High and Selective CO2 Uptake in a Cobalt Adeninate Metal-Organic Framework Exhibiting Pyrimidine- and Amino-Decorated Pores

Department of Chemistry, University of Pittsburgh, 219 Parkman Avenue, Pittsburgh, Pennsylvania 15260, USA.
Journal of the American Chemical Society (Impact Factor: 12.11). 12/2009; 132(1):38-9. DOI: 10.1021/ja909169x
Source: PubMed


The synthesis and structure of Co(2)(ad)(2)(CO(2)CH(3))(2) x 2 DMF x 0.5 H(2)O (bio-MOF-11) is described. Pyrimidine and amino groups of adeninate (ad) decorate the pores of the framework. The porosity of this material was studied, and its CO(2) and H(2) adsorption properties were evaluated. bio-MOF-11 exhibits a high heat of adsorption for CO(2) (approximately 45 kJ/mol), a high CO(2) capacity (approximately 6 mmol/g, 273 K), and exceptional selectivity for CO(2) over N(2) at 273 K (81:1) and 298 K (75:1).

Download full-text


Available from: Steven J Geib,
  • Source
    • "Currently, a great deal of efforts have been made on the development of solid sorbents for post-combustion capture (PCC) due to their advantages in lower regeneration heat requirement, less amine evaporation and less vessel corrosion. These sorbents include the physi-sorbents such as zeolites [3] [4] [5] and activated carbons [6] [7] and more recently chemi-sorbents such as regenerable alkaline-based adsorbents, amine-functionalized mesoporous silicas [8] [9] [10] [11] and metal organic frameworks (MOFs) [12] [13]. A number of amine-based solid sorbents have demonstrated their high adsorption efficiency and regenerability for the removal of CO 2 from flue gas mixtures [14] [15] [16] [17] [18]. "
    [Show abstract] [Hide abstract]
    ABSTRACT: The high performance of polyethyleneimine (PEI)-based solid adsorbent for CO2 capture has been well recognized in thermogravimetric analysis (TGA) and small-scale fixed bed reactors through the measurements of their equilibrium capacities but has not been really demonstrated on larger scales towards practical utilization. In the present study, a laboratory-scale bubbling fluidized bed reactor loaded with a few kg adsorbent is used to evaluate the adsorption performance of PEI–silica adsorbent under different working conditions including with/without the presence of moisture, different gas–solid contact times, initial bed temperatures, and CO2 partial pressures. The adsorption capacities have shown a clear degradation tendency under dry condition. However, they can be stabilized at a high level of 10.6–11.1% w/w over 60 cycles if moisture (ca. 8.8 vol%) is present in the gas flow during adsorption and desorption. Breakthrough capacities can be stabilized at the level of 7.6–8.2% w/w with the gas–solid contact time of 13 s. The adsorption capacities for the simulated flue gases containing 5% CO2 are only slightly lower than those for the simulated flue gases containing 15% CO2, indicating that the PEI–silica adsorbent is suitable for CO2 capture from flue gases of both coal-fired and natural gas-fired combined cycle power plants. The exothermal heat of adsorption is estimated by the energy balance in the fluidized bed reactor and found to be close (within 10%) to the measured value by TG-DSC. The regeneration heat for the as-prepared PEI–silica adsorbent is found to be 2360 kJ/kgCO2 assuming 75% recovery of sensible heat which is well below the values of 3900–4500 kJ/kgCO2 for a typical MEA scrubbing process with 90% recovery of sensible heat.
    The Chemical Engineering Journal 09/2014; 251:293–303. DOI:10.1016/j.cej.2014.04.063 · 4.32 Impact Factor
    • "Previous research studies have shown that adsorption using aqueous ammonia [5] or solid adsorbents are the methods most likely to be adapted in industrial applications for the efficient capture of CO 2 from flue gases [6]. When multiple CO 2 adsorbents were compared (i.e., porous carbons, carbon–CaO composites, amine-modified mesoporous silicas, N-containing group-bridged metal phosphonates, covalent organic frameworks, metal–organic frameworks and microporous organic polymers), carbon based materials displayed a comparatively high adsorption capacity for CO 2 capture over a wide range of operating conditions [7] [8] [9] [10] [11] [12] [13] [14]. "
    [Show abstract] [Hide abstract]
    ABSTRACT: S-doped microporous carbon materials were synthesized by the chemical activation of a reduced-graphene-oxide/poly-thiophene material. The material displayed a large CO2 adsorption capacity of 4.5 mmol g−1 at 298 K and 1 atm, as well as an impressive CO2 adsorption selectivity over N2, CH4 and H2. The material was shown to exhibit a stable recycling adsorption capacity of 4.0 mmol g−1. The synthesized material showed a maximum specific surface area of 1567 m2 g−1 and an optimal CO2 adsorption pore size of 0.6 nm. The microporosity, surface area and oxidized S content of the material were found to be the determining factors for CO2 adsorption. These properties show that the as synthesized S-doped microporous carbon material can be more effective than similarly prepared N-doped microporous carbons in CO2 capture.
    Carbon 01/2014; 66:320–326. DOI:10.1016/j.carbon.2013.09.006 · 6.20 Impact Factor
  • Source
    • "At 273 K and 1 bar, the CO2/CH4 selectivity is about 4.5:1 (v/v) for TKL-107, 4.4:1 (v/v) for TKL-106 and 4.1:1 (v/v) for TKL-105. On the other hand, the initial slopes of the adsorption isotherms were calculated and the ratios of these slopes could also be used to estimate the adsorption selectivity at very low pressure (Figure S23–25)44. The calculated CO2/N2 selectivity from these data is about 13.8:1 for TKL-107, 15.0:1 for TKL-106, and 15.8:1 for TKL-105, respectively, which were in accord with the isosteric heats (Figure S20). "
    [Show abstract] [Hide abstract]
    ABSTRACT: A new class of metal-organic frameworks (MOFs) has been synthesized by ligand-functionalization strategy. Systematic studies of their adsorption properties were performed at low and high pressure. Importantly, when fluorine was introduced into the framework via the functionalization, both the framework stabilities and adsorption capacities towards H2/CO2 were enhanced significantly. This consequence can be well interpreted by theoretical studies of these MOFs structures. In addition, one of these MOFs TKL-107 was used to fabricate mixed matrix membranes, which exhibit great potential for the application of CO2 separation.
    Scientific Reports 11/2013; 3:3312. DOI:10.1038/srep03312 · 5.58 Impact Factor
Show more