Interaction of Acid Gases SO2 and NO2 with Coordinatively Unsaturated Metal Organic Frameworks: M-MOF-74 (M = Zn, Mg, Ni, Co)

Kui Tan; Sebastian Zuluaga; Hao Wang; Pieremanuele Canepa; Karim Soliman; Jeremy Cure; Jing Li; Timo Thonhauser; Yves J. Chabal

doi:10.1021/acs.chemmater.7b00005

Interaction of Acid Gases SO₂ and NO₂ with Coordinatively Unsaturated Metal Organic Frameworks: M-MOF-74 (M = Zn, Mg, Ni, Co)

Kui Tan, Sebastian Zuluaga, Hao Wang, Pieremanuele Canepa, Karim Soliman, Jeremy Cure, Jing Li, Timo Thonhauser, Yves J. Chabal

School of Arts and Sciences, Chemistry & Chemical Biology

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

96 Scopus citations

Abstract

In situ infrared spectroscopy and ab initio density functional theory (DFT) calculations are combined to study the interaction of the corrosive gases SO₂ and NO₂ with metal organic frameworks M-MOF-74 (M = Zn, Mg, Ni, Co). We find that NO₂ dissociatively adsorbs into MOF-74 compounds, forming NO and NO₃^-. The mechanism is unraveled by considering the Zn-MOF-74 system, for which DFT calculations show that a strong NO₂-Zn bonding interaction induces a significant weakening of the N-O bond, facilitating the decomposition of the NO₂ molecules. In contrast, SO₂ is only molecularly adsorbed into MOF-74 with high binding energy (>90 kJ/mol for Mg-MOF-74 and >70 for Zn-MOF-74). This work gives insight into poisoning issues by minor components of flue gases in metal organic frameworks materials.

Original language	English (US)
Pages (from-to)	4227-4235
Number of pages	9
Journal	Chemistry of Materials
Volume	29
Issue number	10
DOIs	https://doi.org/10.1021/acs.chemmater.7b00005
State	Published - May 23 2017

All Science Journal Classification (ASJC) codes

Chemistry(all)
Chemical Engineering(all)
Materials Chemistry

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title = "Interaction of Acid Gases SO2 and NO2 with Coordinatively Unsaturated Metal Organic Frameworks: M-MOF-74 (M = Zn, Mg, Ni, Co)",

abstract = "In situ infrared spectroscopy and ab initio density functional theory (DFT) calculations are combined to study the interaction of the corrosive gases SO2 and NO2 with metal organic frameworks M-MOF-74 (M = Zn, Mg, Ni, Co). We find that NO2 dissociatively adsorbs into MOF-74 compounds, forming NO and NO3-. The mechanism is unraveled by considering the Zn-MOF-74 system, for which DFT calculations show that a strong NO2-Zn bonding interaction induces a significant weakening of the N-O bond, facilitating the decomposition of the NO2 molecules. In contrast, SO2 is only molecularly adsorbed into MOF-74 with high binding energy (>90 kJ/mol for Mg-MOF-74 and >70 for Zn-MOF-74). This work gives insight into poisoning issues by minor components of flue gases in metal organic frameworks materials.",

author = "Kui Tan and Sebastian Zuluaga and Hao Wang and Pieremanuele Canepa and Karim Soliman and Jeremy Cure and Jing Li and Timo Thonhauser and Chabal, {Yves J.}",

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doi = "10.1021/acs.chemmater.7b00005",

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TY - JOUR

T1 - Interaction of Acid Gases SO2 and NO2 with Coordinatively Unsaturated Metal Organic Frameworks

T2 - M-MOF-74 (M = Zn, Mg, Ni, Co)

AU - Tan, Kui

AU - Zuluaga, Sebastian

AU - Wang, Hao

AU - Canepa, Pieremanuele

AU - Soliman, Karim

AU - Cure, Jeremy

AU - Li, Jing

AU - Thonhauser, Timo

AU - Chabal, Yves J.

PY - 2017/5/23

Y1 - 2017/5/23

N2 - In situ infrared spectroscopy and ab initio density functional theory (DFT) calculations are combined to study the interaction of the corrosive gases SO2 and NO2 with metal organic frameworks M-MOF-74 (M = Zn, Mg, Ni, Co). We find that NO2 dissociatively adsorbs into MOF-74 compounds, forming NO and NO3-. The mechanism is unraveled by considering the Zn-MOF-74 system, for which DFT calculations show that a strong NO2-Zn bonding interaction induces a significant weakening of the N-O bond, facilitating the decomposition of the NO2 molecules. In contrast, SO2 is only molecularly adsorbed into MOF-74 with high binding energy (>90 kJ/mol for Mg-MOF-74 and >70 for Zn-MOF-74). This work gives insight into poisoning issues by minor components of flue gases in metal organic frameworks materials.

AB - In situ infrared spectroscopy and ab initio density functional theory (DFT) calculations are combined to study the interaction of the corrosive gases SO2 and NO2 with metal organic frameworks M-MOF-74 (M = Zn, Mg, Ni, Co). We find that NO2 dissociatively adsorbs into MOF-74 compounds, forming NO and NO3-. The mechanism is unraveled by considering the Zn-MOF-74 system, for which DFT calculations show that a strong NO2-Zn bonding interaction induces a significant weakening of the N-O bond, facilitating the decomposition of the NO2 molecules. In contrast, SO2 is only molecularly adsorbed into MOF-74 with high binding energy (>90 kJ/mol for Mg-MOF-74 and >70 for Zn-MOF-74). This work gives insight into poisoning issues by minor components of flue gases in metal organic frameworks materials.

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JO - Chemistry of Materials

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ER -

Interaction of Acid Gases SO₂ and NO₂ with Coordinatively Unsaturated Metal Organic Frameworks: M-MOF-74 (M = Zn, Mg, Ni, Co)

Abstract

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