光谱学与光谱分析 |
|
|
|
|
|
Studies on IR Spectroscopy and Quantum Chemical Calculation of Chloroaluminate Ionic Liquids Acidity |
WU Qin1,2,HAN Ming-han2*,XIN Hong-liang2,DONG Bin-qi2,JIN Yong2 |
1. School of Chemical Engineering and Environment, Beijing Institute of Technology, Beijing 100081, China 2. Department of Chemical Engineering, Tsinghua University, Beijing 100084, China |
|
|
Abstract The acidity of chloroaluminate ionic liquids and the interaction mechanism of Lewis acid site Al2Cl-7 of chloroaluminate ionic liquid and pyridine were experimentally investigated by IR characterization by using pyridine as molecular probe and increasing pyridine adsorption, and theoretically confirmed by quantum chemical calculations at density functional theory (DFT) and ab initio levels. It was found that the anions,Al2Cl-7 and AlCl-4,which could withdraw lone pair electrons of pyridine, were characteristic of Lewis acid. Therefore, they displayed pyridine coordinated to Lewis acidic site using pyridine as probe. The acidity of Al2Cl-7 was found stronger than that of AlCl-4 by analyzing IR absorption frequency, bond length and charge distribution. The mechanism of forming and evolvement of the Lewis acid site Al2Cl-7 of chloroaluminate ionic liquid was proposed. When the amount of pyridine is small, only the adsorption state of Py-Al2Cl-7 exists. The highly Lewis acidic adsorption state of Py-Al2Cl-7 complex was converted into Py-AlCl-4 complex and Py-AlCl3 complex with increasing pyridine contents, leading to the changes in IR absorption spectra.
|
Received: 2007-01-29
Accepted: 2007-05-08
|
|
Corresponding Authors:
HAN Ming-han
E-mail: hanmh@mail.tsinghua.edu.cn
|
|
[1] DENG You-quan(邓有全). Ionic Liquids: Properties, Preparations and Application (离子液体——性质、制备与应用). Beijing: SINOPEC Press(北京:中国石化出版社),2006. 1. [2] Xin H L, Wu Q, Han M H, et al. Applied Catalysis A: General,2005,292(1-2): 354. [3] Cole A C, Jensen J L, Ntai L, et al. J. Am. Chem. Soc.,2002, 124(21): 5962. [4] Yoo K, Namboodiri V V, Varma R S, et al. Journal of Catalysis,2004,222(2): 511. [5] Gu Y L, Shi F, Deng Y Q. Journal of Molecular Catalysis A: Chemical,2004,212(1-2): 71. [6] Piao L Y, Fu X, Yang Y L, et al. Catal. Today,2004, 93: 301. [7] Zawodzinski T A, Osteryoung R A. Inorg. Chem., 1989, 28(9): 1710. [8] Welton T. Chem. Rev., 1999, 99(8): 2071. [9] Seddon K R. Journal of Chemical Technology and Biotechnology, 1997, 68(4): 351. [10] Wilkes J S. Green Chemistry,2002, 4(2): 73. [11] WU Qin, DONG Bin-qi, HAN Ming-han, et al(吴 芹, 董斌琦, 韩明汉, 等). Spectroscopy and Spectral Analysis(光谱学与光谱分析),2007,27(3): 460. [12] Kline C H, Turkevich J J. Chem. Phys., 1944, 12(7): 300. [13] Ferreira M L, Volpe M. Journal of Molecular Catalysis A: Chemical,2002, 184(1-2): 349. [14] Daturi M, Appel L G. Journal of Catalysis,2002,209(2): 427. [15] Zaki M I, Hussein G A M, Mansour S A A, et al. Colloids and Surfaces A: Physicochem. Eng. Aspects, 1997, 127(1-3): 47. [16] Mohamed M M. Spectrochimica Acta, 1995, A51(1): 1. [17] Bourne K H, Cannings F R, Pitkethly R C. J. Phys. Chem., 1970, 74(10): 2197. [18] Cannings F R. J. Phys. Chem., 1968, 72(13): 4691. |
[1] |
QIAN Duo, SU Wen-en, LIU Zhi-yuan, GAO Xiao-yu, YI Yu-xin, HU Cong-cong, LIU Bin, YANG Sheng-yuan*. Soy Protein Gold Nanocluster as an “Off-On” Fluorescent Probe for the Detection of Bacillus Anthracis Biomarkers DPA[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2023, 43(06): 1815-1820. |
[2] |
ZHANG Dian-kai1, LI Yan-hong1*, ZI Chang-yu1, ZHANG Yuan-qin1, YANG Rong1, TIAN Guo-cai2, ZHAO Wen-bo1. Molecular Structure and Molecular Simulation of Eshan Lignite[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2022, 42(04): 1293-1298. |
[3] |
TIAN Peng1, XIAO Xue-song1, SU Gui-tian1, DUAN Han-feng1,JIN Yao-dong1, SONG Yang-yang1, HUANG Tao2, ZHANG Hang1*. Fluorescence Spectra Analysis of N-n-Octyl Oyridine Acetate Ionic Liquid in Different Solvents[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2022, 42(01): 147-151. |
[4] |
JIANG Shuang-cheng1, FAN Dan-yang2, LIU Yue2, WANG Jia-bin3, LÜ Hai-xia2*. Modification of Ternary Layered Hydroxide and Removing for Orange Ⅱ With Spectroscopy[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2021, 41(12): 3957-3962. |
[5] |
LIU Zheng-jiang1, ZHANG Qian-cheng2, MA Hui-yan2*, LIU Ju-ming2. Spectral Characteristics of Hangjin2# Clay and Its Mechanism in Heterogeneous Fenton Reaction[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2021, 41(11): 3512-3517. |
[6] |
XU Ning1, 2, LIU Mu-hua1, 2, YUAN Hai-chao1, 2, HUANG Shuang-gen1, 2, WANG Xiao1, 2, ZHAO Jin-hui1, 2*, CHEN Jian1, 2, WANG Ting1, 2, HU Wei1, 2, SONG Yi-xin1, 2. Rapid Identification of Sulfamethazine and Sulfadiazine Residues in Chicken Based on SERS[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2021, 41(03): 924-931. |
[7] |
WANG Xiao-hui1, XU Tao-tao1, 2, HUANG Yi-qun3, OU Yi-ming1,4, LAI Ke-qiang1, 2, FAN Yu-xia1, 2*. Rapid Detection of Acid Orange Ⅱ by Surface-Enhanced Raman Spectroscopy Coated with Different Nano-Substrates[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2020, 40(01): 136-141. |
[8] |
FU Yun-peng, QI Ying, HU Xiao-peng, TONG Rui, FANG Guo-zhen*, WANG Shuo. Study on the Determination of Basic Orange Ⅱ and Acid Orange Ⅱ in Food by TLC-SERS[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2018, 38(08): 2419-2424. |
[9] |
CHEN Zhuo1, SU Yu-qing2, SONG Shan1, YAO Jun-xue1*. Determination of Manganese in Water Samples by Cloud Point Extraction with MN-CCA-CPC Flame Atomic Absorption Spectrometry[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2018, 38(08): 2595-2599. |
[10] |
SU Ya-jing, FAN Ting-ting, ZHANG Mei-na, LI Xia*. 4,4’-Bipyridine Bridged Chain Zn(Ⅱ) Complex: Synthesis, Crystal Structure and Fluorescence Sensitization for Tb (Ⅲ) Ion[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2018, 38(07): 2170-2174. |
[11] |
LUO Li-lin, WANG Qiu-shuang, XIE Mei-ting, XI Yu-xin, LI Xia*. The Synthesis, Crystal Structure and Fluorescence Properties of Zinc Complex with 2-(3’,4’-Dicarboxyphenoxy) Benzoate[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2017, 37(09): 2809-2812. |
[12] |
YANG Rui-qin1, XING Zhuo1, ZHOU Hong2 . Spectrophotometric Determination of the Amount of Zinc on the Imprint Left on Hands by Zinc Coatings with 5-Br-PADAP as the Chromogenic Reagent[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2016, 36(12): 4017-4020. |
[13] |
CHEN Qing-hui1, WAN Yao-yu1, LI Qian2, YAO Jun-xue1* . Determination of Cadmium in Shrimp and Shell Fish Samples by Coprecipitation Enrichment with Mn(Ⅱ)-5-Br-PADAP Flame Atomic Absorption Spectrometry[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2016, 36(10): 3351-3354. |
[14] |
ZHANG Tian-yao1,2, ZHANG Zhao-hui1,2*, ZHAO Xiao-yan1,2, ZHANG Han1,2, YAN Fang1,2, QIAN Ping3 . Terahertz Absorption Spectra Simulation of Glutamine Based on Quantum-Chemical Calculation[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2015, 35(08): 2073-2077. |
[15] |
ZOU Shun-ying1, SUN Wen-hao2*, GONG Wei-tao3* . New Bipyridinium Salt: Synthesis and Application as a Fluorescence Enhancement Probe of Nitrate Ion[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2015, 35(06): 1597-1600. |
|
|
|
|