Highly Selective CO2 Uptake in Uninodal 6-Connected “mmo” Nets Based upon MO42– (M = Cr, Mo) Pillars

Mohamed, Mona H.; Elsaidi, Sameh K.; Wojtas, Łukasz; Pham, Tony; Forrest, Katherine A.; Tudor, Brant; Space, Brian; Zaworotko, Michael J.

doi:10.1021/ja309452y

Cited by 113 publications

(76 citation statements)

References 61 publications

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“…Several types of MOFs have been proposed for CO 2 capture, including (i) MOFs with open metal sites, [25][26][27][28][29][30][31][32][33][34][35][36][37] (ii) MOFs without open metals sites, [38][39][40][41][42][43][44][45][46][47][48][49][50][51][52][53][54][55] (iii) MOFs with narrow pore size via interpenetration 10,56,57 or shortening the size of the ligands, 10,41 and (iv) MOFs decorated with specific functional groups, including (NH 2 , OH, etc.). 23,51,[58][59][60][61][62][63][64] Functionalization of these types of MOFs may be carried out by post-synthetic modification (PSM) on the open metal sites, 47,[65][66]…”

Section: Discussionmentioning

confidence: 99%

Low concentration CO2 capture using physical adsorbents: Are metal–organic frameworks becoming the new benchmark materials?

Belmabkhout¹,

Guillerm²,

Eddaoudi³

2016

Chemical Engineering Journal

293

168

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KeywordsCO 2 capture, traces CO 2 removal, air capture, physical adsorbents, MOFs AbstractThe capture and separation of traces and concentrated CO 2 from important commodities such as CH 4 , H 2 , O 2 and N 2, is becoming important in many areas related to energy security and environmental sustainability. While trace CO 2 concentration removal applications have been modestly studied for decades, the spike in interest in the capture of concentrated CO 2 was motivated by the need for new energy vectors to replace highly concentrated carbon fuels and the necessity to reduce emissions from fossil fuel-fired power plants. CO 2 capture from various gas streams, at different concentrations, using physical adsorbents, such as activated carbon, zeolites, and metal-organic frameworks (MOFs), is attractive. However, the adsorbents must be designed with consideration of many parameters including CO 2 affinity, kinetics, energetics, stability, capture mechanism, in addition to cost. Here, we perform a systematic analysis regarding the key technical parameters that are required for the best CO 2 capture performance using physical adsorbents. We also experimentally demonstrate a suitable 2 material model of Metal Organic Framework as advanced adsorbents with unprecedented properties for CO 2 capture in a wide range of CO 2 concentration. These recently developed class of MOF adsorbents represent a breakthrough finding in the removal of traces CO 2 using physical adsorption.This platform shows colossal tuning potential for more efficient separation agents.

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Section: Discussionmentioning

confidence: 99%

Low concentration CO2 capture using physical adsorbents: Are metal–organic frameworks becoming the new benchmark materials?

Belmabkhout¹,

Guillerm²,

Eddaoudi³

2016

Chemical Engineering Journal

293

168

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“…These materials are already known to exhibit exceptional properties in terms of CO 2 adsorption and separations . Herein, two microporous mmo topology networks, the CROFOUR‐1‐Ni prototypal mmo network and a new variant, CROFOUR‐2‐Ni (see Scheme ), have been investigated for Xe and Kr adsorption and separation by collecting pure gas adsorption isotherms and column breakthrough experiments for various Xe/Kr gas mixtures.…”

Section: Methodsmentioning

confidence: 99%

Hybrid Ultra‐Microporous Materials for Selective Xenon Adsorption and Separation

et al. 2016

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The demand for Xe/Kr separation continues to grow due to the industrial significance of high-purity Xe gas.Current separation processes rely on energy intensive cryogenic distillation. Therefore,l ess energy intensive alternatives,s uch as physisorptive separation, using porous materials,a re required. Herein we showt hat an underexplored class of porous materials called hybrid ultra-microporous materials (HUMs) affords new benchmark selectivity for Xe separation from Xe/Kr mixtures.The isostructural materials,CROFOUR-1-Ni and CROFOUR-2-Ni, are coordination networks that have coordinatively saturated metal centers and two distinct types of micropores,o ne of which is lined by CrO 4 2À (CROFOUR) anions and the other is decorated by the functionalizedo rganic linker.T hese nets offer unprecedented selectivity towards Xe.M odelling indicates that the selectivity of these nets is tailored by synergy between the pore sizea nd the strong electrostatics afforded by the CrO 4 2À anions.Xenon (Xe) and Krypton (Kr) separation is of industrial interest because these gases present either commercial value as acommodity or an environmental threat. [1] High-purity Xe gas is valuable because of its applications in imaging, lighting, lasers,and medical science.The existing technology for Xe/Kr separation uses cryogenic distillation, which is energetically demanding and laborious.T his was reflected in our recent economic analysis,w hich suggests that metal-organic framework (MOF) based separation at room temperature could be more cost effective than cryogenic distillation in the context of nuclear reprocessing plants.The radioactive 85 Kr and 133 Xe can be introduced to the atmosphere during nuclear reprocessing operations,which means that they need to be captured and sequestered safely. [2] Although Xe is generated as fission product, by the time the fuel is reprocessed, all the radioactive isotopes of Xe have decayed to very low concentrations. Radioactive 85 Kr has al ong half-life (t 1/2 = 10.8 years) and therefore must be captured and removed to prevent its uncontrolled release into the atmosphere.Further presence of any trace amounts of radioactive Kr in Xe rich stream as ab yproduct is not suitable for practical use.T hese factors incentivize the development of an alternative technology for aless energy-intensive,more cost-effective,and safer process to capture Kr and Xe from reprocessing operations.I nt his regard, Zeolites and activated carbon have been evaluated for Xe/Kr separation at ambient conditions,h owever their low Xe selectivity and adsorption capacity renders them impractical. [3] Metal-organic materials (MOMs) [4] have also been widely investigated in terms of this gas separation due to their promising features including their inherent structural modularity,e xtra-large surface area, good thermal stability and recyclability. [5] However, MOMs that rely on unsaturated metal centers have many drawbacks,s uch as their strong tendency to interact with water and the high energy costs associated with their activati...

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“…1,4,10 A subset of MOMs have been shown to display remarkable potential for industrial applications in CO 2 capture/storage and separations. 11−14 In addition, a number of MOMs have the capability to store large amounts of CH 4 at near-ambient temperatures and high pressures. Indeed, some MOMs have already been demonstrated to surpass the old U.S. Department of Energy (DOE) target for on-board methane storage, 3,15−21 which is 180 v(STP)/v under 35 bar and near-ambient temperature.…”

Section: Introductionmentioning

confidence: 99%

Theoretical Investigations of CO₂ and CH₄ Sorption in an Interpenetrated Diamondoid Metal–Organic Material

et al. 2014

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Grand canonical Monte Carlo (GCMC) simulations of CO2 and CH4 sorption and separation were performed in dia-7i-1-Co, a metal–organic material (MOM) consisting of a 7-fold interpenetrated net of Co2+ ions coordinated to 4-(2-(4-pyridyl)ethenyl)benzoate linkers. This MOM shows high affinity toward CH4 at low loading due to the presence of narrow, close fitting, one-dimensional hydrophobic channels—this makes the MOM relevant for applications in low-pressure methane storage. The calculated CO2 and CH4 sorption isotherms and isosteric heat of adsorption, Qst, values in dia-7i-1-Co are in good agreement with the corresponding experimental results for all state points considered. The experimental initial Qst value for CH4 in dia-7i-1-Co is currently the highest of reported MOM materials, and this was further validated by the simulations performed herein. The simulations predict relatively constant Qst values for CO2 and CH4 sorption across all loadings in dia-7i-1-Co, consistent with the one type of binding site identified for the respective sorbate molecules in this MOM. Examination of the three-dimensional histogram showing the sites of CO2 and CH4 sorption in dia-7i-1-Co confirmed this finding. Inspection of the modeled structure revealed that the sorbate molecules form a strong interaction with the organic linkers within the constricted hydrophobic channels. Ideal adsorbed solution theory (IAST) calculations and GCMC binary mixture simulations predict that the selectivity of CO2 over CH4 in dia-7i-1-Co is quite low, which is a direct consequence of the MOM’s high affinity toward both CO2 and CH4 as well as the nonspecific mechanism shown here. This study provides theoretical insights into the effects of pore size on CO2 and CH4 sorption in porous MOMs and its effect upon selectivity, including postulating design strategies to distinguish between sorbates of similar size and hydrophobicity.

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Highly Selective CO₂ Uptake in Uninodal 6-Connected “mmo” Nets Based upon MO₄^2– (M = Cr, Mo) Pillars

Cited by 113 publications

References 61 publications

Low concentration CO2 capture using physical adsorbents: Are metal–organic frameworks becoming the new benchmark materials?

Low concentration CO2 capture using physical adsorbents: Are metal–organic frameworks becoming the new benchmark materials?

Hybrid Ultra‐Microporous Materials for Selective Xenon Adsorption and Separation

Theoretical Investigations of CO₂ and CH₄ Sorption in an Interpenetrated Diamondoid Metal–Organic Material

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Highly Selective CO2 Uptake in Uninodal 6-Connected “mmo” Nets Based upon MO42– (M = Cr, Mo) Pillars

Cited by 113 publications

References 61 publications

Low concentration CO2 capture using physical adsorbents: Are metal–organic frameworks becoming the new benchmark materials?

Low concentration CO2 capture using physical adsorbents: Are metal–organic frameworks becoming the new benchmark materials?

Hybrid Ultra‐Microporous Materials for Selective Xenon Adsorption and Separation

Theoretical Investigations of CO2 and CH4 Sorption in an Interpenetrated Diamondoid Metal–Organic Material

Contact Info

Product

Resources

About

Highly Selective CO₂ Uptake in Uninodal 6-Connected “mmo” Nets Based upon MO₄^2– (M = Cr, Mo) Pillars

Theoretical Investigations of CO₂ and CH₄ Sorption in an Interpenetrated Diamondoid Metal–Organic Material