以天然蛭石(Verm)为原料,通过无机酸改性和有机改性制备出3-氨丙基三乙氧基硅烷改性蛭石(APTES-Verm)。采用傅里叶变换红外光谱仪、热分析仪、场发射扫描电子显微镜、多分子层吸附模型等多种表征手段分析了Verm、酸改性蛭石(a-Verm)和APTES-Verm这3种吸附材料的结构和物理化学性质,并研究了APTES-Verm对环境水体中4种常见的重金属污染物——Cu(Ⅱ)、Pb(Ⅱ)、Cd(Ⅱ)、Hg(Ⅱ)离子的吸附性能。结果表明:用无机酸处理后,得到了比表面积增大、表面富含反应性硅羟基(Si—OH)的a-Verm;a-Verm经过进一步的有机改性后,在Si—OH基团的桥梁作用下,接枝上APTES,相应引入了大量对重金属离子具有吸附作用的—NH2基团。制备的APTES-Verm对Pb(Ⅱ)离子的吸附具有明显的选择性,吸附量达到210.865mg/g。
APTES modified vermiculite (APTES-Verm) was synthesized with vermiculite (Verm) by inorganic acid modification and organic modification methods successively.The surface properties and structures of Verm,Acid-modified Verm (a-Verm) and APTES-Verm were analyzed by FT-IR,TG-DTG,SEM and BET.The adsorption test was studied for the four common heavy metal ions,Cu(Ⅱ),Pb(Ⅱ),Cd(Ⅱ) and Hg(Ⅱ) in the environment.The results show that:the surface area of vermiculite was greatly increased by acid modification,and the Si—OH groups were exposed on the surfaces of vermiculite;the organic modification reaction grafted APTES onto the surfaces of a-Verm successfully,introduced a large amount of —NH2 groups with excellent adsorption function;the surface properties of vermiculite were improved by surface modification methods,the adsorption capacity of vermiculite was greatly improved,and the adsorption for Pb(Ⅱ) showed obvious selectivity in comparison with Cu(Ⅱ),Cd(Ⅱ) and Hg(Ⅱ),the adsorption capacity for Pb(Ⅱ) was 210.865mg/g.
[1] Uddin M K.A review on the adsorption of heavy metals by clay minerals,with special focus on the past decade[J].Che-mical Engineering Journal,2017,308:438-462.
[2] 吴大清,刁桂仪.矿物表面活性及其量度[J].矿物学报,2001,21(3):307-311.
[3] 刘福生,张建洪.蛭石改性处理研究现状评述[J].矿产综合利用,2002(2):24-28.
[4] 韩玲玲,曹惠昌,代淑娟,等.重金属污染现状及治理技术研究进展[J].有色矿冶,2011,27(3):94-97.
[5] 彭同江,孙红娟,等.金云母-蛭石间层矿物阳离子交换容量的影响因素研究[J].矿物岩石,2009,29(1):14-19.
[6] Temuujin J,Okada K,Mac Kenzie K J.Preparation of porous silica from vermiculite by selective leaching[J].Applied Clay Science,2003,22(4):187-195.
[7] Panuccio M R,Sorgonà A,Rizzo M,et al.Cadmium adsorption on vermiculite,zeolite and pumice:batch experimental studies[J].Journal of Environmental Management,2009,90(1):364-374.
[8] Stylianou M A,Inglezakis V J,Moustakas K G,et al.Removal of Cu(Ⅱ) in fixed bed and batch reactors using natural zeolite and exfoliated vermiculite as adsorbents[J].Desalination,2007,215(1/2/3):133-142.
[9] Malandrino M,Abollino O,Giacomino A.Adsorption of heavy metals on vermiculite:influence of pH and organic ligands[J].Journal of Colloid and Interface Science,2006,299(2):537-546.
[10] Lytuong Tran,Wu Pingxiao.Highly enhanced adsorption for the removal of Hg(Ⅱ) from aqueous solution by mercaptoethylamine/mercaptopropyltrimethoxysilane functionalized vermiculites[J].Journal of Colloid and Interface Science,2015,445:348-356.
[11] 李红玲,董斌,韩延安,等.钛酸酯偶联剂的偶联机理及研究进展[J].表面技术,2012,41(4):99-102.
[12] 周世一,林金辉,雷景新.铝酸酯偶联剂表面改性微晶白云母/PVC复合材料的制备及力学性能[J].高分子材料科学与工程,2012,28(3):153-160.
[13] 吴铁力,韦藤幼,潘远凤,等.活性白土的硬脂酸表面改性及其表征非金属矿[J].非金属矿,2011,34(4):32-34.
[14] Zhou Shouyong,Xue Ailian,Zhao Yijiang,et al.Competitive adsorption of Hg2+,Pb2+ and Co2+ ions on polyacrylamide/attapulgite[J].Desalination,2011,270(1/2/3):269-274.
[15] Wang Xiaohuan,Wang Chuanyi.Chitosan-poly(vinyl alcohol)/attapulgite nanocomposites for copper(Ⅱ) ions removal:pH dependence and adsorption mechanisms[J].Colloids and Surfaces A:Physicochemical and Engineering Aspects,2016,500:186-194.
[16] 姚超,李锦春,丁永红.纳米凹凸棒石表面硅烷偶联剂改性研究[J].非金属矿,2007,30(6):1-3.
[17] Xue Ailian,Zhou Shouyong,Zhao Yijiang,et al.Effective NH2-grafting on attapulgite surfaces for adsorption of reactive dyes[J].Journal of Hazardous Materials,2011,194:7-14.
[18] Suárez Barrios M,Flores González L V,Vicente Rodríguez M A,et al.Acid activation of a palygorskite with HCl:development of physico-chemical,textural and surface properties[J].Applied Clay Science,1995,10(3):247-258.
[19] Jeon C,Höll W H.Chemical modification of chitosan and equilibrium study for mercury ion removal[J].Water Research,2003,37(19):4770-4780.
[20] Zhao Yijiang,Chen Yan,Li Meisheng.Adsorption of Hg2+ from aqueous solution onto polyacrylamide/attapulgite[J].Journal of Hazardous Materials,2009,171(1/2/3):640-646.
基金资助
国家自然科学基金项目(U1403295,U1703129)