配位聚合物{[K(H_(2)O)]_(3)[Fe(C_(2)O_(4))_(3)]}_(n)结晶过程的原位微量热、结构及吸附性质  

In-situ Microcalorimetric,Structural and Adsorption Properties of Coordination Polymer{[K(H_(2)O)]_(3)[Fe(C_(2)O_(4))_(3)]}_(n) During its Crystallization Process

作　　者：王豆豆 辛月坤 林泽 安秦东 李扬[1] 解凤霞[1] WANG Doudou;XIN Yuekun;LIN Ze;AN Qindong;LI Yang;XIE Fengxia(College of Environment and Chemical Engineering,Xi'an Polytechnic University,Xi'an 710600 China)

机构地区：[1]西安工程大学环境与化学工程学院,陕西西安710600

出　　处：《化工技术与开发》2025年第3期28-33,43,共7页Technology & Development of Chemical Industry

基　　金：大学生创新创业训练计划项目(S202310709009)。

摘　　要：本文采用原位微量热法,对配位聚合物三草酸合铁酸三水合钾{[K(H_(2)O)]_(3)[Fe(C_(2)O_(4))_(3)]}_(n)单晶的构筑过程进行了研究,首次呈现了{[K(H_(2)O)]_(3)[Fe(C_(2)O_(4))_(3)]}_(n)单晶结晶过程中能量变化的特征热谱曲线,并给出了该单晶的结构。{[K(H_(2)O)]_(3)[Fe(C_(2)O_(4))_(3)]}_(n)结晶过程的热谱曲线由2个典型的吸热曲线组成,分别对应晶体的成核过程和生长过程。成核与生长之间存在潜伏期。成核过程的热动力学参数为:活化能103.23kJ·mol^(-1),机理函数积分式G(α)=[1-(1-α)^(1/2)]^(1/2);生长过程的热动力学参数为:活化能143.70kJ·mol^(-1),机理函数G(α)=[1-(1-α)^(1/3)]^(1/2)。对量热过程的结晶产物进行了X射线单晶衍射分析,分析结果表明该晶体属于单斜晶系。草酸根中的氧原子与金属离子形成了配位键,配位数为6,其空间构型为畸变的八面体。该配位聚合物的水分子不是游离水,3个水分子分别与3个钾离子配位,同时Fe^(3+)和K^(+)之间通过配体草酸根的氧原子桥连构成了三维网状结构。单晶解析证实该配位聚合物具有空穴结构,且该空穴对酸性铬深绿G有较好的吸附降解作用。The construction process of the coordination polymer{[K(H_(2)O)]_(3)[Fe(C_(2)O_(4))_(3)]}_(n) was studied by in situ microcalorimetry,the characteristic thermal spectrum of the energy change during the crystallization process was presented for the first time.The thermal spectrum of the crystallization process of{[K(H_(2)O)]_(3)[Fe(C_(2)O_(4))_(3)]}_(n) is composed of two typical endothermic curves,which correspond to the nucleation and growth processes,respectively.There was an incubation period between growth and nucleation.The thermodynamic data for the nucleation process are:E=103.23 kJ/mol,G(α)=[1-(1-α)^(1/2)]^(1/2),that for the growth process are:E=143.70kJ/mol,G(α)=[1-(1-α)^(1/3)]^(1/2).The crystalline product of the calorimetric process was analyzed by X-ray single crystal diffraction,and the analysis results show that the crystal belongs to the monoclinic crystal system.The O atom in oxalate and Fe^(3+)form a coordination bond,the coordination number is 6,and its spatial structure is deformed octahedron.The water in the coordination polymer is not free water.They are coordinated with three potassium ions.Fe^(3+)and K^(+)are connected by the oxygen atom of the ligand oxalate to form a three-dimensional structure.The single crystal analysis confirms that the coordination compound has a cavity structure and a good adsorption effect on acidic chromium green G.

关 键 词：原位微量热 结晶过程 晶体结构 吸附 

分 类 号：O631.3[理学—高分子化学]