高校化学工程学报
高校化學工程學報
고교화학공정학보
JOURNAL OF CHEMICAL ENGINEERING OF CHINESE UNIVERSITIES
2014年
4期
695-700
,共6页
解凤霞%张丹%张欣欣%华敏
解鳳霞%張丹%張訢訢%華敏
해봉하%장단%장흔흔%화민
配位聚合物%合成%晶体结构%热分解动力学
配位聚閤物%閤成%晶體結構%熱分解動力學
배위취합물%합성%정체결구%열분해동역학
coordination polymer%synthesis%crystal structure%thermal decomposition kinetics
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)。
採用溶劑擴散法閤成瞭過渡金屬配位聚閤物:[Cu(py)2(m-bdc)]n (m-bdc =間苯二甲痠,py =吡啶),根據X-單晶衍射給齣配閤物的結構,該配閤物是由間苯二甲痠根橋連的具有二維無限網狀結構的聚閤物,為單斜晶繫,P 21/c空間群,晶胞參數: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。應用非等溫動力學研究技術研究瞭配閤物的熱分解機理,採用Ozawa法和KAS法給齣瞭配閤物熱分解過程的活化能(Ea),用主麯線法得到瞭配閤物熱分解過程的機理函數積分式 G(α)。結果錶明:[Cu(py)2(m-bdc)]n在170℃開始分解,420℃分解結束。[Cu(py)2(m-bdc)]n的分解過程分兩箇階段完成,兩箇分解階段的錶觀活化能分彆為72.971 kJ?mol-1,179.012 kJ?mol-1;機理函數的積分式分彆為:G(α)=(-ln(1-α))0.48(1)、G(α)=(-ln(1-α))0.83(2)。
채용용제확산법합성료과도금속배위취합물:[Cu(py)2(m-bdc)]n (m-bdc =간분이갑산,py =필정),근거X-단정연사급출배합물적결구,해배합물시유간분이갑산근교련적구유이유무한망상결구적취합물,위단사정계,P 21/c공간군,정포삼수: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。응용비등온동역학연구기술연구료배합물적열분해궤리,채용Ozawa법화KAS법급출료배합물열분해과정적활화능(Ea),용주곡선법득도료배합물열분해과정적궤리함수적분식 G(α)。결과표명:[Cu(py)2(m-bdc)]n재170℃개시분해,420℃분해결속。[Cu(py)2(m-bdc)]n적분해과정분량개계단완성,량개분해계단적표관활화능분별위72.971 kJ?mol-1,179.012 kJ?mol-1;궤리함수적적분식분별위:G(α)=(-ln(1-α))0.48(1)、G(α)=(-ln(1-α))0.83(2)。
A transition-metal coordinated polymer, [Cu(py)2(m-bdc)]n (m-bdc = m-phthalic, py = pyridine) was synthesized using a solvent diffusion method. The crystal structure of the complex was determined by X-ray single crystal diffraction. The result indicates that the polymer is m-phthalic ligand bridged to form a two dimension infinite network structure with a complex crystal data of: monoclinic, space group P 21/c, 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. Thermal decomposition mechanism of the complex was investigated by a non-isothermal kinetic method. Iterative iso-conversional methods were applied to calculate the activation energy and the most probable mechanism function was determined by means of the master plots method.The results show that [Cu(py)2(m-bdc)]n begin to decompose at about 170℃ and fully decomposed at 420℃. The decomposition process of [Cu(py)2(m-bdc)]n can be divided into two stages, whose activation energies and the mechanism functions are: Ea = 72.971 kJ?mol-1, G(α) = (-ln(-α))0.48 (first stage) and Ea = 179.012 kJ?mol-1, G(α)=(-ln(1-α))0.83(second stage), respectively.