磁性印迹交联AA/AM接枝酯化氰乙基木薯淀粉微球的制备与吸附性能

doi:10.16085/j.issn.1000-6613.2018-1272

摘要/Abstract

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Fe₃O₄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Cu²⁺为模板离子，经表面印迹修饰得到一种对Cu²⁺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)。Cu-IIPs粒径分布均匀，平均粒径为15.60μm，对Cu²⁺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Cu²⁺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Cu²⁺发生吸附时的电子转移机制。

关键词: 接枝酯化氰乙基木薯淀粉, 磁性印迹微球, 离子印迹, 铜离子吸附

Abstract:

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 Fe₃O₄ as the nucleus. Subsequently the magnetic imprinted crosslinked acrylic acid/acrylamide grafted-esterified cyanoethyl cassava starch microspheres(Cu-IIPs) with selective adsorption to Cu²⁺was obtained by surface imprinting modification using Cu²⁺ 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 Cu²⁺ 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 Cu-IIPs was studied. The results showed that the magnetic imprinted polymers could form stable coordination compounds with Cu²⁺， and determined the potential adsorption activity sites. The mechanism of electron transfer between adsorbents and Cu²⁺ was explained by frontier molecular orbital theory and electron distribution.

Key words: grafted-esterified cyanoethyl cassava starch, magnetic imprinted microspheres, ion imprinting, copper ion adsorption

中图分类号:

O636.9

李和平, 龚俊, 张淑芬, 张俊, 胡英相. 磁性印迹交联AA/AM接枝酯化氰乙基木薯淀粉微球的制备与吸附性能[J]. 化工进展, 2019, 38(04): 1930-1940.

Heping LI, Jun GONG, Shufen ZHANG, Jun ZHANG, Yingxiang HU. Synthesis and adsorpting property of magnetic imprinted crosslinked acrylic acid/acrylamide grafted-esterified cyanoethyl cassava starch microspheres[J]. Chemical Industry and Engineering Progress, 2019, 38(04): 1930-1940.

图/表 21

图1 磁性交联AA/AM接枝酯化氰乙基木薯淀粉微球(MM-St)形成示意图

图2 Cu-IIPs形成示意图

图3 原木薯淀粉与Cu-IIPs的红外光谱图

图4 原木薯淀粉和Cu-IIPs的TG-DTG曲线

图5 Cu-IIPs和原木薯淀粉的XRD图

图6 原木薯淀粉和Cu-IIPs的SEM图

图7 Cu-IIPs的粒径分布

图8 Cu-IIPs的磁滞回线

图9 吸附剂用量对Cu2+去除率的影响

图10 吸附时间对Cu2+去除率的影响

图11 温度对Cu2+去除率的影响

图12 pH对Cu2+去除率的影响

表1 Cu-IIPs的再生吸附容量

再生次数	Q/mg?g^-1	再生次数	Q/mg?g^-1
0	25.96	3	22.68
1	24.21	4	21.12
2	23.07

图13 Cu-IIPs表面吸附中心单元微观结构

图14 Cu-IIPs表面吸附中心单元微观结构的最高占据轨道和最低空轨道的分布

图15 Cu-IIPs表面吸附中心的总表面电子密度分布

表2 Cu-IIPs的量子化学参数

配合物

E _HOMO

/eV

E _LUMO

/eV

$Δ$ E

/eV

/Debye

/eV

Δ

表2 Cu-IIPs的量子化学参数

配合物

E _HOMO

/eV

E _LUMO

/eV

$Δ$ E

/eV

/Debye

/eV

Δ

Cu-IIPs

-0.231

-0.062

0.169

5.172

0.147

0.0845

0.3006

表3 Cu-IIPs 的Fukui函数计算值

原子	f ⁺	f ^-	原子	f ⁺	f ^-	原子	f ⁺	f ^-
C1	–0.0012	0.0021	O23	0.0168	0.0082	O49	0.0475	0.0059
C2	–0.0021	–0.0032	C25	–0.0011	0.0033	O50	0.0631	–0.0054
C3	–0.0084	0.0004	C28	0.0091	0.0336	O52	0.0469	0.0032
C4	–0.0009	–0.0030	N29	–0.0109	0.0088	S53	0.0961	0.1394
C8	–0.0059	–0.0254	C30	–0.0054	–0.0032	C55	–0.0104	0.0054
O11	0.0007	0.0381	O32	0.0118	0.0070	C58	–0.0135	–0.0064
C12	0.0591	0.0875	C33	–0.0087	0.0033	C60	0.0050	–0.0022
S13	0.1749	0.2235	C34	–0.0108	0.0024	C63	0.0062	–0.0092
O14	0.0046	–0.0013	C35	–0.0120	–0.0025	N66	0.0115	–0.0020
O16	0.0081	–0.0052	C38	–0.0109	–0.0004	C69	0.0070	0.0771
O17	0.0173	0.0032	C40	0.0109	0.0032	O70	0.0085	0.0672
O19	0.0063	–0.0002	C44	0.0092	0.0032	O71	0.0026	0.0300
C20	-0.0053	-0.0050	O47	0.0215	0.0117

图16 Cu-IIPs f+ 指数等值面图

图17 Cu-IIPs与Cu2+的结合图

表4 Cu-IIPs的能量值

产物

E _complex

/eV

E _metal

/eV

E _polymer

/eV

E _binding

/eV

E _binding

/kJ·mol^-1

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