【作者】 杨红；

【导师】 温丽丽；

【作者基本信息】 华中师范大学 ， 无机化学， 2018， 硕士

【摘要】 近几年来,金属-有机框架(MOFs)由于自身独特的性质以及其在催化、气体吸附与分离、药物传递、荧光等方面的潜在应用,得到了广泛关注。本论文合成了一种BODIPY吡啶配体,并选用不同的羧酸配体与过渡金属离子构筑了 10个MOFs,对这些化合物的结构进行了测定并研究了其性能。第一章简要介绍了 MOFs的概念及其合成方法,并主要介绍了由BODIPY配体构筑的MOFs的研究进展。另外,还简单概括了 MOFs在光催化产氢、荧光、非均相催化等方面的潜在应用。第二章选用4,4’-联苯二甲酸(H2bpdc),BODIPY吡啶配体与过渡金属离子构筑了三个]MOFs,分别为[Zn2(BODIPY)(bpdc)2]·H2O(化合物1),[Cd2(BODIPY)2(bpdc)2](化合物2),[Cu6(BODIPY)3(bpdc)6](化合物3)。通过PLATON软件计算得到化合物1的孔洞率为25.6%。真空活化后的化合物1能够吸附CO2气体,并且表现出较高的吸附焓。研究表明化合物1具有较强的荧光,在其他干扰离子的存在下,化合物1能够选择性识别MnO4-。化合物1也能检测马尿酸(HA),马尿酸可以作为甲苯暴露的生物标志物,且化合物1检测HA具有选择性和循环性。将化合物1制备成微米级后,我们将铂纳米粒子负载在其表面,形成Pt/1,在可见光照射下用于光催化产氢。研究发现,在相同的光催化条件下,相对于化合物1(167μmol/g/h),载铂量为0.13 wt%的Pt/1展现了极高的光催化产氢活性(3107μmol/g/h)。且与其他载铂化合物相比,催化剂Pt/1在载铂量非常少的情况下还表现出优良的光催化产氢性能。第三章选用对苯二甲酸(H2bdc)及其衍生物,BODIPY吡啶配体与过渡金属离子构筑 了四个 MOFs,分别为[Cd2(BODIPY)2(bdc)2]·8DMF·3H2O(化合物 4),[Cd(BODIPY)(NH2bdc)](化合物 5),[Cd2(BODIPY)2(OHbdc)2]5DMF(化合物 6)和[Zn2(BODIPY)(CH3bdc)2](化合物7)。其中,化合物4、5和6互为异质同构体。化合物5和6中含有路易斯碱性位点,可以用来催化Knoevenagel缩合反应,且化合物5的催化活性优于化合物6。研究发现,具有吸电子基团的苯甲醛衍生物的催化活性高于给电子基团的底物。五次循环实验以后,化合物5和6依然保持很高的催化活性。第四章选用偶氮苯-4,4’-二羧酸(H2adc),BODIPY 吡啶配体与过渡金属离子用溶剂热法合成了三个MOFs,分别为[Zn3(BODIPY)(adc)3]·2DMF(化合物8)、[Cd2(BODIPY)2(adc)2]·3DMF·4MeOH(化合物 9)和[Mn3(BODIPY)(adc)3(DMF)2]·DMF(化合物10)。通过PLATON软件计算得到化合物10的孔洞率为16.5%,可以吸附CO2,并且化合物10含有路易斯酸性位点,可以用来催化CO2与环氧化物的耦合反应。经研究发现,化合物10对不同尺寸的环氧化底物具有催化选择性。实验表明化合物10的催化活性较好并可以循环使用。第五章对本论文的研究成果及创新点进行了分析,并对构筑结构和功能多样化的MOFs进行了展望。更多还原

【Abstract】 In recent years,metal-organic frameworks(MOFs)have received extensive attentions due to their unique properties and wide potential applications in catalysis,gas adsorption and separation,drug delivery,fluorescence and so on.In this thesis,we have synthesized ten MOFs based on BODIPY-derived bipyridine ligand,and different carboxylic acid ligands in the presence of transition metal ions.The structures of these compounds were determined and their properties were studied.Chapter 1:the concept and synthesis methods of MOFs were briefly introduced.The research progress of MOFs constructed from BODIPY-derived bipyridine ligand was mainly introduced.In addition,the potential applications of MOFs in photocatalytic hydrogen production,fluorescence,and heterogeneous catalysis were summaried.Chapter 2:three new MOFs[Zn2(BODIPY)(bpdc)2]·H2O(compound 1),[Cd2(BODIPY)2(bpdc)2](compound 2),[Cu6(BODIPY)3(bpdc)6](compound 3)were synthesized based on 4,4’-biphenyldicarboxylic acid and BODIPY-derived bipyridine ligand with transition metal ions.The void space of compoud 1 was calculated to be 25.6%by PLATON,and the activated 1 was able to absorb CO2 and showed higher adsorption enthalpy.Compound 1 could selectively recognize MnO4-in the presence of other interfering ions.Compound 1 was also able to detect hippuric acid(HA),which could be used as a biological indicator of toluene exposure.Compound 1 showed selectivity and recyclability for the detection of HA.Pt nanopariticles were supported on micrometers-sized comound 1,denoted as Pt/1,for photocatalytic hydrogen production under visible light irradiation.It was found that Pt/1 catalysts with 0.13 wt%of Pt loading exhibited much higher photocatalytic hydrogen production activity(3107μmol/g/h)than that of compound 1(167 μmol/g/h)under the same photocatalytic conditions.Compared with other platinum-loaded compounds,the catalysts Pt/1 exhibited superior performance of photocatalytic hydrogen production with tiny Pt loading.Chapter 3:four new MOFs[Cd2(BODIPY)2(bdc)2]·8DMF·3H2O(compound 4),[Cd(BODIPY)(NH2bdc)](compound 5),[Cd2(BODIPY)2(OHbdc)2]·5DMF(compound 6)and[Zn2(BODIPY)(CH3bdc)2](compound 7)were synthesized based on BODIPY-derived bipyridine ligand and terephthalic acid and its derivatives in the presence of transition metal ions.Compound 4,5 and 6 were isostructural.Compound 5 and 6 possessed Lewis basic sites,which were used to catalyze Knoevenagel condensation reaction,and the catalytic activity of compound 5 was superior to compound 6.It was found that benzaldehyde derivatives with electron-withdrawing groups were more reactive than those with electron-donating groups.Compound 5 and 6 still remained higher catalytic activity after five cycles.Chapter 4:three new MOFs[Zn3(BODIPY)(adc)3]·2DMF(compound 8),[Cd2(BODIPY)2(adc)2]·3DMF·4MeOH(compound 9)and[Mn3(BODIPY)(adc)3(DMF)2]·DMF(compound 10)were solvothermally synthesized based on BODIPY-derived bipyridine ligand and azobenzene-4,4’-dicarboxylic acid with transition metal ions.The void space of compound 10 was calculated to be 16.5%by PLATON.Compound 10 had adsorption capacity for CO2 and Lewis acid sites,which could be used to catalyze the reaction of CO2 with epoxides.It was found that compound 10 was selective for epoxides of different size.Experiments demonstrated that compound 10 had better catalytic activity and could be recycled.Chapter 5:it summarized the research results and innovation of the thesis,and looked forward to the construction of MOFs with diversified structures and functions.更多还原