| Autor: |
Zhang X; School of Chemistry, University of Manchester , Manchester M13 9PL, U.K., da Silva I; ISIS Facility, STFC Rutherford Appleton Laboratory , Chilton, Oxfordshire OX11 0QX, U.K., Godfrey HGW; School of Chemistry, University of Manchester , Manchester M13 9PL, U.K., Callear SK; ISIS Facility, STFC Rutherford Appleton Laboratory , Chilton, Oxfordshire OX11 0QX, U.K., Sapchenko SA; School of Chemistry, University of Manchester , Manchester M13 9PL, U.K.; Nikolaev Institute of Inorganic Chemistry , Siberian Branch of the Russian Academy of Sciences, Novosibirsk 630090, Russia., Cheng Y; The Chemical and Engineering Materials Division (CEMD), Neutron Sciences Directorate, Oak Ridge National Laboratory , Oak Ridge, Tennessee 37831, United States., Vitórica-Yrezábal I; School of Chemistry, University of Manchester , Manchester M13 9PL, U.K., Frogley MD; Diamond Light Source , Harwell Science Campus, Oxfordshire OX11 0DE, U.K., Cinque G; Diamond Light Source , Harwell Science Campus, Oxfordshire OX11 0DE, U.K., Tang CC; Diamond Light Source , Harwell Science Campus, Oxfordshire OX11 0DE, U.K., Giacobbe C; European Synchrotron Radiation Facility , Grenoble 38043, France., Dejoie C; European Synchrotron Radiation Facility , Grenoble 38043, France., Rudić S; ISIS Facility, STFC Rutherford Appleton Laboratory , Chilton, Oxfordshire OX11 0QX, U.K., Ramirez-Cuesta AJ; The Chemical and Engineering Materials Division (CEMD), Neutron Sciences Directorate, Oak Ridge National Laboratory , Oak Ridge, Tennessee 37831, United States., Denecke MA; School of Chemistry, University of Manchester , Manchester M13 9PL, U.K., Yang S; School of Chemistry, University of Manchester , Manchester M13 9PL, U.K., Schröder M; School of Chemistry, University of Manchester , Manchester M13 9PL, U.K. |
| Abstrakt: |
During nuclear waste disposal process, radioactive iodine as a fission product can be released. The widespread implementation of sustainable nuclear energy thus requires the development of efficient iodine stores that have simultaneously high capacity, stability and more importantly, storage density (and hence minimized system volume). Here, we report high I 2 adsorption in a series of robust porous metal-organic materials, MFM-300(M) (M = Al, Sc, Fe, In). MFM-300(Sc) exhibits fully reversible I 2 uptake of 1.54 g g -1 , and its structure remains completely unperturbed upon inclusion/removal of I 2 . Direct observation and quantification of the adsorption, binding domains and dynamics of guest I 2 molecules within these hosts have been achieved using XPS, TGA-MS, high resolution synchrotron X-ray diffraction, pair distribution function analysis, Raman, terahertz and neutron spectroscopy, coupled with density functional theory modeling. These complementary techniques reveal a comprehensive understanding of the host-I 2 and I 2 -I 2 binding interactions at a molecular level. The initial binding site of I 2 in MFM-300(Sc), I 2 I , is located near the bridging hydroxyl group of the [ScO 4 (OH) 2 ] moiety [I 2 I ···H-O = 2.263(9) Å] with an occupancy of 0.268. I 2 II is located interstitially between two phenyl rings of neighboring ligand molecules [I 2 II ···phenyl ring = 3.378(9) and 4.228(5) Å]. I 2 II is 4.565(2) Å from the hydroxyl group with an occupancy of 0.208. Significantly, at high I 2 loading an unprecedented self-aggregation of I 2 molecules into triple-helical chains within the confined nanovoids has been observed at crystallographic resolution, leading to a highly efficient packing of I 2 molecules with an exceptional I 2 storage density of 3.08 g cm -3 in MFM-300(Sc). |
