【作者】 李俊；

【导师】 李珺；

【作者基本信息】 西北大学 ， 无机化学， 2021， 硕士

【摘要】 共价有机聚合物由轻质元素通过共价键连接,拥有较低的密度、高的热稳定性以及固有的多孔性,在气体吸附、非均相催化、能量存储等领域展现了广泛的应用潜力。它的结构和大小的控制相对灵活,可以根据需要引入不同的连接体,以及设计具有不同结构和性质的配体,合成更多具有不同功能的共价有机聚合物材料,以供各种研究领域使用。卟啉具有优良的物理和化学性质,以卟啉为单元,构筑卟啉基的共价有机聚合物,研究其作为非均相催化剂的性能,对于发展卟啉非均相催化剂的研究具有重要意义。首先,本论文设计合成了一种醛基卟啉,5,10,15,20-四（4-（4-甲酰基）苯氧基）苯基卟啉（H₂Pp）及其相应的锌卟啉（ZnPp）和钴卟啉（CoPp）。通过紫外-可见光谱（UV-vis）、傅里叶红外光谱（FT-IR）、基质辅助激光解析电离-飞行时间质谱（MALDI-TOF MS）、¹H核磁谱（¹H NMR）等对合成的卟啉和金属卟啉进行了光谱表征,证明了卟啉及金属卟啉分子结构的正确性。其次,将三种醛基卟啉（H₂Pp、ZnPp、CoPp）分别与对苯二胺（PDA）,苯四胺四盐酸盐（BTA）,四胺基苯基甲烷（TAPM）通过席夫碱反应得到了三种类型的亚胺键连接的卟啉基共价有机多孔聚合物:MPp-PDA,MPp-BTA,MPp-TAPM（M=2H,Zn,Co）,通过固体紫外-可见光谱（UV-vis-DRS）、红外光谱（FT-IR）、热重分析（TG）、扫描电镜（SEM）、透射电镜（TEM）、粉末X-射线衍射（XRD）以及BET测试等手段对聚合物进行了结构及形貌分析表征,证明了卟啉基共价有机聚合物被成功合成。探究了聚合物作为光催化剂对苯甲硫醚的光催化氧化活性,结果表明:室温下,以聚合物为光催化剂,氧分子为氧化剂,在可见光照射下,MPp-PDA,MPp-BTA,MPp-TAPM（M=2H,Zn,Co）对苯甲硫醚氧化为苯甲亚砜都具有高的光催化活性,其中H₂Pp-PDA的催化活性最高,并且催化剂经过五次循环实验,催化效果并无明显降低。对比H₂Pp-PDA反应前和五次反应后的FT-IR光谱,可看出五次循环后催化剂的结构基本不变。以MPp-BTA为催化剂,研究了常压（0.1MPa CO₂）条件下,以TBAB为助催化剂,催化二氧化碳和环氧化物的环加成反应,ZnPp-BTA和CoPp-BTA获得了高的催化转化率,催化剂循环五次后仍展现出良好的催化活性。更多还原

【Abstract】 ovalent organic polymers are composed of light elements,have low density,excellent thermal and chemical stability and other advantages.The control of its structure and size is relatively flexible,and different linkers can be introduced as needed to design ligands with different structures and properties,and more covalent organic polymer materials with better functions can be synthesized for various uses.Porphyrins have excellent physical and chemical properties,porphyrins were be used a unit to build a porphyrin-based covalent organic polymer,the study of its performance as a heterogeneous catalyst,for the development of porphyrins heterogeneous catalyst research has important significance.First,a new porphyrin was designed and synthesized:5,10,15,20-tetra（4-（4-aldehyde）phenoxy）phenyl porphyrin（H₂Pp）,5,10,15,20-tetra（4-（4-aldehyde）phenoxy）phenyl zinc porphyrin（ZnPp）and 5,10,15,20-tetra（4-（4-aldehyde）phenoxy）phenyl cobalt porphyrin（CoPp）.Then characterized by UV-vis,IR,MALDI-TOF MS and ¹H NMR.Secondly,three types of imine-bonded covalent organic porous polymers（MPp-PDA,MPp-BTA,MPp-TAPM（M=2H,Zn,Co））were obtained by reacting MPp（M=2H,Zn,Co）with PDA,BTA,and TAPM By a Schiff base reaction.Then,a series of characterizations UV-vis-DRS,FT-IR,XRD,TG,SEM,TEM and BET tests were carried out,proving that the porphyrin-based covalent organic polymer was successfully synthesized.The photocatalytic oxidation activity of the polymer as a photocatalyst to phenylene sulfide was investigated.The results showed that at room temperature,the polymer was used as the catalyst,and the oxygen molecule was used as the oxidant,under visible light irradiation,the three polymers all improved the photocatalytic oxidation efficiency of phenylene sulfide,especially H₂Pp-PDA.Taking H₂Pp-PDA as an example,five cycles of experiments were carried out under the same catalytic conditions,and the catalytic effect did not decrease.After the reaction,FT-IR was carried out on H₂Pp-PDA,and it can be seen that the structure did not change significantly from before and after.Using MPp-BTA as catalyst,the catalytic activity of cycloaddition reaction of carbon dioxide and epoxide was studied under atmospheric pressure（0.1MPa CO2）with TBAB as co-catalyst,high catalytic conversion was obtained,and the catalyst still showed good catalytic activity after five cycles.更多还原