Confinement of Iodine Molecules into Triple-Helical Chains within Robust Metal-Organic Frameworks

Xinran Zhang; Ivan Da Silva; Harry G.W. Godfrey; Samantha K. Callear; Sergey A. Sapchenko; Yongqiang Cheng; Inigo Vitórica-Yrezábal; Mark D. Frogley; Gianfelice Cinque; Chiu C. Tang; Carlotta Giacobbe; Catherine Dejoie; Svemir Rudić; Anibal J. Ramirez-Cuesta; Melissa A. Denecke; Sihai Yang; Martin Schröder

doi:10.1021/jacs.7b08748

Confinement of Iodine Molecules into Triple-Helical Chains within Robust Metal-Organic Frameworks

Xinran Zhang, Ivan Da Silva, Harry G.W. Godfrey, Samantha K. Callear, Sergey A. Sapchenko, Yongqiang Cheng, Inigo Vitórica-Yrezábal, Mark D. Frogley, Gianfelice Cinque, Chiu C. Tang, Carlotta Giacobbe, Catherine Dejoie, Svemir Rudić, Anibal J. Ramirez-Cuesta, Melissa A. Denecke, Sihai Yang, Martin Schröder

Spectroscopy

Research output: Contribution to journal › Article › peer-review

243 Scopus citations

Abstract

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 I₂ adsorption in a series of robust porous metal-organic materials, MFM-300(M) (M = Al, Sc, Fe, In). MFM-300(Sc) exhibits fully reversible I₂ uptake of 1.54 g g^-1, and its structure remains completely unperturbed upon inclusion/removal of I₂. Direct observation and quantification of the adsorption, binding domains and dynamics of guest I₂ 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-I₂ and I₂-I₂ binding interactions at a molecular level. The initial binding site of I₂ in MFM-300(Sc), I₂^I, is located near the bridging hydroxyl group of the [ScO₄(OH)₂] moiety [I₂^I···H-O = 2.263(9) Å] with an occupancy of 0.268. I₂^II is located interstitially between two phenyl rings of neighboring ligand molecules [I₂^II···phenyl ring = 3.378(9) and 4.228(5) Å]. I₂^II is 4.565(2) Å from the hydroxyl group with an occupancy of 0.208. Significantly, at high I₂ loading an unprecedented self-aggregation of I₂ molecules into triple-helical chains within the confined nanovoids has been observed at crystallographic resolution, leading to a highly efficient packing of I₂ molecules with an exceptional I₂ storage density of 3.08 g cm^-3 in MFM-300(Sc).

Original language	English
Pages (from-to)	16289-16296
Number of pages	8
Journal	Journal of the American Chemical Society
Volume	139
Issue number	45
DOIs	https://doi.org/10.1021/jacs.7b08748
State	Published - Nov 15 2017

Funding

M.S. thanks the ERC for an Advanced Grant (AdG 226593), EPSRC (EP/I011870) and the University of Manchester for funding, and acknowledges the Russian Ministry of Science and Education for the award of a Russian Megagrant (14.Z50.31.0006). We are especially grateful to STFC for access to TOSCA, to Oak Ridge National Laboratory (ORNL) for access to the Beamline VISION, to Diamond Light Source for access to Beamlines I11(EE14341) and B22(SM14938) and to the European Synchrotron Radiation Facility (ESRF) for access to Beamline ID22. The computing resources were made available through the VirtuES and ICEMAN projects, funded by Laboratory Directed Research and Development program at ORNL. X.R. Zhang acknowledges financial support from Chinese Scholarship Council for providing the studentship. S.A.S. thanks the Russian Science Foundation for the financial support (Grant 17-73-10254).

Access to Document

10.1021/jacs.7b08748

Cite this

Zhang, X., Da Silva, I., Godfrey, H. G. W., Callear, S. K., Sapchenko, S. A., Cheng, Y., Vitórica-Yrezábal, I., Frogley, M. D., Cinque, G., Tang, C. C., Giacobbe, C., Dejoie, C., Rudić, S., Ramirez-Cuesta, A. J., Denecke, M. A., Yang, S., & Schröder, M. (2017). Confinement of Iodine Molecules into Triple-Helical Chains within Robust Metal-Organic Frameworks. Journal of the American Chemical Society, 139(45), 16289-16296. https://doi.org/10.1021/jacs.7b08748

@article{8dc258e7b22546e4a88c30a248ceb903,

title = "Confinement of Iodine Molecules into Triple-Helical Chains within Robust Metal-Organic Frameworks",

abstract = "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 I2 adsorption in a series of robust porous metal-organic materials, MFM-300(M) (M = Al, Sc, Fe, In). MFM-300(Sc) exhibits fully reversible I2 uptake of 1.54 g g-1, and its structure remains completely unperturbed upon inclusion/removal of I2. Direct observation and quantification of the adsorption, binding domains and dynamics of guest I2 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-I2 and I2-I2 binding interactions at a molecular level. The initial binding site of I2 in MFM-300(Sc), I2I, is located near the bridging hydroxyl group of the [ScO4(OH)2] moiety [I2I···H-O = 2.263(9) {\AA}] with an occupancy of 0.268. I2II is located interstitially between two phenyl rings of neighboring ligand molecules [I2II···phenyl ring = 3.378(9) and 4.228(5) {\AA}]. I2II is 4.565(2) {\AA} from the hydroxyl group with an occupancy of 0.208. Significantly, at high I2 loading an unprecedented self-aggregation of I2 molecules into triple-helical chains within the confined nanovoids has been observed at crystallographic resolution, leading to a highly efficient packing of I2 molecules with an exceptional I2 storage density of 3.08 g cm-3 in MFM-300(Sc).",

author = "Xinran Zhang and {Da Silva}, Ivan and Godfrey, {Harry G.W.} and Callear, {Samantha K.} and Sapchenko, {Sergey A.} and Yongqiang Cheng and Inigo Vit{\'o}rica-Yrez{\'a}bal and Frogley, {Mark D.} and Gianfelice Cinque and Tang, {Chiu C.} and Carlotta Giacobbe and Catherine Dejoie and Svemir Rudi{\'c} and Ramirez-Cuesta, {Anibal J.} and Denecke, {Melissa A.} and Sihai Yang and Martin Schr{\"o}der",

note = "Publisher Copyright: {\textcopyright} 2017 American Chemical Society.",

year = "2017",

month = nov,

day = "15",

doi = "10.1021/jacs.7b08748",

language = "English",

volume = "139",

pages = "16289--16296",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "45",

}

Zhang, X, Da Silva, I, Godfrey, HGW, Callear, SK, Sapchenko, SA, Cheng, Y, Vitórica-Yrezábal, I, Frogley, MD, Cinque, G, Tang, CC, Giacobbe, C, Dejoie, C, Rudić, S, Ramirez-Cuesta, AJ, Denecke, MA, Yang, S & Schröder, M 2017, 'Confinement of Iodine Molecules into Triple-Helical Chains within Robust Metal-Organic Frameworks', Journal of the American Chemical Society, vol. 139, no. 45, pp. 16289-16296. https://doi.org/10.1021/jacs.7b08748

TY - JOUR

T1 - Confinement of Iodine Molecules into Triple-Helical Chains within Robust Metal-Organic Frameworks

AU - Zhang, Xinran

AU - Da Silva, Ivan

AU - Godfrey, Harry G.W.

AU - Callear, Samantha K.

AU - Sapchenko, Sergey A.

AU - Cheng, Yongqiang

AU - Vitórica-Yrezábal, Inigo

AU - Frogley, Mark D.

AU - Cinque, Gianfelice

AU - Tang, Chiu C.

AU - Giacobbe, Carlotta

AU - Dejoie, Catherine

AU - Rudić, Svemir

AU - Ramirez-Cuesta, Anibal J.

AU - Denecke, Melissa A.

AU - Yang, Sihai

AU - Schröder, Martin

PY - 2017/11/15

Y1 - 2017/11/15

N2 - 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 I2 adsorption in a series of robust porous metal-organic materials, MFM-300(M) (M = Al, Sc, Fe, In). MFM-300(Sc) exhibits fully reversible I2 uptake of 1.54 g g-1, and its structure remains completely unperturbed upon inclusion/removal of I2. Direct observation and quantification of the adsorption, binding domains and dynamics of guest I2 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-I2 and I2-I2 binding interactions at a molecular level. The initial binding site of I2 in MFM-300(Sc), I2I, is located near the bridging hydroxyl group of the [ScO4(OH)2] moiety [I2I···H-O = 2.263(9) Å] with an occupancy of 0.268. I2II is located interstitially between two phenyl rings of neighboring ligand molecules [I2II···phenyl ring = 3.378(9) and 4.228(5) Å]. I2II is 4.565(2) Å from the hydroxyl group with an occupancy of 0.208. Significantly, at high I2 loading an unprecedented self-aggregation of I2 molecules into triple-helical chains within the confined nanovoids has been observed at crystallographic resolution, leading to a highly efficient packing of I2 molecules with an exceptional I2 storage density of 3.08 g cm-3 in MFM-300(Sc).

AB - 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 I2 adsorption in a series of robust porous metal-organic materials, MFM-300(M) (M = Al, Sc, Fe, In). MFM-300(Sc) exhibits fully reversible I2 uptake of 1.54 g g-1, and its structure remains completely unperturbed upon inclusion/removal of I2. Direct observation and quantification of the adsorption, binding domains and dynamics of guest I2 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-I2 and I2-I2 binding interactions at a molecular level. The initial binding site of I2 in MFM-300(Sc), I2I, is located near the bridging hydroxyl group of the [ScO4(OH)2] moiety [I2I···H-O = 2.263(9) Å] with an occupancy of 0.268. I2II is located interstitially between two phenyl rings of neighboring ligand molecules [I2II···phenyl ring = 3.378(9) and 4.228(5) Å]. I2II is 4.565(2) Å from the hydroxyl group with an occupancy of 0.208. Significantly, at high I2 loading an unprecedented self-aggregation of I2 molecules into triple-helical chains within the confined nanovoids has been observed at crystallographic resolution, leading to a highly efficient packing of I2 molecules with an exceptional I2 storage density of 3.08 g cm-3 in MFM-300(Sc).

UR - http://www.scopus.com/inward/record.url?scp=85034242059&partnerID=8YFLogxK

U2 - 10.1021/jacs.7b08748

DO - 10.1021/jacs.7b08748

M3 - Article

C2 - 29020767

AN - SCOPUS:85034242059

SN - 0002-7863

VL - 139

SP - 16289

EP - 16296

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 45

ER -

Confinement of Iodine Molecules into Triple-Helical Chains within Robust Metal-Organic Frameworks

Abstract

Funding

Access to Document

Other files and links

Fingerprint

Cite this