高核簇基MOFs的构筑及后合成金属离子替换过程研究
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- 英文论文题名：The construction and postsynthetic metal exchange process of a highnuclear cluster based MOF
- 论文作者：殷政 ; 王鹊桥 ; 陈慧君 ; 曾明华
- 英文论文作者：Zheng Yin ; Que-Qiao Wang ; Hui-Jun Chen ; Ming-Hua Zeng ; Guangxi Normal University ; Shaanxi University of Science and Technology
- 年：2016
- 作者机构：广西师范大学化学与药学学院;陕西科技大学化学化工学院;
- 论文关键词：金属-有机框架 ; 高核簇 ; 后合成修饰 ; 金属离子替换
- 会议召开时间：2016-07-01
- 会议录名称：中国化学会第30届学术年会摘要集-第三十二分会： 多孔功能材料
- 语种：中文
- 分类号：O641.4
- 学会代码：ZGHY
- 会议名称：中国化学会第30届学术年会-第三十二分会 ; 多孔功能材料
- 会议地点：中国辽宁大连
- 主办单位：中国化学会
- 学会名称：中国化学会
- 页数：1
- 文件大小：217k
- 原文格式：D
- 会议级别：全国
摘要
基于金属簇核的金属-有机框架(MOFs)类化合物由于其丰富功能应用一直是当前化学及材料科学研究热点~[1]。尽管已经高度发展,多核尤其是高核数簇基MOFs却十分罕见。相比低核数MOFs,这类高核数MOFs具有高连接、不易穿插、高孔穴率等显著优点~[2]。采用螯合型短桥配体乳酸(H_2Lac)控制簇核形成,线型苯双羧酸桥联配体(H_2L)连接簇,构筑了含{Zn_(22)}巨大簇核、孔穴率高达71%、阴离子框架型MOFs—~[NH_22(CH_3)_2]_4[Zn_(22)(lac)_(12)(L)_(12)]·Guest(1)。Lac-连接四,五,六配位三种Zn~(2+)形成直径约18.0?的簇核,簇核内部还含有直径达7.2?的孔穴。化合物1簇核上的Zn~(2+)可通过后合成离子替换的方式被Co~(2+),Ni~(2+),Cu~(2+),Fe~(3+)等部分或全部取代。跟踪了后合成金属离子取代反应过程,研究了温度,溶液共存阴离子等对离子取代速率及完整性的影响。发现Co~(2+)替换Zn~(2+)时,六配位、五配位、四配位Zn~(2+)被依次替换;Co~(2+)完全取代后框架稳定性明显提升,CO_2吸附量增大6倍。
Cluster based MOFs are one of the current hot topics in chemistry and material science due to their rich function.Though great advance of MOFs,those with highnuclear cluster are rare.Such MOFs are quite helpful for the preparation of highly porous framework with high-connection but without self-interpenetration.The use of mixed ligands of linear H_2L and multidentate lactic acid produced a novel highly porous negative framework of[(CH_3)_2NH_2]_4[Zn_(22)(lac)_2(L)_(12)].guest(1) with unexpected giant {Zn_(22)} cluster and void volume of 71%.The Zn~(2+) in the cluster can be partly or completely replaced by Co~(2+),Ni~(2+),Cu~(2+) or Fe~(3+).The exchange rate and degree is affected by co-existed anion in solution and temperature.The 6-,5-and 4-coordinated Zn~(2+) was replaced by Co~(2+) in sequence.The resulting Co(II) analogue shows higher framework rigidity and also six-time increased CO_2 sorption.
Cluster based MOFs are one of the current hot topics in chemistry and material science due to their rich function.Though great advance of MOFs,those with highnuclear cluster are rare.Such MOFs are quite helpful for the preparation of highly porous framework with high-connection but without self-interpenetration.The use of mixed ligands of linear H_2L and multidentate lactic acid produced a novel highly porous negative framework of[(CH_3)_2NH_2]_4[Zn_(22)(lac)_2(L)_(12)].guest(1) with unexpected giant {Zn_(22)} cluster and void volume of 71%.The Zn~(2+) in the cluster can be partly or completely replaced by Co~(2+),Ni~(2+),Cu~(2+) or Fe~(3+).The exchange rate and degree is affected by co-existed anion in solution and temperature.The 6-,5-and 4-coordinated Zn~(2+) was replaced by Co~(2+) in sequence.The resulting Co(II) analogue shows higher framework rigidity and also six-time increased CO_2 sorption.
引文
[1]Metal-organic frameworks issue.Chem.Soc.Rev.2014,43,5415.
[2]Zhang,W.X.;Zeng,M.H.;Chen,X.M.et al.Coord.Chem.Rev.2015,293-294,263.
[2]Zhang,W.X.;Zeng,M.H.;Chen,X.M.et al.Coord.Chem.Rev.2015,293-294,263.