1623061-09-5Relevant articles and documents
Pore Environment Effects on Catalytic Cyclohexane Oxidation in Expanded Fe2(dobdc) Analogues
Xiao, Dianne J.,Oktawiec, Julia,Milner, Phillip J.,Long, Jeffrey R.
, p. 14371 - 14379 (2016)
Metal-organic frameworks are a new class of heterogeneous catalysts in which molecular-level control over both the immediate and long-range chemical environment surrounding a catalytic center can be readily achieved. Here, the oxidation of cyclohexane to
Elucidating CO2 Chemisorption in Diamine-Appended Metal-Organic Frameworks
Forse, Alexander C.,Milner, Phillip J.,Lee, Jung-Hoon,Redfearn, Halle N.,Oktawiec, Julia,Siegelman, Rebecca L.,Martell, Jeffrey D.,Dinakar, Bhavish,Porter-Zasada, Leo B.,Gonzalez, Miguel I.,Neaton, Jeffrey B.,Long, Jeffrey R.,Reimer, Jeffrey A.
, p. 18016 - 18031 (2018)
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 13 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 the 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.
Cooperative Carbon Dioxide Adsorption in Alcoholamine- and Alkoxyalkylamine-Functionalized Metal–Organic Frameworks
Forse, Alexander C.,Kim, Eugene J.,Lee, Jung-Hoon,Long, Jeffrey R.,Mao, Victor Y.,McGuirk, C. Michael,Milner, Phillip J.,Neaton, Jeffrey B.,Porter-Zasada, Leo B.,Reimer, Jeffrey A.,Siegelman, Rebecca L.
supporting information, p. 19468 - 19477 (2020/02/11)
A series of structurally diverse alcoholamine- and alkoxyalkylamine-functionalized variants of the metal–organic framework Mg2(dobpdc) are shown to adsorb CO2 selectively via cooperative chain-forming mechanisms. Solid-state NMR spec
