Molecular Mechanisms of Water-Mediated Proton Transport in MIL-53 Metal–Organic Frameworks

2013 ◽  
Vol 117 (38) ◽  
pp. 19508-19516 ◽  
Author(s):  
Francesco Paesani
Keyword(s):  
Proton Transport ◽  
Molecular Mechanisms ◽  
Metal Organic Frameworks ◽  
Metal Organic

Proton Transport in Metal–Organic Frameworks

2020 ◽  
Vol 120 (16) ◽  
pp. 8416-8467 ◽  
Author(s):  
Dae-Woon Lim ◽  
Hiroshi Kitagawa
Keyword(s):  
Proton Transport ◽  
Metal Organic Frameworks ◽  
Metal Organic

scholarly journals Elucidating CO2 Chemisorption in Diamine-Appended Metal–Organic Frameworks

2018 ◽  
Author(s):  
Alexander C. Forse ◽  
Phillip J. Milner ◽  
Jung-Hoon Lee ◽  
Halle N. Redfearn ◽  
Julia Oktawiec ◽  
...  
Keyword(s):  
Carbon Capture ◽  
Density Functional ◽  
Molecular Mechanisms ◽  
Metal Organic Frameworks ◽  
Carbamic Acid ◽  
Co2 Uptake ◽  
Functional Theory ◽  
Ammonium Carbamate ◽  
Co2 Chemisorption ◽  
Metal Organic

The widespread deployment of carbon capture and sequestration as a climate change mitigation strategy could be facilitated by the development of more energy-efficient adsorbents. Diamine-appended metal–organic frameworks of the type diamine–M2(dobpdc) (M = Mg, Mn, Fe, Co, Ni, Zn; dobpdc4− = 4,4′-dioxidobiphenyl-3,3′-dicarboxylate) have shown promise for carbon capture applications, although questions remain regarding the molecular mechanisms of CO2 uptake in these materials. Here, we leverage the crystallinity and tunability of this class of frameworks to perform a comprehensive study of CO2 chemisorption. Using multinuclear nuclear magnetic resonance (NMR) spectroscopy experiments and van der Waals-corrected density functional theory (DFT) calculations for thirteen diamine–M2(dobpdc) variants, we demonstrate that the canonical CO2 chemisorption products—ammonium carbamate chains and carbamic acid pairs—can be readily distinguished, and that ammonium carbamate chain formation dominates for diamine–Mg2(dobpdc) materials. In addition, we elucidate a new chemisorption mechanism in the material dmpn Mg2(dobpdc) (dmpn = 2,2-dimethyl-1,3-diaminopropane), which involves formation of a 1:1 mixture of ammonium carbamate and carbamic acid and accounts for the unusual adsorption properties of this material. Finally, we show that the presence of water plays an important role in directing the mechanisms for CO2 uptake in diamine–M2(dobpdc) materials. Overall, our combined NMR and DFT approach enables a thorough depiction and understanding of CO2 adsorption within diamine–M2(dobpdc) compounds, which may aid similar studies in other amine-functionalized adsorbents in the future.

scholarly journals Elucidating CO2 Chemisorption in Diamine-Appended Metal–Organic Frameworks

2018 ◽  
Author(s):  
Alexander C. Forse ◽  
Phillip J. Milner ◽  
Jung-Hoon Lee ◽  
Halle N. Redfearn ◽  
Julia Oktawiec ◽  
...  
Keyword(s):  
Carbon Capture ◽  
Density Functional ◽  
Molecular Mechanisms ◽  
Metal Organic Frameworks ◽  
Carbamic Acid ◽  
Co2 Uptake ◽  
Functional Theory ◽  
Ammonium Carbamate ◽  
Co2 Chemisorption ◽  
Metal Organic

The widespread deployment of carbon capture and sequestration as a climate change mitigation strategy could be facilitated by the development of more energy-efficient adsorbents. Diamine-appended metal–organic frameworks of the type diamine–M2(dobpdc) (M = Mg, Mn, Fe, Co, Ni, Zn; dobpdc4− = 4,4′-dioxidobiphenyl-3,3′-dicarboxylate) have shown promise for carbon capture applications, although questions remain regarding the molecular mechanisms of CO2 uptake in these materials. Here, we leverage the crystallinity and tunability of this class of frameworks to perform a comprehensive study of CO2 chemisorption. Using multinuclear nuclear magnetic resonance (NMR) spectroscopy experiments and van der Waals-corrected density functional theory (DFT) calculations for thirteen diamine–M2(dobpdc) variants, we demonstrate that the canonical CO2 chemisorption products—ammonium carbamate chains and carbamic acid pairs—can be readily distinguished, and that ammonium carbamate chain formation dominates for diamine–Mg2(dobpdc) materials. In addition, we elucidate a new chemisorption mechanism in the material dmpn Mg2(dobpdc) (dmpn = 2,2-dimethyl-1,3-diaminopropane), which involves formation of a 1:1 mixture of ammonium carbamate and carbamic acid and accounts for the unusual adsorption properties of this material. Finally, we show that the presence of water plays an important role in directing the mechanisms for CO2 uptake in diamine–M2(dobpdc) materials. Overall, our combined NMR and DFT approach enables a thorough depiction and understanding of CO2 adsorption within diamine–M2(dobpdc) compounds, which may aid similar studies in other amine-functionalized adsorbents in the future.

Proton Transport through Robust CPO-27-type Metal Organic Frameworks

2014 ◽  
Vol 118 (37) ◽  
pp. 21663-21670 ◽  
Author(s):  
Cecilia Solís ◽  
Daniel Palaci ◽  
Francesc X. Llabrés i Xamena ◽  
José M. Serra
Keyword(s):  
Proton Transport ◽  
Metal Organic Frameworks ◽  
Metal Organic

Probing Molecular Mechanisms of Self-Assembly in Metal–Organic Frameworks

ACS Nano ◽  
2016 ◽  
Vol 11 (1) ◽  
pp. 258-268 ◽  
Author(s):  
Debasmita Biswal ◽  
Peter G. Kusalik
Keyword(s):  
Self Assembly ◽  
Molecular Mechanisms ◽  
Metal Organic Frameworks ◽  
Metal Organic

scholarly journals Elucidating CO2 Chemisorption in Diamine-Appended Metal–Organic Frameworks

2018 ◽  
Author(s):  
Alexander C. Forse ◽  
Phillip J. Milner ◽  
Jung-Hoon Lee ◽  
Halle N. Redfearn ◽  
Julia Oktawiec ◽  
...  
Keyword(s):  
Carbon Capture ◽  
Density Functional ◽  
Molecular Mechanisms ◽  
Metal Organic Frameworks ◽  
Carbamic Acid ◽  
Co2 Uptake ◽  
Functional Theory ◽  
Ammonium Carbamate ◽  
Co2 Chemisorption ◽  
Metal Organic

The widespread deployment of carbon capture and sequestration as a climate change mitigation strategy could be facilitated by the development of more energy-efficient adsorbents. Diamine-appended metal–organic frameworks of the type diamine–M2(dobpdc) (M = Mg, Mn, Fe, Co, Ni, Zn; dobpdc4− = 4,4′-dioxidobiphenyl-3,3′-dicarboxylate) have shown promise for carbon capture applications, although questions remain regarding the molecular mechanisms of CO2 uptake in these materials. Here, we leverage the crystallinity and tunability of this class of frameworks to perform a comprehensive study of CO2 chemisorption. Using multinuclear nuclear magnetic resonance (NMR) spectroscopy experiments and van der Waals-corrected density functional theory (DFT) calculations for thirteen diamine–M2(dobpdc) variants, we demonstrate that the canonical CO2 chemisorption products—ammonium carbamate chains and carbamic acid pairs—can be readily distinguished, and that ammonium carbamate chain formation dominates for diamine–Mg2(dobpdc) materials. In addition, we elucidate a new chemisorption mechanism in the material dmpn Mg2(dobpdc) (dmpn = 2,2-dimethyl-1,3-diaminopropane), which involves formation of a 1:1 mixture of ammonium carbamate and carbamic acid and accounts for the unusual adsorption properties of this material. Finally, we show that the presence of water plays an important role in directing the mechanisms for CO2 uptake in diamine–M2(dobpdc) materials. Overall, our combined NMR and DFT approach enables a thorough depiction and understanding of CO2 adsorption within diamine–M2(dobpdc) compounds, which may aid similar studies in other amine-functionalized adsorbents in the future.

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