one of its cationic surfactant forms (γ-ZrP/SUR⁺) for removing crystal violet from aqueous solutions. The intercalation reactions have conducted along two different intervals of time (24 and 48?h). The intercalation process has followed up by X-ray diffractometry (XRD), UV–Visible and FT-IR spectrophotometries. Regarding γ-ZrP, XRD patterns show that obtained phases are impure, even after 48?h of the reaction time at a maximum dye loading of 18%. On the other side, γ-ZrP/SUR⁺ gives an impure phase after 24?h while a pure one (2.47?nm) is obtained after 48?h at a maximum dye loading of 19%. In both cases, the observed dye loading values are approximately equal to the one calculated by molecular modeling (ca. 20%). The used analysis approaches prove that dye uptake capacity is a function of the reaction time and inclination angle of the dye molecules inside the solid matrices, where the highest dye uptakes are observed with γ-ZrP and γ-ZrP/SUR⁺ after 48?h of the reaction time. This time (48?h) is long enough for the dye molecules to be sufficiently accumulated inside the interlayer regions, in such situation dye molecules are forced to stand up perpendicular to the inorganic layers. With respect to intercalation properties, the difference between γ-ZrP and γ-ZrP/SUR⁺ could be referred to the difference between their gallery heights (1.22 and 3.00?nm, respectively). The pre-intercalation of γ-ZrP with the surfactant molecules assists the inclusion and intercalation of the huge dye molecules into the interlayer region.     

A new method of immobilizing ionic liquids into layered zirconium phosphates

In this work, a new method of a series of ion liquids (ILs) 1-alkyl-3-methylimidazolium chloride [Cnmim]Cl (n = 2, 4, 6, 8) intercalation into layered zirconium phosphates was investigated. It was found that theα-ZrP-2BA (i.e. pre-intercalated BA was arranged in a bilayer mode in the galleries ofα-ZrP) was a suitable host for intercalation ILs: ILs was inserted through exchanging pre-intercalated BA. And the intercalation orientation was investigated by use of X-ray diffraction (XRD) experiments and molecular modeling calculation.     

The Ion-exchange Capacity of Ti and Zr Lamellar Hydrogenphosphates. TG measurements

Thermogravimetric data were used to calculate the number of acidic Brönsted sites in lamellar α-titanium (α-TiP), γ-titanium (γ-TiP), α-zirconium (α-ZrP) and γ-zirconium (γ-ZrP) hydrogenphosphates. The numbers of acidic sites calculated for these lamellar compounds were 7.81, 5.67, 6.33 and 5.56 for α-TiP, γ-TiP, α-ZrP and γ-ZrP, respectively. These values are in good agreement with those found through potentiometric titration. The data obtained prove that thermogravimetric measurements can be used as a reliable analytical tool to follow the ion-exchange capacity of this kind of crystalline lamellar compounds.     

Intercalation of porphyrin (TMPyP) and copper-porphyrin into γ-zirconium phosphate

Water-soluble ,,,-tetrakis(4-N-methylpyridyl)porphine(TMPyP) was directly intercalated into -zirconium phosphate (-ZrP) with expansion of the interlayer distance from 12.3 to a maximum of 17.2 Å, indicating parallel orientation of porphyrin to the layer of -ZrP. Diffuse reflectance spectra of the intercalate shows that the porphyrin is protonated in the interlayer space. Uptake of Cu²⁺ ions into the porphyrin intercalate takes place with further increase in the interlayer distance. It was observed that TMPyP metalated Cu²⁺ in -ZrP. Copper porphyrin can also be taken up quite easily and an interlayer spacing of 18.6 Å is attained.     

Intercalation of n-Alkylamines and n-Alkyldiamines into γ-Zirconium Phenylphosphonate Phosphate

Crystalline -zirconium phenylphosphonate phosphate was prepared according to Yamanaka's method and the intercalation behavior of n-alkylamines and n-alkyldiamines were investigated. In the case of n-alkylamines, a linear increase in interlayer distance was observed up to a carbon atom number of 12, whereas in n-alkyldiamines, only two di-amines, ethylenediamine and propylenediamine, were intercalated with respective increases in the interlayer distance. The increment of interlayer distance in both monoamines and diamines indicates the formation of a monomolecular layer in the interlayer region of the host, in contrast to the case in -zirconium phosphate as a host.     

原位插层聚合法制备聚丙烯酰胺/α-磷酸锆纳米复合材料及其结构表征

聚合物／层状无机物纳米复合材料因具有常规复合材料所没有的结构、形态及较常规聚合物基复合材料更优异的性能而引起人们的广泛关注．α-磷酸锆（α-ZrP）作为一种合成的结构规整的层状无机物，其离子交换容量（600mmol／100g）是粘土的6倍，并具有长径比可控和粒子尺寸分布较窄等特点，是制备聚合物／层状无机物纳米复合材料的优良基体．以往的研究工作主要集中于金属氧化物／α-ZrP层柱材料和聚电解质膜两类复合材料，有关聚合物／α-ZrP插层复合材料的研究报道较少．聚丙烯酰胺（PAM）是一种具有广泛用途的水溶性高分子，作为聚电解质，