摘要
以木薯淀粉为主要原料,通过醚化、酯化、接枝三步反应,合成了交联AA/AM接枝酯化氰乙基木薯淀粉。然后以Fe_3O_4为磁性核中心,在反相乳液中制得磁性复合改性淀粉微球;进一步以Cu~(2+)为模板离子,经表面印迹修饰得到一种对Cu~(2+)具有选择吸附性的磁性印迹交联AA/AM接枝酯化氰乙基木薯淀粉衍生物微球(Cu-ⅡPs)。CuⅡPs粒径分布均匀,平均粒径为15.60μm,对Cu~(2+)的吸附率可达98.18%。采用红外光谱、扫描电子显微镜、X射线衍射仪、振动样品磁强计和综合热分析仪对Cu-ⅡPs的结构进行了表征。通过量子化学计算,对优化结构的Cu-ⅡPs的前线轨道、电子密度分布以及Fukui指数进行分析,研究了Cu-ⅡPs的吸附机理,说明Cu-ⅡPs能够与Cu~(2+)形成稳定的配合物,确定了可能的吸附活性位点。通过分子前线轨道理论和电荷分布解释了吸附剂与Cu~(2+)发生吸附时的电子转移机制。
The crosslinked acrylic acid/acrylamide grafted-esterified cyanoethyl cassava starch was synthesized by using cassava starch as main raw material through three steps of etherification esterification and grafting. Then magnetic composite modified starzzch microspheres were prepared in inverse emulsion by using Fe_3O_4 as the nucleus. Subsequently the magnetic imprinted crosslinked acrylic acid/acrylamide grafted-esterified cyanoethyl cassava starch microspheres(Cu-ⅡPs) with selective adsorption to Cu~(2+)was obtained by surface imprinting modification using Cu~(2+)as template ion. The particle size of Cu-ⅡPs was uniformly distributed with the averages particle size of 15.60μm. And the adsorption ratio of Cu-ⅡPs to Cu~(2+)can reach to 98.18%. The structure of the Cu-ⅡPs were characterized by IR, SEM,XRD, VSM and TG-DTG techniques. The frontier orbitals,electron density distribution and Fukui index of optimized Cu-ⅡPs were analysed by quantum chemical calculation. The adsorption mechanism of CuⅡPs was studied. The results showed that the magnetic imprinted polymers could form stable coordination compounds with Cu~(2+), and determined the potential adsorption activity sites. The mechanism of electron transfer between adsorbents and Cu~(2+)was explained by frontier molecular orbital theory and electron distribution.
引文
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