Functionalizing porous zirconium terephthalate UiO-66(Zr) for natural gas upgrading: a computational exploration

Yang, Qingyuan; Wiersum, Andrew D.; Llewellyn, Philip L.; Guillerm, Vincent; Serre, Christian; Maurin, Guillaume

doi:10.1039/c1cc13543k

Cited by 349 publications

(342 citation statements)

References 25 publications

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“…The decreasing order of CO 2 uptake values at 25 bar is 2 > 1 = UiO-66 > 3. As predicted in a previous report by computational methodology, 47 the introduction of polar functional groups such as -CO 2 H and -SO 3 H in the UiO-66 framework enhances the CO 2 uptake values, in spite of the lower specific Langmuir surface areas of the functionalized compounds compared to the unfunctionalized UiO-66. In sharp contrast to the CO 2 uptake sequence, the CH 4 adsorption capacity of the compounds decreases in the order UiO-66 > 2 > 3 > 1.…”

Section: Gas Sorption Propertiesmentioning

confidence: 70%

“…This selectivity trend is also in agreement with the previously predicted sequence of CO 2 /CH 4 selectivity of the compounds. 47 It is noteworthy that similar or even higher CO 2 / CH 4 selectivity values have formerly been achieved by a variety of MOFs. 68,[71][72][73][74][75][76][77] In the previous theoretical study, 47 In order to determine the dynamic CO 2 /CH 4 adsorption selectivities of the UiO-66-X compounds, breakthrough experiments have been performed using equimolar mixtures of the two gases at 298 K. The methods for the breakthrough experiments and the corresponding curves (Fig.…”

Section: Gas Sorption Propertiesmentioning

confidence: 99%

“…21,[39][40][41][42][43][44][45][46] Especially, the amino-and the dimethyl-functionalized UiO-66 solids have shown improved CO 2 uptakes over the unfunctionalized material. 39,47 In an elaborate computational study, 47 the effect of organic functionalization on the CO 2 /CH 4 adsorption selectivity has been explored. The simulations suggested that the attachment of polar functional groups such as -SO 3 H and -CO 2 H to the UiO-66 framework would lead to improvement of both CO 2 adsorption capacity and CO 2 /CH 4 separation performance.…”

Section: Introductionmentioning

confidence: 99%

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Enhanced selectivity of CO2 over CH4 in sulphonate-, carboxylate- and iodo-functionalized UiO-66 frameworks

et al. 2013

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aThree new functionalized UiO-66-X (X = -SO 3 H, 1; -CO 2 H, 2; -I; 3) frameworks incorporating BDC-X (BDC: 1,4-benzenedicarboxylate) linkers have been synthesized by a solvothermal method using conventional electric heating. The as-synthesized (AS) as well as the thermally activated compounds were characterized by X-ray powder diffraction (XRPD), diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy, thermogravimetric (TG), and elemental analysis. The occluded H 2 BDC-X molecules can be removed by exchange with polar solvent molecules followed by thermal treatment under vacuum leading to the empty-pore forms of the title compounds. Thermogravimetric analysis (TGA) and temperature-dependent XRPD (TDXRPD) experiments indicate that 1, 2 and 3 are stable up to 260, 340 and 360°C, respectively. The compounds maintain their structural integrity in water, acetic acid and 1 M HCl, as verified by XRPD analysis of the samples recovered after suspending them in the respective liquids. As confirmed by N 2 , CO 2 and CH 4 sorption analyses, all of the thermally activated compounds exhibit significant microporosity (S Langmuir : 769-842 m 2 g −1 ), which are comparable to that of the parent UiO-66 compound. Compared to the unfunctionalized UiO-66 compound, all the three functionalized solids possess higher ideal selectivity in adsorption of CO 2 over CH 4 at 33°C.

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Section: Gas Sorption Propertiesmentioning

confidence: 70%

Section: Gas Sorption Propertiesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Enhanced selectivity of CO2 over CH4 in sulphonate-, carboxylate- and iodo-functionalized UiO-66 frameworks

et al. 2013

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“…Compared to traditional materials, they have advantages of low density, high specific area, and more tunable structures. Besides, they are synthesized under milder conditions, thus, MOFs have drawn much attention in recent years [7][8][9][10][11] and many researches [12][13][14][15][16][17][18][19][20][21][22] have been carried out to study the performance of MOFs. For example, we have studied the adsorption separation of CO2/N2, CO2/CH4, and CH4/N2 by ZIFs [5].…”

Section: Introductionmentioning

confidence: 99%

Molecular Simulation Studies of Flue Gas Purification by Bio-MOF

Zhi

Liu

et al. 2015

Energies

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Abstract:As a new branch of MOFs which are composed of biocompatible metal ions and organic ligands, bio-metal-organic frameworks (bio-MOFs) have attracted much attention recently. Bio-MOFs feature multiple Lewis basic sites which have strong interaction with CO2 molecules, thus they have great potential in the separation and purification of gas mixtures containing CO2. In this work, molecular simulation studies were carried out to investigate the adsorption and diffusion behaviors of CO2/N2 gas mixtures in bio-MOF-11. Results show that bio-MOF-11 displays excellent adsorption selectivity towards CO2 in CO2/N2 gas mixtures which was dominated by electrostatic interaction between material and CO2. In addition, we found both CO2 and N2 molecules were preferably adsorbed around the pyrimidine ring and exocyclic amino and transferred to the secondary favorable adsorption sites (methyl groups) with increasing pressure. Bio-MOF-11 membranes show superior permeation selectivity, but low permeability for CO2/N2 gas systems. The reason is that the small pores restrict the movement of gas molecules, leading to the observed low permeability. The information obtained in this work can be applied to other theoretical and experimental studies of bio-MOFs adsorbents and membranes in the future.

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“…This reverse shape selectivity might be attributed to the rotational freedom of the molecules within the small cages [14]. Hexane isomers adsorption might be modified by adjusting the dimensions of the windows through the introduction of different functional groups in substitution to one proton of the terephthalate linker, as already reported for the CO 2 adsorption over gases such as CH 4 and N 2 [15]. This selectivity increase could be related with the significant reduction of the ability to rotate of the aromatic ring upon the grafting of a -NH 2 group [16].…”

Section: Introductionmentioning

confidence: 87%

Hexane isomers sorption on a functionalized metal–organic framework

Mendes

Ragon

Rodrigues

et al. 2013

Microporous and Mesoporous Materials

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a b s t r a c tA series of functionalized porous Zr terephthalate MOFs of the UiO-66(Zr) structure type bearing either Br, NH 2 or NO 2 groups have been synthesized at the multi-gram scale through an atmospheric pressure solvothermal route with the final aim of investigating the influence of functionalization on the separation of hexane isomers (22DMB, 23DMB, 3MP and nHEX).The studies performed in a fixed bed adsorption column with equimolar mixtures at temperatures between 343 and 423 K and partial pressure up to 10 kPa have shown that the Br, NO 2 and NH 3 forms exhibit an uptake reaching 15%, being the sorption selectivity hierarchy on the whole comparable to the bared UiO-66 solid: 22DMB % 23DMB > 3MP ) nHEX. The 22DMB/nHEX selectivity reaches approximately three at low uptake while the 22DMB/3MP selectivity of UiO-66_NO 2 is nearly constant (1.3).

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Functionalizing porous zirconium terephthalate UiO-66(Zr) for natural gas upgrading: a computational exploration

Cited by 349 publications

References 25 publications

Enhanced selectivity of CO2 over CH4 in sulphonate-, carboxylate- and iodo-functionalized UiO-66 frameworks

Enhanced selectivity of CO2 over CH4 in sulphonate-, carboxylate- and iodo-functionalized UiO-66 frameworks

Molecular Simulation Studies of Flue Gas Purification by Bio-MOF

Hexane isomers sorption on a functionalized metal–organic framework

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