配位聚合物[Cu(py)2(m-bdc)]n的合成、晶体结构及热分解动力学Synthesis, Crystal Structure and Thermal Decomposition Kinetics of a Complex Polymer [Cu(py)2(m-bdc)]n
解凤霞,张丹,张欣欣,华敏
摘要(Abstract)：
采用溶剂扩散法合成了过渡金属配位聚合物:[Cu(py)2(m-bdc)]n(m-bdc=间苯二甲酸,py=吡啶),根据X-单晶衍射给出配合物的结构,该配合物是由间苯二甲酸根桥连的具有二维无限网状结构的聚合物,为单斜晶系,P 21/c空间群,晶胞参数:a=1.0017(5)nm,b=1.1358(6)nm,c=1.7014(7)nm,α=γ=90°,β=114.38(2)°,V=1.7631(15)nm3,Z=15,Dc=1.454 g·cm-3。应用非等温动力学研究技术研究了配合物的热分解机理,采用Ozawa法和KAS法给出了配合物热分解过程的活化能(Ea),用主曲线法得到了配合物热分解过程的机理函数积分式G(α)。结果表明:[Cu(py)2(m-bdc)]n在170℃开始分解,420℃分解结束。[Cu(py)2(m-bdc)]n的分解过程分两个阶段完成,两个分解阶段的表观活化能分别为72.971 kJ·mol-1,179.012 kJ·mol-1;机理函数的积分式分别为:G(α)=(-ln(1-α))0.48(1)、G(α)=(-ln(1-α))0.83(2)。
关键词(KeyWords)： 配位聚合物;合成;晶体结构;热分解动力学
基金项目(Foundation): 西安工程大学博士基金(BS0902)
作者(Author): 解凤霞,张丹,张欣欣,华敏
参考文献(References)：
- [1]Cui Y J,Yue Y F,Qian G D.Luminescent functional metal_organic frameworks[J].Chem Rev,2012,112(2):1126-1162.
- [2]Dybtsev D N,Chun H,Yoon S H,et al.Microporous manganese formate:a simple metal-organic porous material with high framework stability and highly selective gas sorption properties[J].J Am Chem Soc,2004,126(1):32-33.
- [3]Petit C,Mendoza B,Bandosz T J.Reactive adsorption of ammonia on Cu-based MOF/graphene composites[J].Langmuir,2010,26(19):15302-15309.
- [4]Barthelet K,Marrot J,Riou D,et al.Breathing hybrid organic-inorganic solid with very large pores and high magnetic characteristics[J].Anges Chem,2004,114(2):291-294.
- [5]Chen W,Wang J Y,Chen C,et al.Photoluminescent metal-organic polymer constructed from trimetallic clusters and mixed carboxylates[J].Inorg Chem,2003,42(4):944-946.
- [6]Braun M E,Steffek C D,Kim J.1,4-Benzene dicarboxylate derivatives as links in the design of paddle-wheel units and metal-organic frameworks[J].Chem Commun,2001,24:2532-2533.
- [7]Chen X M,Liu G F.Double-stranded helices and molecular zippers assembled from single-stranded coordination polymers directed by supramolecular[J].Chem Eur J,2002,8(20):4811-4817.
- [8]Bourne S A,Lu J,Mondal A.Self-assembly of nanometer-scale secondary building units into an undulating two-dimensional network with two types of hydrophobic cavity[J].Angew Chem Int Ed,2001,40(11):2111-2113.
- [9]Moulton B,Lu J,Hajndl R.Crystal engineering of a nanoscale kagome lattice[J].Angew Chem Int Ed,2002,41(15):2821-2824.
- [10]WU Xin-min(吴新民),LIU Jian-hua(刘建华),LI Wei(李巍).Thermal decomposition kinetics of complexes of rare earth with amino acid RE(Val)Cl36H2O(RE=Nd,Sm)(稀土氨基酸配合物RE(Val)Cl36H2O(RE=Nd,Sm)的热分解动力学)[J].Acta Phys Chim Sin(物理化学学报),2006,22(8):942-946.
- [11]FENG Jin-ling(冯金玲),ZHANG Jian-guo(张建国),ZHANG Tong-lai(张同来).Synthesis,crystal structure,thermal behavior and sensitivity of[Mn(AZT)2(H2O)4](HTNR)24H2O([Mn(AZT)2(H2O)4](HTNR)24H2O的合成、晶体结构、热行为及感度性质)[J].Acta Phys Chim Sin(物理化学学报),2010,26(9):2410-2416.
- [12]ZHANG Jin(张进),ZHANG Tong-lai(张同来),YANG Li(杨利).Preparation,crystal structure and thermal decomposition character of[Ni(CHZ)3]SO43H2O([Ni(CHZ)3]SO43H2O的合成、晶体结构及热分解特性)[J].Acta Phys Chim Sin(物理化学学报),2008,24(5):760-766.
- [13]ZHANG Heng(张衡),ZHAO Feng-qi(赵凤起),YI Jian-hua(仪建华).Preparation,thermal behavior and non-isothermal decomposition reaction kinetics of Zr(3-NO2-PHT)22H2O(3-硝基邻苯二甲酸锆的制备、热分解机理及非等温反应动力学)[J].Acta Phys Chim Sin(物理化学学报),2008,24(12):2263-2267.
- [14]Mocioiu O C,Zaharescu M,Jitianu G.Kinetic parameters determination in non-isothermal conditions for the crystallization of a silica-soda-lead glass[J].J Thermal Anal and Calorimetry,2006,86(2):429-436.
- [15]Chunxiu G,Yufang S,Donghua C.Comparative method to evaluate reliable reliable kinetic triplets of thermal decomposition reactions[J].J Thermal Anal and Calorimetry,2004,76(1):203-216.
- [16]HU Rong-zu(胡荣祖),GAO Sheng-li(高胜利),ZHAO Feng-qi(赵凤起).Thermal analysis kinetics(热分析动力学)[M].2nd ed(第2版).Beijing(北京):Science Press(科学出版社),2008.