本文主要研究内容
作者李丹丹（2019）在《Cu/Ag参与构筑的多酸基金属有机框架的合成、结构及性质》一文中研究指出：多酸基金属有机框架(POMOF)是一类包含多酸阴离子单元的具有开放框架结构的有机-无机杂化化合物。由于其结构新颖且性能优良,解决了多酸材料化面临的易溶于水,易团聚的问题,极大地扩展了多酸的应用范围,这类化合物在过去十几年间发展迅速,成为多酸化学领域的热门研究方向之一。本文选取不同种类的含氮有机配体以及双功能配体,在水热条件下与Cu/Ag以及经典Keggin/Dawson型多酸阴离子进行组装,成功合成了三个系列的多酸基金属有机框架化合物,对所得化合物进行了单晶结构测试及一系列表征,并系统地研究了部分化合物在催化以及吸附有机染料方面的性能。主要内容及所合成化合物的晶体学数据如下:1.以2-比吡嗪羧酸(pzc)为有机配体,成功制备了两例基于Dawson/Keggin型多酸阴离子的三维框架化合物1,2。其中,化合物1中的吡嗪(pz)配体由部分pzc配体原位热解脱羧形成。该化合物在空气中及pH=1-12的水溶液中能够稳定存在,并可作为高效多相催化剂用于醇类氧化,在一定条件下产物收率达97%,TOF高达9690 h-1。1.H[CuⅠ5CuⅡ(pZc)2(pz)4.5{P2W18O62}]·6H2O(1)三斜晶系,P-1 空间群,= 13.136(4)A,b = 17.177(5)A,c = 20.598(7)A,αα=89.288(6)°,β=87.601(6)°,γ=70.447(6)°,V= 4376(2)A3,Z=2,Ri=0.0895,wR2=0.2099[I>2σ(I)].2.[CuⅠ4(H2O)2CuⅡ(pzc)4{SiW12O40}]H2O(2)单斜晶系,P21/n空间群,a= 11.402(3)A,b=23.045(7)A,c= 13.012(4)A,β=111.537(4)°,V= 3180.3(17)A3,Z=2,RR1=0.1118,w =0.2472[I>2σ(I)].Ⅱ.以1,2,4-三:氮唑(trz)为配体,成功制备了两例基于{Cu6(trz)6}大环的]Keggin型多酸基金属有机框架3,4,两例基于{Cu4Cl(trz)4}大环的Keggin型多酸基金属有机框架5,6以及一例具有螺旋结构的Dawson型多酸基金属有机框架7。其中,化合物3-6对烷烃的选择性氧化均表现出较高催化活性。而化合物7则拥有目前已报道的Dawson型多酸化合物中的最高配位数,并能够在室温下有效吸附阳离子染料亚甲基蓝(MB)。3.[CuI6(trz)6{PW12O40}2](3)三方晶系,R-3空间群,a=b=17.5420(18)A,c=22.802(2)A,V=6076.6(14)A3,Z= 3,Ri = 0.0288,wR2 = 0.0629[I>2σ(I)].4.[CuI3(trz)3{PMo12O40}](4)三方晶系,R-3空间群,a=b=17.502(9)A,c=23.071(12)A,V= 6121(7)A3,Z=5.99994,Ri = 0.0228,wR2 = 0.0620[I>2σ(I)].5,H[CuⅠ12(trz)8Cl2{PW12O40}](5)单斜晶系,C2/c空间群,0=20.418(13),b=20.446(13),c=16.913(11),β=117.720(10)°,V= 6250(7)A3,ZZ= 4,R1= 0.1413,wR2 = 0.4206[I>2σ(I)].6.[CuI12(trz)8Cl{PMo12O40}](6)三斜晶系,P-1 空间群,a= 11.309(12)A,b= 11.337(10)A,c= 14.292(14)A,αa=105.350(12)°,β= 112.459(14)°,γ= 100.382(11)°,V= 1549(3)A3,ZZ= 1,RRi = 0.1661,wR2=0.4206[I>2σ(I)].7.H[Agio(H3trz)5(H2trz)2(trz){P2W18O62}].·5H2O(7)斜方晶系,C2221空间群,a= 14.613(3)A,b=23.052(6)A,c=23.485(5)A,V=7911(3)A3,Z = 4,Ri = 0.0474,wR2 = 0.1111[I>2σ(I)].3.以吡嗪(pz)为配体,成功合成了三例非穿插多酸基金属有机框架8-10。这三例化合物不仅展现出多样的结构特征,并且均能有效吸附MB染料,其中,化合物8的效果最佳。8.[Ag5(pz)5{PW12O40}(OH)2].2.5H2O(8)单斜晶系,C2/c空间群,a=23.100(3)A,b=20.534(2)A,c=12.4320(14)A,β=97.667(2)°,V= 5844.3(12)A3,Z = 4,Ri= 0.0603,wR2 = 0.1441[I>2σ(I)].9.[Ag6(H2O)(pz)7{P2W18O62}]·3H2O(9)单斜晶系,C2/c空间群,a=26.403(12)A,b=13.432(6)A,c=23.639(10)A,β=97.519(7)°,V= 8311(6)A3,Z= 4,Ri= 0.0498,wR2 = 0.1312[I>2σ(I)].10.[CuI3(pz)3{PMo12O400}]H2O(10)立方晶系,空间群,aa=b=c=26.0817(12)A,v= 17742(2)A3,Z=16.00032,Ri = 0.0738,wR2 = 0.1649[I>2σ(I)]。
Abstract
duo suan ji jin shu you ji kuang jia (POMOF)shi yi lei bao han duo suan yin li zi chan yuan de ju you kai fang kuang jia jie gou de you ji -mo ji za hua hua ge wu 。you yu ji jie gou xin ying ju xing neng you liang ,jie jue le duo suan cai liao hua mian lin de yi rong yu shui ,yi tuan ju de wen ti ,ji da de kuo zhan le duo suan de ying yong fan wei ,zhe lei hua ge wu zai guo qu shi ji nian jian fa zhan xun su ,cheng wei duo suan hua xue ling yu de re men yan jiu fang xiang zhi yi 。ben wen shua qu bu tong chong lei de han dan you ji pei ti yi ji shuang gong neng pei ti ,zai shui re tiao jian xia yu Cu/Agyi ji jing dian Keggin/Dawsonxing duo suan yin li zi jin hang zu zhuang ,cheng gong ge cheng le san ge ji lie de duo suan ji jin shu you ji kuang jia hua ge wu ,dui suo de hua ge wu jin hang le chan jing jie gou ce shi ji yi ji lie biao zheng ,bing ji tong de yan jiu le bu fen hua ge wu zai cui hua yi ji xi fu you ji ran liao fang mian de xing neng 。zhu yao nei rong ji suo ge cheng hua ge wu de jing ti xue shu ju ru xia :1.yi 2-bi bi qin suo suan (pzc)wei you ji pei ti ,cheng gong zhi bei le liang li ji yu Dawson/Kegginxing duo suan yin li zi de san wei kuang jia hua ge wu 1,2。ji zhong ,hua ge wu 1zhong de bi qin (pz)pei ti you bu fen pzcpei ti yuan wei re jie tuo suo xing cheng 。gai hua ge wu zai kong qi zhong ji pH=1-12de shui rong ye zhong neng gou wen ding cun zai ,bing ke zuo wei gao xiao duo xiang cui hua ji yong yu chun lei yang hua ,zai yi ding tiao jian xia chan wu shou lv da 97%,TOFgao da 9690 h-1。1.H[CuⅠ5CuⅡ(pZc)2(pz)4.5{P2W18O62}]·6H2O(1)san xie jing ji ,P-1 kong jian qun ,= 13.136(4)A,b = 17.177(5)A,c = 20.598(7)A,αα=89.288(6)°,β=87.601(6)°,γ=70.447(6)°,V= 4376(2)A3,Z=2,Ri=0.0895,wR2=0.2099[I>2σ(I)].2.[CuⅠ4(H2O)2CuⅡ(pzc)4{SiW12O40}]H2O(2)chan xie jing ji ,P21/nkong jian qun ,a= 11.402(3)A,b=23.045(7)A,c= 13.012(4)A,β=111.537(4)°,V= 3180.3(17)A3,Z=2,RR1=0.1118,w =0.2472[I>2σ(I)].Ⅱ.yi 1,2,4-san :dan zuo (trz)wei pei ti ,cheng gong zhi bei le liang li ji yu {Cu6(trz)6}da huan de ]Kegginxing duo suan ji jin shu you ji kuang jia 3,4,liang li ji yu {Cu4Cl(trz)4}da huan de Kegginxing duo suan ji jin shu you ji kuang jia 5,6yi ji yi li ju you luo xuan jie gou de Dawsonxing duo suan ji jin shu you ji kuang jia 7。ji zhong ,hua ge wu 3-6dui wan ting de shua ze xing yang hua jun biao xian chu jiao gao cui hua huo xing 。er hua ge wu 7ze yong you mu qian yi bao dao de Dawsonxing duo suan hua ge wu zhong de zui gao pei wei shu ,bing neng gou zai shi wen xia you xiao xi fu yang li zi ran liao ya jia ji lan (MB)。3.[CuI6(trz)6{PW12O40}2](3)san fang jing ji ,R-3kong jian qun ,a=b=17.5420(18)A,c=22.802(2)A,V=6076.6(14)A3,Z= 3,Ri = 0.0288,wR2 = 0.0629[I>2σ(I)].4.[CuI3(trz)3{PMo12O40}](4)san fang jing ji ,R-3kong jian qun ,a=b=17.502(9)A,c=23.071(12)A,V= 6121(7)A3,Z=5.99994,Ri = 0.0228,wR2 = 0.0620[I>2σ(I)].5,H[CuⅠ12(trz)8Cl2{PW12O40}](5)chan xie jing ji ,C2/ckong jian qun ,0=20.418(13),b=20.446(13),c=16.913(11),β=117.720(10)°,V= 6250(7)A3,ZZ= 4,R1= 0.1413,wR2 = 0.4206[I>2σ(I)].6.[CuI12(trz)8Cl{PMo12O40}](6)san xie jing ji ,P-1 kong jian qun ,a= 11.309(12)A,b= 11.337(10)A,c= 14.292(14)A,αa=105.350(12)°,β= 112.459(14)°,γ= 100.382(11)°,V= 1549(3)A3,ZZ= 1,RRi = 0.1661,wR2=0.4206[I>2σ(I)].7.H[Agio(H3trz)5(H2trz)2(trz){P2W18O62}].·5H2O(7)xie fang jing ji ,C2221kong jian qun ,a= 14.613(3)A,b=23.052(6)A,c=23.485(5)A,V=7911(3)A3,Z = 4,Ri = 0.0474,wR2 = 0.1111[I>2σ(I)].3.yi bi qin (pz)wei pei ti ,cheng gong ge cheng le san li fei chuan cha duo suan ji jin shu you ji kuang jia 8-10。zhe san li hua ge wu bu jin zhan xian chu duo yang de jie gou te zheng ,bing ju jun neng you xiao xi fu MBran liao ,ji zhong ,hua ge wu 8de xiao guo zui jia 。8.[Ag5(pz)5{PW12O40}(OH)2].2.5H2O(8)chan xie jing ji ,C2/ckong jian qun ,a=23.100(3)A,b=20.534(2)A,c=12.4320(14)A,β=97.667(2)°,V= 5844.3(12)A3,Z = 4,Ri= 0.0603,wR2 = 0.1441[I>2σ(I)].9.[Ag6(H2O)(pz)7{P2W18O62}]·3H2O(9)chan xie jing ji ,C2/ckong jian qun ,a=26.403(12)A,b=13.432(6)A,c=23.639(10)A,β=97.519(7)°,V= 8311(6)A3,Z= 4,Ri= 0.0498,wR2 = 0.1312[I>2σ(I)].10.[CuI3(pz)3{PMo12O400}]H2O(10)li fang jing ji ,kong jian qun ,aa=b=c=26.0817(12)A,v= 17742(2)A3,Z=16.00032,Ri = 0.0738,wR2 = 0.1649[I>2σ(I)]。
论文参考文献
论文详细介绍
论文作者分别是来自河南大学的李丹丹，发表于刊物河南大学2019-09-20论文，是一篇关于多酸论文,多酸基金属有机框架论文,合成论文,晶体结构论文,催化论文,河南大学2019-09-20论文的文章。本文可供学术参考使用，各位学者可以免费参考阅读下载，文章观点不代表本站观点，资料来自河南大学2019-09-20论文网站，若本站收录的文献无意侵犯了您的著作版权，请联系我们删除。
标签：多酸论文; 多酸基金属有机框架论文; 合成论文; 晶体结构论文; 催化论文; 河南大学2019-09-20论文;