分别以γ-氨丙基和甲基丙烯酸丙酯基修饰介孔分子筛MCM-41内孔壁，将引入的有机官能团与金属配位离子[Mn(phen)2Cl]+通过配位键成键首次合成了锰(II)配位化合物修饰的MCM-41(MCM-ap-Mn(phen)2,MCM-mp-Mn(phen)2)。通过XRD、FTIR、77K氮气吸附-脱附、UV-VIS漫反射光谱和Mn2+电子顺磁共振谱(ESR)表征了复合物MCM-ap-Mn(phen)2和MCM-mp-Mn(phen)2。由于有机基团对MCM-41孔壁的修饰，使复合物的结晶度降低；增加的有机基团和配合物使红外光谱有所改变； BET比表面积，孔容和最可几孔径均下降；γ-氨丙基或甲基丙烯酸丙酯基与Mn2+的配位而使其UV-VIS漫反射吸收光谱在短波长的吸收加强；室温下Mn2+电子顺磁共振表明Mn(II)配位环境几乎没有变化。
The preparation of manganese(II)-phenanthroline complex functionalized MCM-41 was described. The modification of the internal pore surface of mesoporous MCM-41 with 3-aminopropyl or 3-methacryloyloxypropyl and yielded two different functional groups by using 3-aminopropyltriethoxysilane and (3-methacryloyloxypropyl)trimethoxysilane as the precursors.Manganese(II) phenanthroline complex was grafted onto the functional MCM-41 via the coordination of the metal ion with the functional group. The metal ion complex functionalized mesoporous materials were characterized by XRD, FTIR, N2 adsorption/desorption at 77K, solid state diffuse reflectance UV-VIS spectroscopy as well as electron spin resonance (ESR) at room temperature. After the functionalization, the vibrations such as vC＝C, (δCH2 from the organic ligands or Mn(II) complex can be observed clearly. BET surface area, pore volume and most probably diameter decreased correspondingly according to the data of N2 sorption at 77K. In UV-VIS spectra, the absorption at short wavelength was strengthened because of the introduced organic ligands. And the results of ESR suggested that Mn(II) coordination in complexes didn't change remarkably.
参考文献
| [1] | Beck J S, Vartuli J C, Roth W J, et al. J. Am. Chem. Soc, 1992, 114: 10834-10834. |
| [2] | Kresge C T, Leonowicz M E, Roth W J, et al. Nature, 1992, 359: 710-712. |
| [3] | Moiler K, Bein T. Chem. Mater, 1998, 10: 2950-2963. |
| [4] | O'Brien S, Keates J M, Barlow S. Chem. Mater, 1998, 10: 4088-4099. |
| [5] | Aronson B J, Blanford C F, Stein A. Chem. Mater, 1997, 9: 2842-2851. |
| [6] | Sinclair P E, Sankar G, Catlow C R A, et al. J. Phys. Chem. B, 1997, 101: 4232-4237. |
| [7] | Abe T, Tachibana Y, Uematsu T, et al. Chem. Commun, 1995, 1617-1618. |
| [8] | Baltes M, Voort P V, Collart, O, et al. J. Porous Mater, 1998, 5: 317-324. |
| [9] | 龙英才,许太明,孙尧俊,等(LONG Ying-Cai,et al).化学学报(Acta Chimica Sinica), 1999. 57:1014-1021. |
| [10] | Van Rhijn W M, De Vos D E, Sels B F, et al. Chem. Commun, 1998, 317-318. |
| [11] | Corma A, Martinez A, Martinez-Soria V, et al. J. Catal, 1995, 153: 25-31. |
| [12] | Ozin G A, Ozkar S. Chem. Mater, 1992, 4: 511-521. |
| [13] | Tanev P T, Chibwe M, Pinnavaia T J. Nature, 1994, 368: 321-323. |
| [14] | Xu J, Luan Z H, Wasowicz T, et al. Micro. Meso. Mater, 1998, 22: 179-191. |
| [15] | Luan Z, Xu J, Kevan L, Chem. Mater, 1998, 10: 3699-3706. |
| [16] | Rao R R, Weckhuysen B M, Schoonheydt R A. Chem. Commun, 1999, 445-446. |
| [17] | Zheng S, Gao L, Zhang Q, et al. J. Mater. Chem, 2000, 10: 723-727. |
| [18] | 沈昊宇,廖代正,姜宗慧,等(SHEN Hao-Yu, et al).化学学报(Acta Chimica Sinica), 1999, 57 ..316-320. |
| [19] | Kamitsos E I, Patsis A P, Kordas G. Phys. Rev. B, 1993, 48: 12499-12505. |
- 下载量()
- 访问量()
- 您的评分：
-
10%
-
20%
-
30%
-
40%
-
50%