Hydrolytically stable fluorinated metal-organic frameworks for energy-efficient dehydration

Amandine Cadiau; Youssef Belmabkhout; Karim Adil; Prashant Bhatt; Renjith S. Pillai; Aleksander Shkurenko; Charlotte Martineau-Corcos; Guillaume Maurin; Mohamed Eddaoudi

doi:10.1126/science.aam8310

Hydrolytically stable fluorinated metal-organic frameworks for energy-efficient dehydration

Amandine Cadiau, Youssef Belmabkhout, Karim Adil, Prashant Bhatt, Renjith S. Pillai, Aleksander Shkurenko, Charlotte Martineau-Corcos, Guillaume Maurin, Mohamed Eddaoudi

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

252 Scopus citations

Abstract

Natural gas must be dehydrated before it can be transported and used, but conventional drying agents such as activated alumina or inorganic molecular sieves require an energy-intensive desiccant-regeneration step. We report a hydrolytically stable fluorinated metal-organic framework, AlFFIVE-1-Ni (KAUST-8), with a periodic array of open metal coordination sites and fluorine moieties within the contracted square-shaped one-dimensional channel. This material selectively removed water vapor from gas streams containing CO2, N2, CH4, and higher hydrocarbons typical of natural gas, as well as selectively removed both H2O and CO2 in N2-containing streams. The complete desorption of the adsorbed water molecules contained by the AlFFIVE-1-Ni sorbent requires relatively moderate temperature (~105°C) and about half the energy input for commonly used desiccants.

Original language	English (US)
Pages (from-to)	731-735
Number of pages	5
Journal	Science
Volume	356
Issue number	6339
DOIs	https://doi.org/10.1126/science.aam8310
State	Published - May 18 2017

Bibliographical note

KAUST Repository Item: Exported on 2020-10-01
Acknowledged KAUST grant number(s): CCF/1/1972-02-01, CCF/1/1972-8-01, OSR-2017-CPF-3325
Acknowledgements: Research reported in this publication was solely performed at KAUST and was supported by KAUST funds, KAUST funding grants (CCF/1/1972-02-01, CCF/1/1972-8-01, and OSR-2017-CPF-3325), and Aramco. The data reported in the paper are presented in the main text and the supplementary materials. Crystal structures of the as-synthesized AlFFIVE-1-Ni, the dehydrated AlFFIVE-1-Ni, AlFFIVE-1-Ni (rehydrated), AlFFIVE-1-Ni·1.48H2O·0.26CO2, and FeFFIVE-1-Ni are available free of charge from the Cambridge Crystallographic Data Centre (CCDC) under reference nos. CCDC 1538217, 1538215, 1538216, 1538219, and 1538218. A.C., Y.B., K.A., P.M.B., M.E., and KAUST have filed provisional patents (WO2016/162834A1 and WO2016/162835A1) pertaining to the results presented herein. K.A., M.E., and A.C. conceptualized the design and the construction of the reported MOF materials; A.C. carried out the materials synthesis; K.A., A.C., and A.S. conducted and interpreted the crystallographic experiments; P.M.B., Y.B., and A.C. conducted and interpreted low-pressure adsorption experiments; Y.B. and P.M.B. contributed to conceptualizing, designing, conducting, and interpreting calorimetric and mixed adsorption experiments; R.S.P. and G.M. performed andanalyzed the DFT calculations; C.M.-C. conducted and analyzed the solid-state NMR experiments; and K.A., Y.B., A.C., and M.E. wrote the manuscript.

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10.1126/science.aam8310

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@article{83b7105a61e6496f85caf9316d2e0248,

title = "Hydrolytically stable fluorinated metal-organic frameworks for energy-efficient dehydration",

abstract = "Natural gas must be dehydrated before it can be transported and used, but conventional drying agents such as activated alumina or inorganic molecular sieves require an energy-intensive desiccant-regeneration step. We report a hydrolytically stable fluorinated metal-organic framework, AlFFIVE-1-Ni (KAUST-8), with a periodic array of open metal coordination sites and fluorine moieties within the contracted square-shaped one-dimensional channel. This material selectively removed water vapor from gas streams containing CO2, N2, CH4, and higher hydrocarbons typical of natural gas, as well as selectively removed both H2O and CO2 in N2-containing streams. The complete desorption of the adsorbed water molecules contained by the AlFFIVE-1-Ni sorbent requires relatively moderate temperature (~105°C) and about half the energy input for commonly used desiccants.",

author = "Amandine Cadiau and Youssef Belmabkhout and Karim Adil and Prashant Bhatt and Pillai, {Renjith S.} and Aleksander Shkurenko and Charlotte Martineau-Corcos and Guillaume Maurin and Mohamed Eddaoudi",

note = "KAUST Repository Item: Exported on 2020-10-01 Acknowledged KAUST grant number(s): CCF/1/1972-02-01, CCF/1/1972-8-01, OSR-2017-CPF-3325 Acknowledgements: Research reported in this publication was solely performed at KAUST and was supported by KAUST funds, KAUST funding grants (CCF/1/1972-02-01, CCF/1/1972-8-01, and OSR-2017-CPF-3325), and Aramco. The data reported in the paper are presented in the main text and the supplementary materials. Crystal structures of the as-synthesized AlFFIVE-1-Ni, the dehydrated AlFFIVE-1-Ni, AlFFIVE-1-Ni (rehydrated), AlFFIVE-1-Ni·1.48H2O·0.26CO2, and FeFFIVE-1-Ni are available free of charge from the Cambridge Crystallographic Data Centre (CCDC) under reference nos. CCDC 1538217, 1538215, 1538216, 1538219, and 1538218. A.C., Y.B., K.A., P.M.B., M.E., and KAUST have filed provisional patents (WO2016/162834A1 and WO2016/162835A1) pertaining to the results presented herein. K.A., M.E., and A.C. conceptualized the design and the construction of the reported MOF materials; A.C. carried out the materials synthesis; K.A., A.C., and A.S. conducted and interpreted the crystallographic experiments; P.M.B., Y.B., and A.C. conducted and interpreted low-pressure adsorption experiments; Y.B. and P.M.B. contributed to conceptualizing, designing, conducting, and interpreting calorimetric and mixed adsorption experiments; R.S.P. and G.M. performed andanalyzed the DFT calculations; C.M.-C. conducted and analyzed the solid-state NMR experiments; and K.A., Y.B., A.C., and M.E. wrote the manuscript.",

year = "2017",

month = may,

day = "18",

doi = "10.1126/science.aam8310",

language = "English (US)",

volume = "356",

pages = "731--735",

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TY - JOUR

T1 - Hydrolytically stable fluorinated metal-organic frameworks for energy-efficient dehydration

AU - Cadiau, Amandine

AU - Belmabkhout, Youssef

AU - Adil, Karim

AU - Bhatt, Prashant

AU - Pillai, Renjith S.

AU - Shkurenko, Aleksander

AU - Martineau-Corcos, Charlotte

AU - Maurin, Guillaume

AU - Eddaoudi, Mohamed

N1 - KAUST Repository Item: Exported on 2020-10-01 Acknowledged KAUST grant number(s): CCF/1/1972-02-01, CCF/1/1972-8-01, OSR-2017-CPF-3325 Acknowledgements: Research reported in this publication was solely performed at KAUST and was supported by KAUST funds, KAUST funding grants (CCF/1/1972-02-01, CCF/1/1972-8-01, and OSR-2017-CPF-3325), and Aramco. The data reported in the paper are presented in the main text and the supplementary materials. Crystal structures of the as-synthesized AlFFIVE-1-Ni, the dehydrated AlFFIVE-1-Ni, AlFFIVE-1-Ni (rehydrated), AlFFIVE-1-Ni·1.48H2O·0.26CO2, and FeFFIVE-1-Ni are available free of charge from the Cambridge Crystallographic Data Centre (CCDC) under reference nos. CCDC 1538217, 1538215, 1538216, 1538219, and 1538218. A.C., Y.B., K.A., P.M.B., M.E., and KAUST have filed provisional patents (WO2016/162834A1 and WO2016/162835A1) pertaining to the results presented herein. K.A., M.E., and A.C. conceptualized the design and the construction of the reported MOF materials; A.C. carried out the materials synthesis; K.A., A.C., and A.S. conducted and interpreted the crystallographic experiments; P.M.B., Y.B., and A.C. conducted and interpreted low-pressure adsorption experiments; Y.B. and P.M.B. contributed to conceptualizing, designing, conducting, and interpreting calorimetric and mixed adsorption experiments; R.S.P. and G.M. performed andanalyzed the DFT calculations; C.M.-C. conducted and analyzed the solid-state NMR experiments; and K.A., Y.B., A.C., and M.E. wrote the manuscript.

PY - 2017/5/18

Y1 - 2017/5/18

N2 - Natural gas must be dehydrated before it can be transported and used, but conventional drying agents such as activated alumina or inorganic molecular sieves require an energy-intensive desiccant-regeneration step. We report a hydrolytically stable fluorinated metal-organic framework, AlFFIVE-1-Ni (KAUST-8), with a periodic array of open metal coordination sites and fluorine moieties within the contracted square-shaped one-dimensional channel. This material selectively removed water vapor from gas streams containing CO2, N2, CH4, and higher hydrocarbons typical of natural gas, as well as selectively removed both H2O and CO2 in N2-containing streams. The complete desorption of the adsorbed water molecules contained by the AlFFIVE-1-Ni sorbent requires relatively moderate temperature (~105°C) and about half the energy input for commonly used desiccants.

AB - Natural gas must be dehydrated before it can be transported and used, but conventional drying agents such as activated alumina or inorganic molecular sieves require an energy-intensive desiccant-regeneration step. We report a hydrolytically stable fluorinated metal-organic framework, AlFFIVE-1-Ni (KAUST-8), with a periodic array of open metal coordination sites and fluorine moieties within the contracted square-shaped one-dimensional channel. This material selectively removed water vapor from gas streams containing CO2, N2, CH4, and higher hydrocarbons typical of natural gas, as well as selectively removed both H2O and CO2 in N2-containing streams. The complete desorption of the adsorbed water molecules contained by the AlFFIVE-1-Ni sorbent requires relatively moderate temperature (~105°C) and about half the energy input for commonly used desiccants.

UR - http://hdl.handle.net/10754/625006

UR - http://science.sciencemag.org/content/356/6339/731.full

UR - http://www.scopus.com/inward/record.url?scp=85019881607&partnerID=8YFLogxK

U2 - 10.1126/science.aam8310

DO - 10.1126/science.aam8310

M3 - Article

C2 - 28522529

SN - 0036-8075

VL - 356

SP - 731

EP - 735

JO - Science

JF - Science

IS - 6339

ER -

Hydrolytically stable fluorinated metal-organic frameworks for energy-efficient dehydration

Abstract

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CCDC 1538218: Experimental Crystal Structure Determination : catena-[bis(mu-pyrazine)-bis(mu-fluoro)-aqua-trifluoro-iron-nickel tetrahydrate]

CCDC 1538216: Experimental Crystal Structure Determination : catena-[bis(mu-pyrazine)-bis(mu-fluoro)-aqua-trifluoro-aluminium-nickel unknown solvate]

CCDC 1538215: Experimental Crystal Structure Determination : catena-[bis(mu-pyrazine)-bis(mu-fluoro)-trifluoro-aluminium-nickel]

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Hydrolytically stable fluorinated metal-organic frameworks for energy-efficient dehydration

Abstract

Bibliographical note

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Datasets

CCDC 1538218: Experimental Crystal Structure Determination : catena-[bis(mu-pyrazine)-bis(mu-fluoro)-aqua-trifluoro-iron-nickel tetrahydrate]

CCDC 1538216: Experimental Crystal Structure Determination : catena-[bis(mu-pyrazine)-bis(mu-fluoro)-aqua-trifluoro-aluminium-nickel unknown solvate]

CCDC 1538215: Experimental Crystal Structure Determination : catena-[bis(mu-pyrazine)-bis(mu-fluoro)-trifluoro-aluminium-nickel]

Cite this