Abstract: The adsorption energy, adsorption equilibrium configuration and electron density difference of the molecular forms and ionic forms of methyl primary amine, secondary amine, tertiary amine and quaternary ammonium salt adsorbed on the (001) surface of montmorillonite were simulated by density functional theory (DFT). The transmittance of supernatant of montmorillonite suspension, adsorption amount of surfacant and surface contact angle were measured. The results showed that the adsorption energy of ionic forms of methyl amines on the surface of montmorillonite was much larger than that of molecular form, so the ionic forms could be adsorbed on the surface stably. The adsorption energies of methyl amines on montmorillonite surface was affected by the degree of substitution of methyl group for H atoms on N atom of alkylamine. The larger the degree of substitution, the smaller the adsorption energy, and the poorer the hydrophobicity modification ability of methyl amines for the montmorillonite surface. The methyl amines cations were adsorbed on montmorillonite mainly through electrostatic interaction and hydrogen bonding. The experimental results of the supernatant of the montmorillonite suspension, adsorption amount of surfactant and surface contact angle were consistent with the results of the simulation.
1 Yuan Xiaotao, Yu Jiang, Liu Huizhou, et al. Synthesis and characterization of novel organic/inorganic pillared clays[J]. Acta Chim Sin,2004,62(11):1049(in Chinese). 原小涛, 余江, 刘会洲, 等. 新型无机/有机复合柱撑粘土材料的合成与表征[J].化学学报,2004,62(11):1049. 2 Chen Jiaxin, An Taicheng, Ding Xuejun, et al. Preparation of TiO2 pillared clays modified by different surfactants and its photocatalytic activity[J]. Bull Mineralogy, Petrology Geochem,2005,24(4):286(in Chinese). 陈嘉鑫, 安太成, 丁雪军, 等. 不同表面活性剂修饰TiO2柱撑粘土的制备及其光催化活性研究[J]. 矿物岩石地球化学通报,2005,24(4):286. 3 Prats S A, dos Santos Martins M A, et al. Polyacry-lamide application versus forest residue mulching for reducing post-fire runoff and soil erosion[J]. Sci Total Environment,2014,468:464. 4 Wang Yu, Wang Lei, Si Youbin, et al. Biodegradation of atrazine in soils by clay minerals immobilized a degradation bacterium[J]. J Agro-Environment Sci,2009,28(11):2401(in Chinese). 汪玉, 王磊, 司友斌, 等. 粘土矿物固定化微生物对土壤中阿特拉津的降解研究[J]. 农业环境科学学报,2009,28(11):2401. 5 Wu Q, Li Z, Hong H. Adsorption of the quinolone antibiotic nalidixic acid onto montmorillonite and kaolinite[J]. Appl Clay Sci,2013,74:66. 6 Mo Cehui, Huang Xiandong, Wu Xiaolian, et al. Adsorption equilibrium and kinetics of quinolone antibiotics on montmorillonite[J]. J Hunan University: Nat Sci,2011,38(6):64(in Chinese). 莫测辉,黄显东,吴小莲, 等. 蒙脱石对喹诺酮类抗生素的吸附平衡及动力学特征[J]. 湖南大学学报:自然科学版,2011,38(6):64. 7 Chen Jun, Min Fanfei, Peng Chenliang. Characteristics of the hydrophobic aggregation of fine particles in coal slurry water under the action of quaternary ammonium salt[J]. J China University of Mi-ning Technology,2015,44(2):332(in Chinese). 陈军, 闵凡飞, 彭陈亮, 等. 煤泥水中微细粒在季铵盐作用下的疏水聚团特性[J]. 中国矿业大学学报,2015,44(2):332. 8 Hu Y, Liu L, Min F, et al. Hydrophobic agglomeration of colloidal kaolinite in aqueous suspensions with dodecylamine[J]. Colloids Surf A,2013,434:281. 9 Regan T, Ohldag H, Stamm C, et al. Chemical effects at metal/oxi-de interfaces studied by X-ray absorption spectroscopy[J]. Phys Rev B,2001,64(21):214422. 10 Aprile A, Ciuchi F, Pinalli R, et al. Probing molecular recognition at the solid-gas interface by sum-frequency vibrational spectroscopy[J]. J Phys Chem Lett,2016,7(15):3022. 11 Alvim R S, Miranda C R. First principles characterization of silicate sites in clay surfaces[J]. Phys Chem Chem Phys,2015,17(7):4952. 12 Ngouana W B F, Kalinichev A G. Structural arrangements of isomorphic substitutions in smectites: Molecular simulation of the swelling properties, interlayer structure, and dynamics of hydrated Cs-montmorillonite revisited with new clay models[J]. J Phys Chem C,2014,118(24):12758. 13 陈建华. 硫化矿物浮选固体物理研究[M]. 长沙: 中南大学出版社,2015. 14 Rath S S, Sahoo H, et al. Density functional calculations of amines on the (101) face of quartz[J]. Minerals Eng,2014,69:57. 15 张乃娴. 粘土矿物研究方法[M]. 北京: 科学出版社,1990. 16 Wu Meizhi, Liu Yali, Zeng Ming, et al. Determination of cationic surface-active agent by mmarker bromothymol blue spectrophotometric methods[J]. Fine Chem Intermediates,2002,32(6):55(in Chinese). 吴美芝,吴亚利,曾明. 溴百里酚蓝标记分光光度法测定废水中季胺盐型表面活性剂[J]. 精细化工中间体,2002,32(6):55. 17 Peng C, Min F, Liu L, et al. A periodic DFT study of adsorption of water on sodium-montmorillonite (001) basal and (010) edge surface[J]. Appl Surf Sci,2016,387:308. 18 Wendler K, Thar J, Zahn S, et al. Estimating the hydrogen bond energy[J]. J Phys Chem A,2010,114(35):9529. 19 Scheiner S. Effect of C-H…O hydrogen bond length on the geometric and spectroscopic features of the peptide unit of proteins[J]. Int J Quantum Chem,2010,110(15):2775. 20 Steiner T. The hydrogen bond in the solid state[J]. Angew Chem Int Ed,2002,41:48.
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2017, Vol. 31 
