4-MAA与2-NSA共插层镁铝水滑石的制备和光物理性质

doi:10.3724/SP.J.1077.2012.00122

摘要/Abstract

摘要：

在乙二醇介质中, 通过离子交换法, 成功地将一对具有给体-受体性质的发色团4-甲氧基苯乙酸(4-MAA)与2-萘磺酸(2-NSA)共插入到层状镁铝水滑石层间, 组装得到晶相单一的共插层类水滑石. 产物采用XRD、FTIR、TG-DTA等测试技术进行结构表征, 采用UV-Vis吸收光谱和荧光光谱研究其光谱特性. 并用G03w软件包中ab initio 分子轨道法(HF/6-31G)计算了客体分子结构和电荷分布, 认为4-MAA阴离子是以单层形式以45°倾斜排布在层板之间, 而2-NSA是以单层形式垂直排布层板之间. 结果表明, 给体-受体进入层间后, 不仅客体与主体层板存在静电力和氢键相互作用, 而且在限域空间内客体之间发生了相互作用, 产生了给体-受体间的能量转移过程.

关键词: 水滑石, 共插层, 给体-受体, 能量转移

Abstract:

A pair of chromophores with donor-acceptor properties, 4-methoxyphenylacetic acid (4-MAA) and 2-naphthalene sulfonic acid (2-NSA), were intercalated into the layered double hydroxide (LDH), [Mg_0.66Al_0.34(OH)₂](CO₃)_0.17·0.67H₂O by the method of ion-exchange procedures in ethylene glycol. The obtained co-intercalation compounds were characterized by X-ray diffraction, infrared and thermogravimetry techniques. The photochemical properties of the obtained compounds were studied by UV-Vis absorption and fluorescence spectroscopy. The guest molecular sizes and structures were investigated utilizing an ab initio (HF/6-31G) method by G03w. It was believed that the molecular axis of the interlayer 4-MAA molecule was tilted approximately 45°to the layers, and the molecular axis of the interlayer 2-NSA molecule was perpendicular to the plane of the host layer. Both of them were arranged in monolayer between the metal hydroxide layers. These results indicate that the confinement of the pair of chromophores, 4-MAA-2-NSA, within the interlayer region of hydrotalcites are in favor of guest-host interaction and guest-guest interaction, and that the pair of chromophores, 4-MAA-2-NSA can give rise to energy transfer processes because of the characteristics of their excited states.

Key words: hydrotalcites, co-intercalation, donor-acceptor, energy transfer

中图分类号:

O641

李蕾, 朱凯, 张立, 陈大舟. 4-MAA与2-NSA共插层镁铝水滑石的制备和光物理性质[J]. 无机材料学报, 2012, 27(2): 122-128.

LI Lei, ZHU Kai, ZHANG Li, CHEN Da-Zhou. Preparation and Photophysical Properties of Materials Obtained by Co-intercalation of 4-MAA and 2-NSA into Mg-Al-LDH[J]. Journal of Inorganic Materials, 2012, 27(2): 122-128.

图/表 13

图1 (a)Mg-Al-CO3-LDH, (b)Mg-Al-4-MAA-LDH和(c) Mg- Al-2-NSA-LDH的XRD图谱

Fig. 1 XRD patterns of (a) Mg-Al-CO3-LDH, (b) Mg-Al-4- MAA-LDH and (c) Mg-Al-2-NSA-LDH

图2 (a)Mg-Al-CO3-LDH、(b) 2-NSA、(c) Mg-Al-2-NSA-LDH、(d) 4-MAA和(e) Mg-Al-4-MAA-LDH的FTIR图谱

Fig. 2 FTIR spectra of (a) Mg-Al-CO3-LDH, (b) 2-NSA, (c) Mg-Al-2-NSA-LDH, (d) 4-MAA and (e) Mg-Al-4-MAA-LDH

图3 Mg-Al-4-MAA-LDH(A)和Mg-Al-2-NSA-LDH(B)的TG-DTA曲线

Fig. 3 TG-DTA curves of Mg-Al-4-MAA-LDH (A) and Mg- Al-2-NSA-LDH(B)

Table 1 Chemical compositions of co-intercalation compounds

Sample (n_4-MAA/n_2-NSAin mixture of solution)	Composition
3:1	[Mg_0.66 Al_0.34 (OH) ₂] (4-MAA)_0.22 (2-NSA)_0.10·0.67H₂O
2:1	[Mg_0.66 Al_0.34 (OH) ₂] (4-MAA)_0.17(2-NSA)_0.15·0.66H₂O
1:1	[Mg_0.66 Al_0.34 (OH) ₂] (4-MAA)_0.11(2-NSA)_0.21·0.67H₂O
1:2	[Mg_0.66 Al_0.34 (OH) ₂] (4-MAA)_0.08(2-NSA)_0.24·0.64H₂O
1:3	[Mg_0.66 Al_0.34 (OH) ₂] (4-MAA)_0.05(2-NSA)_0.27·0.63H₂O

图4 不同客体投料摩尔比共插层产物的DTA曲线

Fig. 4 DTA curves of co-intercalation compounds with different n4-MAA/n2-NSA in mixture of solution

图5 (a) 2-NSA、(b) 4-MAA、(c) Mg-Al-2-NSA-LDH和(d) Mg-Al- 4-MAA-LDH的紫外可见光谱

Fig. 5 UV-Vis spectra of (a)2-NSA, (b)4-MAA, (c) Mg-Al-2- NSA-LDH and (d) Mg-Al-4-MAA-LDH

图6 不同客体投料摩尔比共插层产物的紫外吸收光谱

Fig. 6 UV spectra of co-intercalation compounds with different n4-MAA/n2-NSA in mixture of solution

图7 (a) Mg-Al-4-MAA-LDH、(b) 4-MAA、(c) Mg-Al-2- NSA-LDH和(d) 2-NSA的发射光谱(λexc=274 nm)

Fig. 7 Emission spectra of (λexc=274 nm) (a) Mg-Al-4-MAA- LDH, (b) 4-MAA, (c) Mg-Al-2-NSA-LDH and (d) 2-NSA

图8 不同客体投料摩尔比共插层产物的发射光谱 (λexc=274 nm)

Fig. 8 Emission spectra of co-intercalation compounds with different n4-MAA/n2-NSA in mixture of solution(λexc=274 nm)

图9 4-MAA和2-NSA的吸收和发射光谱

Fig. 9 Absorption and emission spectra of 4-MAA and 2-NSA

图10 (a) 4-MAA和(b) 2-NSA阴离子的分子结构表2 4-MAA和2-NSA阴离子中氧原子的电荷布居

Fig. 10 Molecular structure of (a) 4-MAA and (b) 2-NSA anion

Table 2 Calculated charges for O of 4-MAA and 2-NSA anions

Anion	Calculated charges
Anion	O¹	O²	O³
4-MAA	-0.7533	-0.7503	-0.6669
2-NSA	-0.6939	-0.7812	-0.6903

图11 (a) Mg-Al-4-MAA-LDH、(b) Mg-Al-2-NSA-LDH和(c) 4-MAA和2-NSA共插产物的结构模型

Fig. 11 Schematic illustration of (a) Mg-Al-4-MAA-LDH, (b) Mg-Al-2-NSA-LDH and (c) co-intercalation compounds

参考文献 13

[1]	Khan A I, O’Hare D. Intercalation chemistry of layered double hydroxides: recent developments and applications. Journal of Materials Chemistry, 2002, 12: 3191-3198.
[2]	Cavani F, Trifiro F, Vaccari A. Hydrotalcite-type anionic clays: preparation, properties and applications. Catalysis Today, 1991, 11(2): 173-301.
[3]	段雪,张法智. 插层组装与功能材料. 北京: 化学工业出版社, 2007.
[4]	Ogawa M, Kuroda K. Photofunctions of intercalation compounds. Chemical Reviews, 1995, 95(2): 399-438.
[5]	Li L, Liu S J, Li B S, et al. Preparation and photochemical characterization of compounds by intercalation of organic UV absorbents into Zn-Al hydrotalcite-like compounds. Chinese Journal of Inorganic Chemistry, 2007, 23(3): 407-414.
[6]	Tanaka T, Nishimoto S, Kameshima Y, et al. A novel nanocomposite material prepared by intercalating photoresponsive dendrimers into a layered double hydroxide. Journal of Solid State Chemistry, 2010, 183(3): 479-484.
[7]	Wang Z L, Kang Z H, Wang E B, et al. Intercalation and photophysical properties of the tetra-(8-hydroxyquinolinato) boron complex and 3,3’,4,4’-benzophenone tetracarboxylic anion into Mg-Al layered double hydroxides. Inorganic Chemistry, 2006, 45(11): 4364-4371.
[8]	Malherbe F, Besse J P. Investigating the effects of guest-host interactions on the properties of anion-exchanged Mg-Al hydrotalcites. Journal of Solid State Chemistry, 2000, 155(2): 332-341.
[9]	Aloisi G G, Costantino U, Elisei F, et al. Preparation and photo-physical characterisation of nanocomposites obtained by intercalation and co-intercalation of organic chromophores into hydrotalcite-like compounds. Journal of Materials Chemistry, 2002, 12: 3316-3323.
[10]	Latterini L, Nocchetti M, Aloisi G G, et al. Organized chromophores in layered inorganic matrices. Inorganica Chimica Acta, 2007, 360(3): 728-740.
[11]	LI Lei, WEN Zheng, CHEN Da-Zhou, et al. Preparation and characterization of chromophores pillared Zn-Al-LDH. Journal of Inorganic Materials, 2009, 24(5): 1019-1024.
[12]	LI Lei, ZHANG Li, CHEN Da-Zhou, et al. Preparation and photophysical properties of chromophores pillared Mg-Al-LDH. Journal of Inorganic Materials., 2010, 25(11): 1133-1138.
[13]	王宗明,何欣翔,孙殿卿. 实用红外光谱学, 2版. 北京: 石油工业出版社, 1990.

[1]	刘雯雯, 苗雨欣, 张轶扉, 王心宇, 兰玉婷, 赵震. 不同形貌MgAl LDH的制备及Pt/LDH的催化加氢性能[J]. 无机材料学报, 2021, 36(12): 1283-1289.
[2]	周雄, 方立志, 黄双武, 夏海平, 胡建旭, 章践立, 陈宝玖. Ce ³⁺/Yb ³⁺共掺LiLuF₄单晶的紫外和近红外发光研究[J]. 无机材料学报, 2020, 35(5): 556-560.
[3]	张炜, 刘晨, 陈元涛, 吴王锁. Mg-Al-Ce水滑石吸附去除水中的硼[J]. 无机材料学报, 2020, 35(3): 337-344.
[4]	张晓锋,张冠华,孟跃,薛继龙,夏盛杰,倪哲明. 席夫碱钴改性CoCr-LDHs材料光催化降解亚甲基蓝研究[J]. 无机材料学报, 2019, 34(9): 974-982.
[5]	李盛菘, 郑永超, 孟澍临, 吴骊珠, 钟近艺, 赵冲林. 核壳型量子点-纳米金颗粒组装体高效检测神经性毒剂模拟剂[J]. 无机材料学报, 2019, 34(8): 893-898.
[6]	王巧, 周庆, 安爽, 杨浩, 黄利宏. 铁助剂对乙酸自热重整制氢用Co_xAl₃Fe_yO_m±δ催化剂的影响[J]. 无机材料学报, 2019, 34(8): 811-816.
[7]	邵蒙蒙, 蒋军辉, 夏盛杰, 倪哲明, 刘凤仙. 含Sn水滑石可见光催化降解对氯苯酚的研究[J]. 无机材料学报, 2016, 31(1): 7-7.
[8]	徐金芳, 邵蒙蒙, 倪哲明, 肖雪春. 反相气相色谱法探究镁铁水滑石及其改性材料的表面性质[J]. 无机材料学报, 2015, 30(9): 971-976.
[9]	杜宝中, 唐晓庆, 彭振国, 米海涛. 磺基水杨酸插层Mg/Cu/Zn/Al-LDHs的组装、表征及紫外性能[J]. 无机材料学报, 2014, 29(4): 352-356.
[10]	魏淑林, 许银生, 张培晴, 陈飞飞, 聂秋华, 徐铁峰, 戴世勋. Tm³⁺/Ho³⁺共掺硫卤玻璃的2.00 μm荧光特性研究[J]. 无机材料学报, 2012, 27(7): 711-715.
[11]	赵策, 曾虹燕, 王亚举, 刘平乐, 李玉芹, 杨永杰. Mg-Al水滑石“记忆效应”及其对Cr(VI)阴离子吸附性能研究[J]. 无机材料学报, 2011, 26(8): 874-880.
[12]	杜宝中, 邰炜, 骆薇, 彭振国. 别嘌醇插层Zn/Al-NO₃-LDH复合材料的组装及缓释性能[J]. 无机材料学报, 2011, 26(12): 1293-1298.
[13]	李蕾, 张立, 陈大舟, 汤桦. 荧光发色团插层镁铝水滑石的制备和光物理性质[J]. 无机材料学报, 2010, 25(11): 1133-1138.
[14]	李蕾,文征,陈大舟,汤华. 生色基团插层锌铝水滑石的制备和性质[J]. 无机材料学报, 2009, 24(5): 1019-1024.
[15]	赵月昌,刘玲,程文萍,吴海虹,杨建国,何鸣元. MgAlZnFeCe类水滑石水热合成、表征及其FCC硫转移性能的研究[J]. 无机材料学报, 2009, 24(1): 171-174.