摘要
本论文是在广西高校科研项目“聚硫醚蔗渣纤维素改性及对持久性污染物的捕集(201203YB061)'’和广西民族大学科研项目“金属有机骨架材料的合成、表征及吸附性能研究(2011MDYB041)”的支持下,针对我国的酸雨(S02)及温室气体(C02)等大气污染问题,用水热法合成新型金属有机骨架材料(Metal-organic Frameworks, MOFs),并将其作为新型吸附剂,吸附典型气态污染物C02和S02,探究MOFs材料的吸附性能、吸附动力学方程、吸附热力学参数和吸附机理,开展新材料在气态污染物控制方面的交叉应用研究,以期为我国大气污染预防和治理提供相关的理论支撑和技术指导。论文的主要内容和研究结果如下：
(1)以1,3,5-苯三甲酸为有机配体,以Zn(NO3)2·6H2O为金属离子,采用水热合成法得到配位聚合物[ZnNa(H3btc)(H2O)2]·(H2O)2。X-射线单晶衍射数据显示,该配位聚合物属于三斜晶系,Znz+离子为五配位双四面体模式,与五个氧原子配位,Na原子有两种均采用扭曲的正八面体配位模式,二个Na原子与两个配位水配位,四个羧酸配位；红外光谱图显示,3155cm-1处有结合O-H的伸缩振动峰,说明配位聚合物中存在水分子并形成了氢键,1613cm-1处有C=O的伸缩振动吸收峰,说明羧基已去质子化,配位成功；比表面积和孔隙分析显示,该配合物BET比表面积为181.92m2/g,平均孔径为1.223840nm,孔隙部分为中孔,部分为微孔；热重分析曲线显示了配合物经历了二次热失重,第一次发生在50℃～200℃,失重量约为20%,第二次失重发生在350℃-580℃,第二阶段失重量较多(约占50%),说明该配合物结构较稳定,低于350℃时不坍塌分解。
(2)在P=20bar,温度分别为20℃、40℃和60℃时,通过配合物[ZnNa(H3btc)(H2O)2]·(H2O)2吸附CO2和8O2气体动力学测试可知,升高温度可缩短吸附时间,但同时也降低了该配合物对CO2和SO2饱和吸附量,拟二级动力学方程能很好地描述[ZnNa(H3btc)(H2O)2]·(H2O)2对C02和S02吸附过程,其反应活化能Eα分别为5.062123和5.182881kJ/mol,这说明该配合物对CO2和SO2的吸附属于物理吸附过程。通过[ZnNa(H3btc)(H2O)2]·-(H20)2吸附C02和S02气体PCT测试可知,该配合物对C02和S02的吸附等温线可用Langmuir等温吸附模型很好的拟合,说明该配合物对C02和802的吸附是单分子层吸附；AH°分别为-22.3734和-7.18521kJ/mol,说明吸附是放热过程；△S°分别为-90.02216不-40.55655J/mol·k,说明气态污染物从气相转到固相,其自由度减小了,吸附减小了固相-气相界面上气态污染物的无序程度；二个吸附反应的吉布斯自由能-20kJ/mol<△G°<0,说明该吸附过程是物理吸附过程,且能自发地达到平衡。
(3)以1,2-苯二胺和2-吡啶甲酸为有机配体原料,以ZnSO4为金属离子,采用水热合成配位聚合物C12H9N3O10Zn2。X-射线单晶衍射数据显示,该配位聚合物属于Monoclinic晶系,Zn2+采用了扭曲的正八面体配位模式,与咪唑羧酸一侧形成了一个五元螯合环,并与另一个配体羧酸上的一个O原子配位,该O原子同时与两个Zn2+配位,Zn2+还与草酸形成另外一个五元螯合环,剩余一个配位点由配位水来填充。红外光谱图显示,3031cm-1处有结合O-H的伸缩振动峰,说明该配位中存在水分子并形成了氢键；1645cm-1处有与金属配位的C=O的伸缩振动吸收峰,说明羧基已去质子化,配位成功；比表面积和孔隙分析显示,该配合物BET比表面积为316.86m2/g,平均孔径为0.998268nm,孔隙部分为中孔,部分为微孔；热重分析显示了该配合物经历了二次热失重,第一次发生在30℃-220℃左右,失重量约为5%,第二次失重发生在300℃-700℃,这一阶段失重量较多(约占40%),说明配合物C12H9N3O10Zn2稳定性一般,温度高于220℃时,结构开始坍塌。
(4)在P=20bar,温度分别为20℃、40℃和60℃时,通过配合物C12H9N3O10Zn2吸附CO2和SO2气体动力学测试可知,升高温度可缩短吸附时间,但同时也降低了该配合物对CO2和SO2饱和吸附量,拟二级动力学方程能很好地描述C12H9N3O10Zn2对CO2和SO2吸附过程,其反应活化能Eα分别为9.39578和15.8717kJ/mol,这说明该配合物对CO2和SO2的吸附属于物理吸附过程。通过C12H9N3O10Zn2吸附CO2和SO2气体PCT测试可知,该配合物对CO2和SO2的吸附等温线可用Langmuir等温吸附模型很好的拟合,说明该配合物对CO2和SO2的吸附是单分子层吸附；△H°分别为-15.4971和-14.0894kJ/mol,说明吸附是放热过程；△S°分别为-69.19102和-65.47137J/mol·k,说明气态污染物从气相转到固相,其自由度减小了,这说明吸附减小了固相-气相界而上气态污染物的无序程度；二个吸附反应的吉布斯自由能-20kJ/mol<△G°<0,说明该吸附过程是物理吸附过程,且能自发地达到平衡。
In support of Guangxi Universities Scientific Research Project (Polythioether bagasse cellulose modified and capture persistent pollutants.201203YB061) and Guangxi University for Nationalities Research Foundation (A study on synthesis, structure and adsorption properties of metal-organic frameworks.2011MDYB041). As to air pollution of CO2and SO2in China, we synthesize a new Metal-organic Frameworks (MOFs) by hydrothermal method, and take it as a new adsorbent to adsorption typical gaseous pollutants, CO2and SO2. Explore the adsorption properties, adsorption kinetics equation, adsorption thermodynamic parameters and adsorption mechanism, of MOFs. And carry out cross-application of new materials in the control of gaseous pollutants in order to provide theoretical support and technical guidance for the prevention and control of air pollution in China. The main contents and results of the paper are as follows:
(1) Take1,3,5-Benzenetricarboxylic acid as organic ligand and Zn(NO3)2·6H2O as metal ions, synthesize of [ZnNa(H3btc)(H2O)2](H2O)2of coordination polymers. X-ray single crystal diffraction data show, the coordination polymer belongs to the triclinic crystal system, Zn2+is pentacoordinated tetrahedral mode and coordinates with five oxygen atoms. The two Na atoms have a distorted octahedral coordination mode, two Na atoms and coordinates with two water ligand and four carboxylic acid ligand; IR spectra show,3155cm-1combined with the O-H stretching vibration, which shows that the water molecules present in the coordination polymers and the formation of hydrogen bonds. The C=O stretching vibration absorption peak at1613cm-1, which shows that the carboxyl deprotonated and Coordinates successfully. Analysis of the specific surface area and pore showed that, the surface area of complexes is large, BET surface area is181.92m2/g, the average pore size is 1.223840nm, one part is the hole, one part is the micropores. Thermogravimetric analysis curve shows that complexes hot weight loss is twice. The first occurred at50℃to200℃, weight loss is of about20%; The second occurred at350℃～580℃, weight loss is of about50%, which shows that the complex structure is more stable and does not decompose below350℃.
(2) In pressure is20bar and temperature is20℃,40℃and60℃,[ZnNa(H3btc)(H2O)2](H2O)2adsorption of CO2and SO2gas dynamics test results show that, elevated temperatures can shorten the absorption time, but it also reduces the amount of the complex adsorption of CO2and SO2saturated. The proposed second-order equation can be well described by [ZnNa(H3btc)(H20)2]-(H2O)2adsorption of CO2and SO2, the activation energy were5.062123and5.182881kJ/mol. This shows that the complex adsorption of CO2and SO2in the process of physical adsorption.[ZnNa(H3btc)(H20)2]-(H2O)2adsorption of CO2and SO2gas PCT test results show, adsorption isotherms complexes of can be used Langmuir adsorption isotherm model well fitted, complex adsorption of CO2and SO2is the monolayer adsorption.△H°are-22.3734and-7.18521kJ/mol, The adsorption is an exothermic process.△S°are-90.02216and-40.55655J/mol-k. Gaseous pollutants transfer from the gas phase to the solid phase, the adsorption reduces the degree of disorder of the gaseous pollutants in the solid phase-gas interface.-20kJ/mol<△G°<0, the adsorption process is physical adsorption process, the adsorption reaction can spontaneously reach equilibrium.
(3) Take1,2-diaminobenzene and2-Picolinic acid as organic ligand and ZnSO4as rnetal ions, synthesize of C12H9N3O10Zn2of coordination polymers. X-ray single crystal diffraction data show, the coordination polymer belongs to the Monoclinic crystal system, coordination mode of Zn2+is distorted octahedral. Zn2+and imidazole carboxylic acid side of the formation of a five-member chelating ring. Zn2+and on another ligand carboxylic acid O atom coordination, Zn2+and on another ligand carboxylic acid O atom coordination. The remaining one with the water. IR cpectra show,3031cm-1combined with the O-H stretching vibration, which shows that the water molecules present in the coordination polymers and the formation of hydrogen bonds. The C=O stretching vibration absorption peak at1645cm-1, which shows that the carboxyl deprotonated and Coordinates successfully. Analysis of the specific surface area and pore showed that, the surface area of complexes is large, BET surface area is316.86m2/g, the average pore size is0.998268nm, one part is the hole, one part is the micropores. Thermogravimetric analysis curve shows that complexes hot weight loss is twice. The first occurred at30℃to220℃, weight loss is of about5%; The second occurred at300℃to700℃, weight loss is of about40%, which shows that the structure of the complex begins to decompose when the temperature is higher than220℃,
(4) In pressure is20bar and temperature is20℃,40℃and60℃, C12H9N3O10Zn2adsorption of CO2and SO2gas dynamics test results show that, elevated temperatures can shorten the absorption time, but it also reduces the amount of the complex adsorption of CO2and SO2saturated. The proposed second-order equation can be well described by C12H9N3O10Zn2adsorption of CO2and SO2, the activation energy were9.39578and15.8717kJ/mol. This shows that the complex adsorption of CO2and SO2in the process of physical adsorption. C12H9N3O10Zn2adsorption of CO2and SO2gas PCT test results show, adsorption isotherms complexes of can be used Langmuir adsorption isotherm model well fitted, complex adsorption of CO2and SO2is the monolayer adsorption.△H°are-15.4971and-14.0894kJ/mol, The adsorption is an exothermic process.△S°are-69.19102and-65.47137J/mol·k. Gaseous pollutants transfer from the gas phase to the solid phase, the adsorption reduces the degree of disorder of the gaseous pollutants in the solid phase·gas interface.-20kJ/mol<△G°<0,the adsorption process is physical adsorption process, the adsorption reaction can spontaneously reach equilibrium.
引文
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