Separation of CO<sub>2</sub> from CH<sub>4</sub> Using Mixed-Ligand Metal−Organic Frameworks

Bae, Yang‐Seop; Mulfort, Karen L.; Frost, Helen; Ryan, P. E.; Punnathanam, Sudeep N.; Broadbelt, Linda J.; Hupp, Joseph T.; Snurr, Randall Q.

doi:10.1021/la800555x

Cited by 569 publications

(381 citation statements)

References 63 publications

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“…[7] In the last decade, metal-organic frameworks (MOFs) have attracted considerable attention for gas storage, separation processes, drug delivery, and catalysis. [8][9][10][11][12] The possibilities to tailor the pore size over a wide range and to include further functionalities in the framework render MOFs particularly interesting for catalytic applications. [13] However, the number of catalytic applications of MOFs is still quite limited.…”

Section: Introductionmentioning

confidence: 99%

Phosphotungstic Acid Encapsulated in Metal–Organic Framework as Catalysts for Carbohydrate Dehydration to 5‐Hydroxymethylfurfural

et al. 2010

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MIL‐101, a chromium‐based metal–organic framework, is known for its very large pore size, large surface area and good stability. However, applications of this material in catalysis are still limited. 5‐Hydroxymethylfurfural (HMF) has been considered a renewable chemical platform for the production of liquid fuels and fine chemicals. Phosphotungstic acid, H3PW12O40 (PTA), encapsulated in MIL‐101 is evaluated as a potential catalyst for the selective dehydration of fructose and glucose to 5‐hydroxymethylfurfural. The results demonstrate that PTA/MIL‐101 is effective for HMF production from fructose in DMSO and can be reused. This is the first example of the application of a metal–organic framework in carbohydrate dehydration.

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Section: Introductionmentioning

confidence: 99%

Phosphotungstic Acid Encapsulated in Metal–Organic Framework as Catalysts for Carbohydrate Dehydration to 5‐Hydroxymethylfurfural

et al. 2010

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“…3 Bae et al synthesized a mixed-ligand MOF, Zn 2 (NDC) 2 (DPNI) [NDC ϭ 2,6-naphthalenedicarboxylate, DPNI ϭ N,N=-di-(4-pyridyl)-1,4,5,8-naphthalene tetracarboxydiimide], and found that this material shows a selectivity of ϳ30 for CO 2 over CH 4 by using the ideal adsorbed solution theory (IAST). 6 Demessence et al synthesized an air-and water-stable MOF, H 3 [(Cu 4 Cl) 3 -(BTTri) 8 ] (H 3 BTTri ϭ1,3,5-tris(1H-1,2,3-triazol-5-yl)benzene). 13 Their results proved that the CO 2 uptakes of this material reach 142.56 mg/g at 298 K and 1 bar, while exhibiting significantly higher uptakes of CO 2 at even lower pressure after functionalized by ethylenediamine.…”

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Doping of Alkali, Alkaline-Earth, and Transition Metals in Covalent-Organic Frameworks for Enhancing CO₂ Capture by First-Principles Calculations and Molecular Simulations

et al. 2010

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We use the multiscale simulation approach, which combines the first-principles calculations and grand canonical Monte Carlo simulations, to comprehensively study the doping of a series of alkali (Li, Na, and K), alkaline-earth (Be, Mg, and Ca), and transition (Sc and Ti) metals in nanoporous covalent organic frameworks (COFs), and the effects of the doped metals on CO 2 capture. The results indicate that, among all the metals studied, Li, Sc, and Ti can bind with COFs stably, while Be, Mg, and Ca cannot, because the binding of Be, Mg, and Ca with COFs is very weak. Furthermore, Li, Sc, and Ti can improve the uptakes of CO 2 in COFs significantly. However, the binding energy of a CO 2 molecule with Sc and Ti exceeds the lower limit of chemisorptions and, thus, suffers from the difficulty of desorption. By the comparative studies above, it is found that Li is the best surface modifier of COFs for CO 2 capture among all the metals studied. Therefore, we further investigate the uptakes of CO 2 in the Lidoped COFs. Our simulation results show that at 298 K and 1 bar, the excess CO 2 uptakes of the Li-doped COF-102 and COF-105 reach 409 and 344 mg/g, which are about eight and four times those in the nondoped ones, respectively. As the pressure increases to 40 bar, the CO 2 uptakes of the Li-doped COF-102 and COF-105 reach 1349 and 2266 mg/g at 298 K, respectively, which are among the reported highest scores to date. In summary, doping of metals in porous COFs provides an efficient approach for enhancing CO 2 capture.

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“…The applicability of IAST to CO 2 / CH 4 separation in MOFs has indeed been validated in recent work by Snurr et al, by comparison with GCMC simulations of the adsorbed mixtures. 13 The method we propose here consists of combining the osmotic ensemble framework (eq 1) with IAST to predict the evolution of structural transitions upon adsorption of gas mixtures. Our theory is thus based exclusively on purecomponent adsorption isotherms.…”

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Prediction of Breathing and Gate-Opening Transitions Upon Binary Mixture Adsorption in Metal−Organic Frameworks

et al. 2009

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Among the numerous applications of metal-organic frameworks (MOFs), a topical class of nanoporous materials, adsorptive separation is gaining considerable attention. Some of the most exciting candidates for gas separation processes exhibit structural transitions, such as breathing and gate opening. While predictive analytical methods are crucial in separation science and have been widely used for rigid nanoporous solids, a lack exists for materials that exhibit flexibility. We propose here a general method predicting, for the first time, the evolution of structural transitions and selectivity upon adsorption of gas mixtures in flexible nanoporous solids.Porous metal-organic frameworks (MOFs) display an extremely large range of crystal structures. The combination of tunable porosity and chemistry of the internal surface opens the way to an extremely rich host-guest chemistry. Many applications have been proposed for MOF materials, including gas storage, catalysis, and sensing. In particular, adsorptive gas separation has seen a rapidly growing interest from the community. Indeed, compared to other classes of microporous materials currently used in gas separation processes (e.g., zeolites, activated carbons, and silica gels), MOFs show a great potential due to the wide possibilities of pre-or postsynthetic functionalization of the organic linker. For a very extensive review of gas adsorption and separation in MOFs, see ref 1.A particularly topical class of MOFs are the materials exhibiting a flexible (or dynamic) porous framework, which respond to pressure, temperature, or adsorption of guest molecules by changes in their structure. These systems have received a lot of focus and include materials displaying such eye-catching phenomena as gate opening 2,3 (transition from a closed, nonmicroporous phase to an open, porous phase), breathing 4 (two successive structural transitions) upon gas adsorption, and swelling with solvent adsorption. 5 These systems have been mainly studied from a structural point of view, and their behavior upon adsorption of various guests has been characterized, while simulations of their guest-induced response have only recently been reported. 6 While many authors have stated that flexible MOFs are good candidates for gas separation, it is to be noted that such predictions are usually based solely on looking at their pure-component adsorption isotherms. An example of direct measurements of adsorption selectivities for a gas mixture in flexible MOFs was provided recently by Denayer et al. on CO 2 /CH 4 separation in materials of the MIL-53 family, by means of breakthrough experiments.7,8 Because the parameter space for studies of binary or ternary mixture coadsorption in nanoporous solids is much bigger than that for pure-component adsorption, and especially so in materials that present multiple metastable structures, there is a strong need for a robust theoretical model to help guide the exploration of a large number of materials and working conditions (temperature, pressure, composition) t...

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Separation of CO₂ from CH₄ Using Mixed-Ligand Metal−Organic Frameworks

Cited by 569 publications

References 63 publications

Phosphotungstic Acid Encapsulated in Metal–Organic Framework as Catalysts for Carbohydrate Dehydration to 5‐Hydroxymethylfurfural

Phosphotungstic Acid Encapsulated in Metal–Organic Framework as Catalysts for Carbohydrate Dehydration to 5‐Hydroxymethylfurfural

Doping of Alkali, Alkaline-Earth, and Transition Metals in Covalent-Organic Frameworks for Enhancing CO₂ Capture by First-Principles Calculations and Molecular Simulations

Prediction of Breathing and Gate-Opening Transitions Upon Binary Mixture Adsorption in Metal−Organic Frameworks

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Separation of CO2 from CH4 Using Mixed-Ligand Metal−Organic Frameworks

Cited by 569 publications

References 63 publications

Phosphotungstic Acid Encapsulated in Metal–Organic Framework as Catalysts for Carbohydrate Dehydration to 5‐Hydroxymethylfurfural

Phosphotungstic Acid Encapsulated in Metal–Organic Framework as Catalysts for Carbohydrate Dehydration to 5‐Hydroxymethylfurfural

Doping of Alkali, Alkaline-Earth, and Transition Metals in Covalent-Organic Frameworks for Enhancing CO2 Capture by First-Principles Calculations and Molecular Simulations

Prediction of Breathing and Gate-Opening Transitions Upon Binary Mixture Adsorption in Metal−Organic Frameworks

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Separation of CO₂ from CH₄ Using Mixed-Ligand Metal−Organic Frameworks

Doping of Alkali, Alkaline-Earth, and Transition Metals in Covalent-Organic Frameworks for Enhancing CO₂ Capture by First-Principles Calculations and Molecular Simulations