Noble Gas Adsorption in Copper Trimesate, HKUST-1: An Experimental and Computational Study

Hulvey, Zeric; Lawler, Keith V.; Qiao, Zhiwei; Jian, Zhou; Fairen‐Jimenez, David; Snurr, Randall Q.; Ushakov, Sergey V.; Navrotsky, Alexandra; Brown, Craig M.; Forster, Paul M.

doi:10.1021/jp408034u

Cited by 95 publications

(128 citation statements)

References 45 publications

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“…As Qst determines the associated temperature change of the adsorbent upon ad-/desorption, it is a key thermodynamic variable in the design of adsorption-based processes (53). Furthermore, the loading dependence of Qst often yields insights into the mechanism of adsorption and the structural characteristics of the material, e.g., adsorbate-adsorbate attractions (54), binding site preferences on heterogeneous surfaces (55), and structural transitions (56).…”

Section: Resultsmentioning

confidence: 99%

Statistical mechanical model of gas adsorption in porous crystals with dynamic moieties

Simon

Braun

Carraro

et al. 2017

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

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Some nanoporous, crystalline materials possess dynamic constituents, for example, rotatable moieties. These moieties can undergo a conformation change in response to the adsorption of guest molecules, which qualitatively impacts adsorption behavior. We pose and solve a statistical mechanical model of gas adsorption in a porous crystal whose cages share a common ligand that can adopt two distinct rotational conformations. Guest molecules incentivize the ligands to adopt a different rotational configuration than maintained in the empty host. Our model captures inflections, steps, and hysteresis that can arise in the adsorption isotherm as a signature of the rotating ligands. The insights disclosed by our simple model contribute a more intimate understanding of the response and consequence of rotating ligands integrated into porous materials to harness them for gas storage and separations, chemical sensing, drug delivery, catalysis, and nanoscale devices. Particularly, our model reveals design strategies to exploit these moving constituents and engineer improved adsorbents with intrinsic thermal management for pressure-swing adsorption processes.metal-organic frameworks | flexible metal-organic frameworks | statistical mechanics | porous materials | gas storage M etal-organic frameworks (MOFs) are porous, crystalline materials with very large internal surface areas (1). The consequent adsorption properties of MOFs have demonstrated promise toward solving paramount energy problems (2) such as in gas storage (3) and gas separations (4). MOFs are also being explored for chemical sensing (5), drug delivery (6), and catalysis (7). In the synthesis of MOFs, metal nodes or clusters and organic linker molecules self-assemble (8). Owing to their modular and versatile chemistry, tens of thousands of MOFs have been synthesized (9).Some MOFs are dynamic/flexible and respond to gas molecules adsorbing into their pores by exhibiting structural changes while retaining their crystallinity (reviews in refs. 10-14). Reported modes of guest-induced structural changes in MOFs include breathing (15), swelling (16), and subnetwork displacement (17), as well as less dramatic changes, such as the rotation of a ligand (18) or deformation (19). In molecular recognition and enzyme catalysis in biology, a conformation change of the enzyme is often involved in substrate binding (20,21). Responsive, dynamic constituents thus may endow MOFs with enzymelike selectivities (11) for selective gas adsorption, chemical sensing, and catalysis.In the long run, a more intimate understanding of MOFs with moving parts may enable the construction of molecular machines (22). Because of their crystallinity and tunability, MOFs are an ideal scaffold on which to organize machine subunits and tune their response to stimuli. Notably, Zhu et al. (23) used a [2] rotaxane molecular switch as a building block in a MOF to construct a conceptual molecular machine.Several reported MOFs possess dynamic constituents, e.g., bridging ligands that can rotate, while maintaini...

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Section: Resultsmentioning

confidence: 99%

Statistical mechanical model of gas adsorption in porous crystals with dynamic moieties

Simon

Braun

Carraro

et al. 2017

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

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“…Despite the importance of MOFs for noble gas storage and separation, only a few studies of krypton and xenon adsorption are reported to date [1][2][3][4][5][6][7][8][9][10][11][12] and only three studies of adsorption sites of noble gases in MOFs by means of X-ray or neutron diffraction, [13][14][15] despite the fact that the major adsorption sites and their binding energies are the key features of a material that determines its adsorption properties at a given temperature and pressure, and their identification is a basis for further modifications of the crystal structure of the MOF in order to achieve maximal storage capacity and selectivity. The study of noble gas adsorption in HKUST-1 15 revealed that the interaction of noble gases with MOFs can be completely different from the adsorption of other atoms and molecules like D 2 , C 2 H 2 , CO 2 , or CH 4 (methane is a nonpolar gas whose diameter and polarizability are similar to those of Kr). These molecules bind to the open metal sites, [16][17][18][19] while structural investigations did not show any evidence of the binding of noble gases Ne, Ar, Kr, and Xe to the open metal sites.…”

Section: Introductionmentioning

confidence: 99%

“…These molecules bind to the open metal sites, [16][17][18][19] while structural investigations did not show any evidence of the binding of noble gases Ne, Ar, Kr, and Xe to the open metal sites. 15 The metal-organic framework CPO-27 (MOF-74) was first synthesized in 2005 20 and is still one of the most interesting MOFs due to several unique characteristics: highest concentration of open metal sites reported to date for MOFs, 21 very high surface area, and uniform 1D channels. Another attractive property of CPO-27 is the existence of a series of isostructural MOFs obtained by replacement of the metal atom, thus providing the unique possibility to investigate the influence of different metal ions (M = Zn, Co, Ni, Mg, Mn, Fe, Cu, Zn/Co, Mg/Ni, Cd) for adsorption properties, [20][21][22][23][24][25][26][27][28][29][30] as well as the possibility to expand the pore apertures of CPO-27 to an isoreticular series with pore apertures ranging from 14 Å to 98 Å, 31 and diverse possibilities for postsynthetic functionalization.…”

Section: Introductionmentioning

confidence: 99%

Understanding the adsorption mechanism of noble gases Kr and Xe in CPO-27-Ni, CPO-27-Mg, and ZIF-8

Magdysyuk

Adams

Liermann³

et al. 2014

Phys. Chem. Chem. Phys.

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An experimental study of Xe and Kr adsorption in metal-organic frameworks CPO-27-Ni, CPO-27-Mg, and ZIF-8 was carried out. In situ synchrotron X-ray powder diffraction experiments allowed precise determination of the adsorption sites and sequence of their filling with increasing of gas pressure at different temperatures. Structural investigations were used for interpretation of gas adsorption measurements.

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“…This is in contrast to what was observed for other gases (e.g., H 2 , CO 2 ), where the adsorbate primary interaction site is the accessible unsaturated Cu(II) center. 27 …”

Section: Hkust-1 (Cu-btc Mof)mentioning

confidence: 99%

Potential of Metal–Organic Frameworks for Separation of Xenon and Krypton

et al. 2014

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* S Supporting Information CONSPECTUS: The total world energy demand is predicted to rise significantly over the next few decades, primarily driven by the continuous growth of the developing world. With rapid depletion of nonrenewable traditional fossil fuels, which currently account for almost 86% of the worldwide energy output, the search for viable alternative energy resources is becoming more important from a national security and economic development standpoint. Nuclear energy, an emission-free, high-energy-density source produced by means of controlled nuclear fission, is often considered as a clean, affordable alternative to fossil fuel. However, the successful installation of an efficient and economically viable industrial-scale process to properly sequester and mitigate the nuclear-fission-related, highly radioactive waste (e.g., used nuclear fuel (UNF)) is a prerequisite for any further development of nuclear energy in the near future. Reprocessing of UNF is often considered to be a logical way to minimize the volume of high-level radioactive waste, though the generation of volatile radionuclides during reprocessing raises a significant engineering challenge for its successful implementation. The volatile radionuclides include but are not limited to noble gases (predominately isotopes of Xe and Kr) and must be captured during the process to avoid being released into the environment. Currently, energy-intensive cryogenic distillation is the primary means to capture and separate radioactive noble gas isotopes during UNF reprocessing. A similar cryogenic process is implemented during commercial production of noble gases though removal from air. In light of their high commercial values, particularly in lighting and medical industries, and associated high production costs, alternate approaches for Xe/Kr capture and storage are of contemporary research interest. The proposed pathways for Xe/Kr removal and capture can essentially be divided in two categories: selective absorption by dissolution in solvents and physisorption on porous materials. Physisorption-based separation and adsorption on highly functional porous materials are promising alternatives to the energy-intensive cryogenic distillation process, where the adsorbents are characterized by high surface areas and thus high removal capacities and often can be chemically fine-tuned to enhance the adsorbate−adsorbent interactions for optimum selectivity. Several traditional porous adsorbents such as zeolites and activated carbon have been tested for noble gas capture but have shown low capacity, selectivity, and lack of modularity. Metal− organic frameworks (MOFs) or porous coordination polymers (PCPs) are an emerging class of solid-state adsorbents that can be tailor-made for applications ranging from gas adsorption and separation to catalysis and sensing. Herein we give a concise summary of the background and development of Xe/Kr separation technologies with a focus on UNF reprocessing and the prospects of MOF-based adsorbents for that particular appl...

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Noble Gas Adsorption in Copper Trimesate, HKUST-1: An Experimental and Computational Study

Cited by 95 publications

References 45 publications

Statistical mechanical model of gas adsorption in porous crystals with dynamic moieties

Statistical mechanical model of gas adsorption in porous crystals with dynamic moieties

Understanding the adsorption mechanism of noble gases Kr and Xe in CPO-27-Ni, CPO-27-Mg, and ZIF-8

Potential of Metal–Organic Frameworks for Separation of Xenon and Krypton

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