通过金属离子刺激调节金属有机骨架结构用于光催化CO2还原
Modulating metal-organic framework structure by metal ion stimulation for photocatalytic CO2 reduction reaction
路新 1钱建磊 1葛发源 2李浩天 1郑和根 2张传磊1
作者信息
- 1. 安庆师范大学化学化工学院,光电磁功能材料安徽省重点实验室,安庆 246133
- 2. 南京大学化学化工学院,配位化学国家重点实验室,南京 210023
- 折叠
摘要
通过自组装得到一种具有适中配位键强度和适度骨架柔性的二维Cd基金属有机骨架(MOF){[Cd(HL)(BPY)0.5(H2O)]· 2H2O}n(1),其中H3L=4,4',4"-(亚硝基三(亚甲基))三苯甲酸,BPY=4,4'-联吡啶).由于其独特的结构特征,在金属离子(Zn2+/Ni2+/Co2+)刺激下,1逐渐转变成相应金属离子主导的MOF结构2、3和4.在此过程中,随着金属离子Cd2+→Zn2+、Cd2+→Ni2+和Cd2+→Co2+的交换,1通道中自由的Cd2+和L3-与MOF的骨架进行融合,导致通道空间的扩大,发生次级构筑单元(SBU)的转变,进而形成可调节的骨架.光催化二氧化碳还原结果表明,由离子交换所得到的新结构在催化效率上并没有很大改观,但在产物选择性上却有极大地提升(其中配合物3展示出100％的CO选择性).
Abstract
A 2D Cd-based metal-organic framework with moderate coordination bond strength and adequate frame-work flexibility was obtained by self-assembly,namely {[Cd(HL)(BPY)0.5(H2O)]·2H2O}n(1),where H3L=4,4',4"-(nitri-lotris(methylene))tribenzoic acid,BPY=4,4'-bipyridine.Due to the unique structural features,under the stimulation of metal ions(Zn2+/Ni2+/Co2+),1 gradually transforms into the MOF structures dominated by the corresponding metal ions(2,3,and 4).During this process,with the exchanges of Cd2+→Zn2+,Cd2→Ni2+,and Cd22→Co2+,the free Cd2+and L3-in the channel of 1 fuse with the backbone,leading to the channel space expansion and secondary building unit(SBU)transformation to form a tunable backbone.The photocatalytic CO2 reduction results show that the new structures obtained by ion exchange do not have a great improvement in catalytic efficiency,but have a great increase in product selectivity(3 demonstrated 100％CO selectivity).CCDC:2299888,1;2299889,2;2299890,3;2299891,4.
关键词
金属有机骨架/离子刺激/结构转换/光催化/二氧化碳还原Key words
metal-organic framework/ionic stimulation/structural transformation/photocatalysis/carbon dioxide reduction引用本文复制引用
基金项目
国家自然科学基金(22101006)
国家自然科学基金(21771101)
安徽省教育厅自然科学研究重大项目(2023AH040071)
安徽省自然科学基金(1908085QB49)
出版年
2024
NETL
NSTL
万方数据