Three N–H Functionalized Metal–Organic Frameworks with Selective CO2 Uptake, Dye Capture, and Catalysis

2014 ◽  
Vol 53 (14) ◽  
pp. 7692-7699 ◽  
Author(s):  
Yu Zhu ◽  
Yan-Mei Wang ◽  
Sheng-Yun Zhao ◽  
Pan Liu ◽  
Chao Wei ◽  
...  
Keyword(s):  
Metal Organic Frameworks ◽  
Co2 Uptake ◽  
Metal Organic

Harnessing solvent effects to integrate alkylamine into metal–organic frameworks for exceptionally high CO2 uptake

2019 ◽  
Vol 7 (13) ◽  
pp. 7867-7874 ◽  
Author(s):  
Hao Li ◽  
Kecheng Wang ◽  
Zhigang Hu ◽  
Ying-Pin Chen ◽  
Wolfgang Verdegaal ◽  
...  
Keyword(s):  
Solvent Effects ◽  
Polar Solvent ◽  
Metal Organic Frameworks ◽  
Co2 Uptake ◽  
High Co2 ◽  
Metal Organic ◽  
Loading Amount

Alkylamine modified MOF prepared with a less polar solvent (cyclohexane) has a higher alkylamine loading amount and higher CO2 uptake than when prepared in a more polar solvent (dichloromethane).

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.

Microporous rod metal–organic frameworks with diverse Zn/Cd–triazolate ribbons as secondary building units for CO2 uptake and selective adsorption of hydrocarbons

2017 ◽  
Vol 46 (3) ◽  
pp. 836-844 ◽  
Author(s):  
Jian-Wei Zhang ◽  
Man-Cheng Hu ◽  
Shu-Ni Li ◽  
Yu-Cheng Jiang ◽  
Quan-Guo Zhai
Keyword(s):  
Selective Adsorption ◽  
Metal Organic Frameworks ◽  
Isosteric Heat ◽  
Heat Of Adsorption ◽  
Co2 Uptake ◽  
Isosteric Heat Of Adsorption ◽  
Secondary Building Units ◽  
Metal Organic

Three rod MOFs exhibiting remarkable CO2 uptake and high CO2 and C2-hydrocarbons over CH4 selectivity, as well as high isosteric heat of adsorption for C2H2.

scholarly journals Molecular Dye-Sensitized Photocatalysis with Metal-Organic Framework and Metal Oxide Colloids for Fuel Production

Energies ◽  
2021 ◽  
Vol 14 (14) ◽  
pp. 4260
Author(s):  
Philip M. Stanley ◽  
Julien Warnan
Keyword(s):  
Synergistic Effects ◽  
Metal Organic Framework ◽  
Metal Organic Frameworks ◽  
Co2 Uptake ◽  
Fuel Production ◽  
Monoclinic Zro2 ◽  
Dye Sensitized ◽  
Host Materials ◽  
Metal Organic ◽  
Co Reduction

Colloidal dye-sensitized photocatalysis is a promising route toward efficient solar fuel production by merging properties of catalysis, support, light absorption, and electron mediation in one. Metal-organic frameworks (MOFs) are host materials with modular building principles allowing scaffold property tailoring. Herein, we combine these two fields and compare porous Zr-based MOFs UiO-66-NH2(Zr) and UiO-66(Zr) to monoclinic ZrO2 as model colloid hosts with co-immobilized molecular carbon dioxide reduction photocatalyst fac-ReBr(CO)3(4,4′-dcbpy) (dcbpy = dicarboxy-2,2′-bipyridine) and photosensitizer Ru(bpy)2(5,5′-dcbpy)Cl2 (bpy = 2,2′-bipyridine). These host-guest systems demonstrate selective CO2-to-CO reduction in acetonitrile in presence of an electron donor under visible light irradiation, with turnover numbers (TONs) increasing from ZrO2, to UiO-66, and to UiO-66-NH2 in turn. This is attributed to MOF hosts facilitating electron hopping and enhanced CO2 uptake due to their innate porosity. Both of these phenomena are pronounced for UiO-66-NH2(Zr), yielding TONs of 450 which are 2.5 times higher than under MOF-free homogeneous conditions, highlighting synergistic effects between supramolecular photosystem components in dye-sensitized MOFs.

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.

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