Strong CO2 binding in a water-stable, triazolate-bridged metal-organic framework functionalized with ethylenediamine.
نویسندگان
چکیده
Reaction of CuCl(2) x 2 H(2)O with 1,3,5-tris(1H-1,2,3-triazol-5-yl)benzene (H(3)BTTri) in DMF at 100 degrees C generates the metal-organic framework H(3)[(Cu(4)Cl)(3)(BTTri)(8)(DMF)(12)] x 7 DMF x 76 H(2)O (1-DMF). The sodalite-type structure of the framework consists of BTTri(3-)-linked [Cu(4)Cl](7+) square clusters in which each Cu(II) center has a terminal DMF ligand directed toward the interior of a large pore. The framework exhibits a high thermal stability of up to 270 degrees C, as well as exceptional chemical stability in air, boiling water, and acidic media. Following exchange of the guest solvent and bound DMF molecules for methanol to give 1-MeOH, complete desolvation of the framework at 180 degrees C generated H(3)[(Cu(4)Cl)(3)(BTTri)(8)] (1) with exposed Cu(II) sites on its surface. Following a previously reported protocol, ethylenediamine molecules were grafted onto these sites to afford 1-en, featuring terminal alkylamine groups. The N(2) adsorption isotherms indicate a reduction in the BET surface area from 1770 to 345 m(2)/g following grafting. The H(2) adsorption data at 77 K for 1 indicate a fully reversible uptake of 1.2 wt % at 1.2 bar, while the CO(2) isotherm at 195 K shows a maximal uptake of 90 wt % at 1 bar. Compared to 1, the alkylamine-functionalized framework 1-en exhibits a higher uptake of CO(2) at 298 K and pressures up to ca. 0.1 bar, as well as a higher CO(2)/N(2) selectivity at all measured pressures. Significantly, 1-en also exhibits an isosteric heat of CO(2) adsorption of 90 kJ/mol, which is much higher than the 21 kJ/mol observed for 1. This chemisorption interaction is the strongest reported to date for a metal-organic framework and points toward the potential utility of alkylamine-appended frameworks for the postcombustion capture of CO(2) from low-pressure flue gas streams.
منابع مشابه
Enhanced carbon dioxide capture upon incorporation of N,N0-dimethylethylenediamine in the metal–organic framework CuBTTri†
High capacity, high selectivity, and low-cost regeneration conditions are the most important criteria by which new adsorbents for post-combustion carbon dioxide capture will be judged. The incorporation of N,N0-dimethylethylenediamine (mmen) into H3[(Cu4Cl)3(BTTri)8 (CuBTTri; H3BTTri 1⁄4 1,3,5-tri(1H1,2,3-triazol-4-yl)benzene), a water-stable, triazolate-bridged framework, is shown to drastical...
متن کاملCarbon dioxide capture in metal-organic frameworks.
Efforts to utilize metal-organic frameworks, a new class of materials exhibiting high surface areas, tunable pore dimensions, and adjustable surface functionality, for CO2 capture will be presented. Open metal coordination sites on the framework surface can deliver a high CO2 loading capacity at low pressures. However, additional criteria such as water stability and the selective binding of CO2...
متن کاملEfficient removal of cobalt(II) ion from aqueous solution using amide-functionalized metal-organic framework
In this study, an amide-functionalized metal-organic framework, namely TMU-24 was selected to adsorb Co(II) from wastewater with an adsorption capacity of 500 mg. g-1 in less than 20 minutes in neutral pH (pH=7). The effect of diverse parameters such as adsorbent dosage, competitive ions, and contact time on the adsorption process was investigated to find the optimal amounts of them. Also, the ...
متن کاملNew amine-functionalized cobalt cluster-based frameworks with open metal sites and suitable pore sizes: multipoint interactions enhanced CO2 sorption.
By employing the mixed-linker synthetic strategy, two new cobalt(II) cluster-based frameworks, [Co(2.5)(btc)(atz)2(Hatz)(DMF)]·2DMF (1) and [Co(2.5)(btc)(Hbtc)0.5(atz)(CH3CN)(H2O)]·H2O (2), constructed from the same initial materials Co(NO3)2, 1,3,5-benzenetricarboxylic acid (H3btc) and 3-amino-1,2,4-triazole (Hatz), have been synthesized by solvothermal reactions. Crystal-structure analyses de...
متن کاملIn this paper, the effect of nanocatalytic metal-organic framework based on copper metal and bis-tetrazolamine (CuBTA) ligand functionalized with cobalt (II) oxide nanoparticles on the thermal decomposition behavior of ammonium perchlorate (AP), using differential survey calorimetry (DSC) has been reviewed. First, the metal-organic framework (CuBTA) was synthesized from the raw materials of cop...
متن کاملذخیره در منابع من
با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید
برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید
ثبت ناماگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید
ورودعنوان ژورنال:
- Journal of the American Chemical Society
دوره 131 25 شماره
صفحات -
تاریخ انتشار 2009