摘要
采用第一性原理和巨正则蒙特卡罗方法,模拟研究了气态碘分子(I2)在共价有机框架材料(COF-103)中的吸附行为,并讨论了气态氧化物、氯化物和挥发性有机化合物(VOCs)等杂质气体的竞争吸附影响.结果表明,I2偏向以垂直方式吸附于COF-103苯环的碳原子位,其中,长程色散相互作用具有重要的贡献,色散能在吸附能中的占比最多可达46%.I2与COF-103之间存在少量电荷转移,且可能形成具有弱共价相互作用的次级键.杂质气体中苯分子(C6H6)的吸附能和等量吸附热最大,与COF-103的亲和性最强,并且可以占据I2的吸附位点,从而引起I2吸附量的显著降低.
In the paper,by combining periodic density functional theory(DFT)and grand canonical Monte Carlo(GCMC)calculations,the adsorption of volatile iodine(I2)onto covalent organic framework(COF-103)was systematically investigated,including the interaction mechanisms and the influence of potential contaminants towards iodine adsorption.These potential contaminants included gaseous oxides,chlorides,and volatile organic compounds.It’s found that I2 prefers to be adsorbed above the carbon atoms of the phenyl ring in vertical mode.Furthermore,the long-range dispersion interaction plays an important role in I2 adsorption onto COF-103,which could contribute up to 46%to the adsorption energy.There is a little charge transfer between I2 and COF-103,and secondary bonds with weak covalent interactions may also be formed.Among all contaminants,benzene has the largest adsorption energy and heat,which indicates the strongest affinity with COF-103.Moreover,benzene could occupy the adsorption site of I2,thus leading to a significant decrease in iodine loading.This work could aid in under⁃standing the interaction mechanisms between volatile iodine and COFs with boron-based linkage and conduce to screening and designing better sorbents for radioiodine capture.
作者
童大银
赵耀林
王禹齐
韩子彤
王杰
张俊
喻晨曦
TONG Dayin;ZHAO Yaolin;WANG Yuqi;HAN Zitong;WANG Jie;ZHANG Jun;YU Chenxi(School of Nuclear Science and Technology,Xi’an Jiaotong University,Xi’an 710049,China;Department of Precision Engineering,Graduate School of Engineering,Osaka University,Osaka 5650871,Japan)
出处
《高等学校化学学报》
SCIE
EI
CSCD
北大核心
2024年第1期84-93,共10页
Chemical Journal of Chinese Universities
基金
国家自然科学基金(批准号:11775168,11275147)
国家留学基金(批准号:202106280125)资助.
关键词
气态碘吸附
共价有机框架
第一性原理
巨正则蒙特卡罗
Volatile iodine adsorption
Covalent organic framework
First-principle
Grand canonical Monte Carlo
