Development of Oxygen Transport Membranes Using Co(II)-complexes Fixed in Zeolites

使用固定在沸石中的 Co(II) 配合物开发氧传输膜

• 批准号: 10555312
• 负责人: SHIOTANI Masan
• 金额: $ 7.42万
• 依托单位: HIROSHIMA UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B).
• 财政年份: 1998
• 资助国家: 日本
• 起止时间: 1998 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-10555312/
• 关键词: adsorptio and desoption of O_2; zeolites; cobalt phthalocvanine; axial ligand; oxygen adduct; ESR; nitrogen oxide; molecular motion; NO; NOx

(1) Cobalt phthalocyanine (Co(II)Ph) complexes were synthesized inside the large cavities of Y-type and MCM41-type zeolites. A formation of the oxygen molecule adducts was clearly observed in both zeolites with Co(II)Ph by ESR method when O_2 molecules were introduced into the CoPc complexes with ammonia, ter-buthylamine and other amines as an axial ligand. Number of the oxygen molecules adducted to Co(II)Pc was studied as a function of axial ligands, oxygen pressures, temperatures, and others. The optimized conditions of O_2 absorption-desoption on the CoPc fixed were discussed based on the experimental results. Furthermore, the reversibility of the O_2 adsorption-desorption reactions and the diffusion and stabilization of un-reacted O_2 molecules were discussed in terms of the stability and bulkiness of the axial ligand used.(2) Effects of axial ligands out O_2/N_2 selectivities of oxygen facilitated transport membranes containing a Co(II)-complex, N,N-bis(3-methoxysalicylidene)-2-methylpropylenediaminato-Co(II), was studied using 4-dimethylaminopyridine (4-DMAP), dimethyl sulfoxide (DMSO) and pyrazine as an axial ligand. The O_2/N_2 selectivities of the membranes resulted in 160, 3 and 2.2, respectively. Based on the results the reaction mechanisms were discussed in terms of oxygenetion and deoxygenation raters.(3) Paramagnetic NO_x(x=1.2) molecules adsorbed on metal ion exchanged zeolites were studied in order to get fundamental information about the relations between the adsorption-desorption reactions and the static-dynamic structures of gaseous molecule related to O_2 in micro-porous crystals.

(1)在Y型和MCM-41型分子筛的大孔道内合成了酞菁钴（Co（II）Ph）配合物。用ESR方法观察到，当O_2分子被引入到以氨、叔丁胺和其它胺为轴向配体的CoPc配合物中时，在两种分子筛中都能清楚地观察到氧分子加合物的形成。加合到Co（II）Pc的氧分子的数量进行了研究作为轴向配体，氧压，温度和其他的函数。在此基础上，探讨了固定化CoPc吸附脱附O_2的最佳条件。此外，还从所用轴向配体的稳定性和大体积两个方面讨论了O_2吸附-脱附反应的可逆性以及未反应O_2分子的扩散和稳定性。(2)以4-二甲氨基吡啶（4-DMAP）、二甲基亚砜（DMSO）和吡嗪为轴向配体，研究了轴向配体对含Co（II）配合物N，N-二（3-甲氧基水杨醛）-2-甲基丙烯二胺合Co（II）氧促进传输膜O2/N2选择性的影响。膜的O_2/N_2选择性分别为160、3和2.2。在此基础上，从加氧速率和脱氧速率两个方面对反应机理进行了探讨。(3)研究了顺磁性NO_x（x=1.2）分子在金属离子交换沸石上的吸附行为，以获得微孔晶体中与O_2有关的气体分子的静动态结构与吸附-脱附反应之间关系的基础信息。

项目成果

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H.Yahiro：“通过 EPR 线形和数值方法研究 Na+ 交换的 A-沸石中 NO 气体的缔合形式和动力学”J.Phys.Chem.A。

A.Volodin: "ESR Study of Monomer and Triplet State Dimer NO Adsorbed on Sulfated Zirconia"Chem.Phys.Lett. 327. 165-170 (2000)

A.Volodin：“硫酸化氧化锆上吸附的单体和三重态二聚体 NO 的 ESR 研究”Chem.Phys.Lett。

W.Liu: "Structure and Dynamics of Trietylamine and Tripropylamine Radical Cations Generated in AlPO_4-5 by Ionizing Radiation"Phys.Chem.Chem.Phys.(in press). (2001)

W.Liu：“AlPO_4-5中电离辐射产生的三乙胺和三丙胺自由基阳离子的结构和动力学”Phys.Chem.Chem.Phys.（出版中）。

S.Yamanouchi et al.: "Effects of Axial Ligands on O_2/N_2 Selectivities of Facilitated Oxygen Transport Membranes Using Cobalt(II) Complex (in Japanese)."J.Chem.Soc.Japan, Chem.Ind.Chem.. 1999. 595-600 (1999)

S.Yamanouchi 等人：“轴向配体对使用钴 (II) 复合物的促进氧运输膜的 O_2/N_2 选择性的影响（日语）。”J.Chem.Soc.Japan、Chem.Ind.Chem.. 1999

M.Shiotani et al.: "Application of ESR to Catalysis : Recent Development."Catalysis. 41. 531-536 (1999)

M.Shiotani 等人：“ESR 在催化中的应用：最新进展”。催化。