Effects of Functionalization, Catenation, and Variation of the Metal Oxide and Organic Linking Units on the Low-Pressure Hydrogen Adsorption Properties of Metal−Organic Frameworks

Rowsell, Jesse L. C.; Yaghi, Omar M.

doi:10.1021/ja056639q

Cited by 1,764 publications

(1,318 citation statements)

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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

298

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

298

168

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“…However, an interpenetrated structure that increases the density of the framework together with a low pore volume yields a low uptake and total hydrogen capacity. The second highest adsorbate density observed belongs to IRMOF-20, a material with a high surface area (4024 m 2 g -1 ) [45] and pore volume, with micropores (1.4 and 1.73 nm) [45][46][47].…”

Section: Analysis and Discussionmentioning

confidence: 99%

Structure–property relationships in metal-organic frameworks for hydrogen storage

Noguera-Díaz

Bimbo

Holyfield

et al. 2016

Colloids and Surfaces A: Physicochemical and Engineering Aspect

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Experimental hydrogen isotherms on several metal-organic frameworks (IRMOF-1, IRMOF-3, IRMOF-9, ZIF-7, ZIF-8, ZIF-9, ZIF-11, ZIF-12, ZIF-CoNIm, MIL-101 (Cr), NH2-MIL-101 (Cr), NH2-MIL-101 (Al), UiO-66, UiO-67 and HKUST-1) synthesized in-house and measured at 77 K and pressures up to 18 MPa are presented, along with N2 adsorption characterization. The experimental isotherms together with literature high pressure hydrogen data were analysed in order to search for relationships between structural properties of the materials and their hydrogen uptakes. The total hydrogen capacity of the materials was calculated from the excess adsorption assuming a constant density for the adsorbed hydrogen. The surface area, pore volumes and pore sizes of the materials were related to their maximum hydrogen excess and total hydrogen capacities. Results also show that ZIF-7 and ZIF-9 (SOD topology) have unusual hydrogen isotherm shapes at relatively low pressures, which is indicative of "breathing", a phase transition in which the pore space increases due to adsorption. This work presents novel correlations using the modelled total hydrogen capacities of several MOFs. These capacities are more practically relevant for energy storage applications than the measured excess hydrogen capacities. Thus, these structural correlations will be advantageous for the prediction of the properties a MOF will need in order to meet the US Department of Energy targets for the mass and volume capacities of on-board storage systems. Such design tools will allow hydrogen to be used as an energy vector for sustainable mobile applications such as transport, or for providing supplementary power to the grid in times of high demand.

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“…1) (9). This material was found to have exceptional separation capacity for gases such as sulfur dioxide, ammonia, and ethylene oxide (10), and H 2 storage capacity (11). Subsequent to this initial discovery, a series of MOFs in which the 5-coordinate zinc(II) ions of MOF-74 are substituted for various divalent metal ions, including nickel, cobalt, manganese, and magnesium, has been described in various reports (12)(13)(14)(15).…”

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confidence: 99%

Highly efficient separation of carbon dioxide by a metal-organic framework replete with open metal sites

Britt

Furukawa

Wang

et al. 2009

Proc. Natl. Acad. Sci. U.S.A.

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1,060

730

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Selective capture of CO2, which is essential for natural gas purification and CO 2 sequestration, has been reported in zeolites, porous membranes, and amine solutions. However, all such systems require substantial energy input for release of captured CO2, leading to low energy efficiency and high cost. A new class of materials named metal-organic frameworks (MOFs) has also been demonstrated to take up voluminous amounts of CO 2. However, these studies have been largely limited to equilibrium uptake measurements, which are a poor predictor of separation ability, rather than the more industrially relevant kinetic (dynamic) capacity. Here carbon dioxide capture ͉ dynamic adsorption ͉ reticular chemistry S elective removal of CO 2 from gaseous mixtures is of paramount importance for the purification of fuel gases such as methane and acetylene and because of the imminent problem of anthropogenic CO 2 emissions. Effective systems for CO 2 removal must combine high selectivity and capacity with minimal energetic input to liberate the captured CO 2 . Materials presently used are amine solutions, zeolites, and porous membranes, but all fall short in one or more of these categories (1). To date, metal-organic frameworks (MOFs) have been shown to exhibit exceptional CO 2 storage capacity under equilibrium conditions where pure CO 2 is introduced into the pores (2-6). However, their capacities are dramatically reduced when exposed to mixtures of gases under dynamic conditions, as would be the case in power plant f lue gas and methane mining applications. A useful measure of dynamic separation capacity is obtained by exposing the material to mixed gas streams and detecting the appearance or ''breakthrough'' of CO 2 from the material. Here, we report that a MOF replete with open magnesium sites, Mg-MOF-74 [Mg 2 (DOT); DOT: 2,5-dioxidoterephthalate], has excellent selectivity, facile regeneration, and among the highest dynamic capacities reported for CO 2 in porous materials. Specifically, when Mg-MOF-74 is subjected to a gas stream containing 20% CO 2 in CH 4 , a percentage in the range relevant to industrial separations, it captures only CO 2 and not CH 4 . The pores retain 89 g of CO 2 per kilogram of material before breakthrough, a value higher than any other achieved in MOFs, and that rivals the highest capacities in zeolites. Remarkably, 87% of the captured CO 2 can be liberated at room temperature, and the remaining amount can be completely removed by mild heating (80°C). Based on this favorable performance, we assert that MOFs represent a competitive class of materials for efficient CO 2 capture, and that Mg-MOF-74 strikes the right balance between high capacity and heat of adsorption, notwithstanding the great opportunities available for functionalizing such MOFs for even further improved performance.In previous work, it has been shown that coordinatively unsaturated (open) metal sites in MOFs can be prepared by removal of coordinated solvent molecules (7,8). Whereas f lexible molecular or polymeric structures rearran...

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Effects of Functionalization, Catenation, and Variation of the Metal Oxide and Organic Linking Units on the Low-Pressure Hydrogen Adsorption Properties of Metal−Organic Frameworks

Cited by 1,764 publications

References 54 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?

Structure–property relationships in metal-organic frameworks for hydrogen storage

Highly efficient separation of carbon dioxide by a metal-organic framework replete with open metal sites

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