Development of Mossbauer Spectrometer System for Characterization of Catalysts and Its Application in Catalysis Chemistry

催化剂表征穆斯堡尔谱仪系统的研制及其在催化化学中的应用

• 批准号: 02554024
• 负责人: TOMINAGA Takeshi
• 金额: $ 8.26万
• 依托单位: University of Tokyo
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Developmental Scientific Research (B)
• 财政年份: 1990
• 资助国家: 日本
• 起止时间: 1990 至 1992
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-02554024/
• 关键词: Mossbauer Spectroscopy; Catalyst; Characterization; Zeolite; Catalyst Preparation; メスバウアー分光法; ハイドロタルサイト; メスバウア-分光法; キャラクタリゼ-ション; 担体

A Mossbauer measurement system was developed for characterization of catalysts and their precursors. The system is composed of Mossbauer spectrometric modules and sample-mounting apparatus specially designed for measurement of unstable compounds and catalysts.The Mossbauer measurement system was applied to characterization of the precursors of silica-supported iron-rhodium catalysts. The Mossbauer spectra indicated that size and composition of iron-containing oxides on silica depended on preparation procedures including temperature of calcination.Phthalocyanineiron (II) synthesized in the zeolite supercage was also characterized by Mossbauer spectroscopy. Pyridine-adduct formation was suppressed by limitation of the residual space of the supercage containing phthalocyanineiron (II) molecule and interaction of pyridine with acid sites on the inner supercage. Mossbauer results demonstrate that the size of supercage and the population of acid sites influenced the reactivity of coordination compounds in the zeolite.Electronic and spin states of several iron (II) octahedral complexes with bidentate amines as ligands synthesized in zeolite supercage were also studied by Mossbauer spectroscopy. The Mossbauer parameters indicated that octahedral structure of some iron (II) complexes was distorted in the supercage due to the steric hindrance of the complex ions in the supercage of the zeolite. Mossbauer spectroscopy also indicated that the steric interaction influenced spincrossover of iron (II) complex with (2-aminomethyl) pyridine synthesized in the supercage.Iron (II) cyano-complexes on hydrotalcite was characterized also by Mossbauer spectroscopy. Preliminary results indicated that iron (II) was oxidized on the surface of hydrotalcite.The results obtained in the application studies demonstrate that Mossbauer characterization system using the devices developed in this research project is quite useful for designing new catalysts.

研制了一套用于催化剂及其前驱体表征的穆斯堡尔谱测量系统。该系统由穆斯堡尔谱模块和专为测定不稳定化合物和催化剂而设计的样品安装装置组成，并应用于硅负载铁铑催化剂前驱体的表征。穆斯堡尔谱表明，在氧化硅上的含铁氧化物的大小和组成取决于包括焙烧温度在内的制备过程.在沸石超笼中合成的酞菁铁（II）也用穆斯堡尔谱进行了表征.吡啶加合物的形成被抑制的限制的超笼含有酞菁铁（II）分子的剩余空间和吡啶与内超笼上的酸位点的相互作用。穆斯堡尔谱学研究表明，超笼的大小和酸中心的分布影响着分子筛中配位化合物的反应活性，并对在超笼中合成的几种铁（II）八面体双齿胺配合物的电子和自旋状态进行了研究。穆斯堡尔参数表明，由于铁（II）配合物离子在沸石超笼中的空间位阻作用，使铁（II）配合物的八面体结构在超笼中发生畸变。穆斯堡尔谱也表明空间位阻作用影响了铁（II）-（2-氨甲基）吡啶配合物在超笼中的自旋交叉，并对铁（II）-氰基配合物在水滑石上的自旋交叉进行了表征。初步研究结果表明，铁在水滑石表面发生了氧化反应，应用研究结果表明，利用本研究所开发的穆斯堡尔谱表征系统对新型催化剂的设计具有重要的指导意义。

项目成果

M.Tanaka et al.: "Mossbauer and ESR study on formation of phthalocyanineiron(II)-pyridine adduct in supercage of NaY,KY,and RbY zeolite" J.Radioanal.Nucl.Chem.,Lett.

M.Tanaka 等人：“Mossbauer 和 ESR 研究 NaY、KY 和 RbY 沸石超笼中酞菁铁 (II)-吡啶加合物的形成”J.Radioanal.Nucl.Chem.,Lett。

M.Tanaka et el.: "Mossbauer and ESR Study of Pyridine-inactive Phthalocyanineiron (II) in Zeolite Supercage" J.Radioanal. Nucl.Chem.,Lett.154. 197-207 (1991)

M.Tanaka 等人：“沸石超级笼中吡啶非活性酞菁铁 (II) 的穆斯堡尔和 ESR 研究”J.Radioanal。

M.Tanaka, Y.Minai, T.Watanabe, and T.Tominaga: "Mossbauer and ESR Study of the Formation of Phthalocyanineiron (II) -pyridine Adduct in the Supercage of NaY,KY,and RbY Zeolite" J.Radioanal.Nucl.Chem., Lett.164(4). 255-64 (1992)

M.Tanaka、Y.Minai、T.Watanabe 和 T.Tominaga：“NaY、KY 和 RbY 沸石超笼中酞菁铁 (II) -吡啶加合物形成的穆斯堡尔和 ESR 研究”J.Radioanal.Nucl

M.Tanaka, Y.Minai, T.Watanabe, and T.Tominaga: "Mossbauer and ESR Study of the Effect of Acid Sites on Formation of Phthalocyanineiron (II) -pyridine Adduct in Zeolite Supercage" Int.J.Rad.Appl.Instr., Part A,Appl.Rad.Isot.45(4). 501-8 (1994)

M.Tanaka、Y.Minai、T.Watanabe 和 T.Tominaga：“穆斯堡尔和 ESR 研究酸性位点对沸石超级笼中酞菁铁 (II) -吡啶加合物形成的影响” Int.J.Rad.Appl。