Adsorbed xenon propellant storage: are nanoporous materials worth the weight?
Nanoporous materials could be used to store xenon propellant onboard spacecraft.
36 MATERIALS SCIENCE↗
Engineering topics
Simon, Cory M.
Publications and source records attributed to Simon, Cory M..
Xenon Gas Separation and Storage using Metal-Organic Frameworks
The global demand for Xe, a noble gas with applications in electronics, lighting, and the medical industry, is expected to rise significantly over the coming decades. However, the low abundance of Xe in the earth’s atmosphere and the costly cryogenic distillation process that is used to obtain Xe commercially via air separation have limited the scale of applications of Xe. A physisorption-based separation using porous materials may be a viable and cost-effective alternative to cryogenic distillation. In particular, metal-organic frameworks (MOFs) have shown promise as highly Xe-selective, porous solids. In this review, we detail the recent advances of MOFs as adsorbents for noble gas adsorption/separation and the role of computer simulation in finding optimal materials for Xe adsorption.
MOFs, Xenon, Krypton↗
High-Throughput Computational Screening of Multivariate Metal–Organic Frameworks (MTV-MOFs) for CO 2 Capture
Multivariate metal–organic frameworks (MTV-MOFs) contain multiple linker types within a single structure. Arrangements of linkers containing different functional groups confer structural diversity and surface heterogeneity and result in a combinatorial explosion in the number of possible structures. Here, we carried out high-throughput computational screening of a large number of computer-generated MTV-MOFs to assess their CO 2 capture properties using grand canonical Monte Carlo simulations. The results demonstrate that functionalization enhances CO 2 capture performance of MTV-MOFs when compared to their parent (unfunctionalized) counterparts, and the pore size plays a dominant role in determining the CO 2 adsorption capabilities of MTV-MOFs irrespective of the combinations of the three functional groups (-F, -NH 2 , and -OCH 3 ) that we explored. We also found that the functionalization of parent MOFs with small pores led to larger enhancements in CO 2 uptake and CO 2 /N 2 selectivity than functionalization in larger-pore MOFs. Free energy contour maps are presented to visually compare the influence of linker functionalization between frameworks with large and small pores.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Materials Genome in Action: Identifying the Performance Limits of Physical Hydrogen Storage
Not Available
36 MATERIALS SCIENCE↗
Impact of the strength and spatial distribution of adsorption sites on methane deliverable capacity in nanoporous materials
The methane deliverable capacity of adsorbent materials is a critical performance metric that will determine the viability of using adsorbed natural gas (ANG) technology in vehicular applications. ARPA-E recently set a target deliverable capacity of 315 cc(STP)/cc that a viable adsorbent material should achieve to yield a driving range competitive with incumbent fuels. However, recent computational screening of hundreds of thousands of materials suggests that the target is unattainable. In this work, we aim to determine whether the observed limits in deliverable capacity (similar to 200 cc(STP)/cc) are fundamental limits arising from thermodynamic or material design constraints. Our efforts focus on simulating methane adsorption isotherms in a large number of systems, resulting in a broad exploration of different combinations of spatial distributions and energetics of adsorption sites. All systems were classified into five adsorption scenarios with varying degrees of realism in the manner that adsorption sites are created and endowed with energetics. The scenarios range from methane adsorption on discrete idealized lattice sites to adsorption in metal-organic frameworks with coordinatively unsaturated sites (CUS) provided by metalated catechol groups. Our findings strongly suggest that the ARPA-E target is unattainable, although not due to thermodynamic constraints but due to material design constraints. On the other hand, we also find that the currently observed deliverable capacity limits may be moderately surpassed. For instance, incorporation of CUS in IRMOF-10 is predicted to yield a 217 cc(STP)/cc deliverable capacity. The modified material has a similar to 0.85 void fraction and a heat of adsorption of similar to 15 kJ/mol. This suggests that similar, moderate improvements over existing materials could be achieved as long as CUS incorporation still maintains a relatively large void fraction. Nonetheless, we conclude that more significant improvements in deliverable capacity will require changes in the currently proposed operation conditions.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Adsorbate-induced lattice deformation in IRMOF-74 series
Here, IRMOF-74 analogues are among the most widely studied metal-organic frameworks (MOFs) for adsorption applications because of their one-dimensional channels and high metal density. Most studies involving the IRMOF-74 series assume that the crystal lattice is rigid. This assumption guides the interpretation of experimental data, as changes in the crystal symmetry have so far been ignored as a possibility in the literature. Here, we report a deformation pattern, induced by the adsorption of argon, for IRMOF-74-V. This work has two main implications. First, we use molecular simulations to demonstrate that the IRMOF-74 series undergoes a deformation that is similar to the mechanism behind breathing MOFs, but is unique because the deformation pattern extends beyond a single unit cell of the original structure. Second, we provide an alternative interpretation of experimental small-angle X-ray scattering profiles of these systems, which changes how we view the fundamentals of adsorption in this MOF series.
36 MATERIALS SCIENCE↗
Statistical mechanical model of gas adsorption in porous crystals with dynamic moieties
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. Here, 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.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Effect of ring rotation upon gas adsorption in SIFSIX-3-M (M = Fe, Ni) pillared square grid networks
The study of the mobility/rotation of the organic linkers in porous metal-organic frameworks could provide a valuable information about the guest/framework interaction and the factors control the kinetics of adsorption. Here, we analyzed the dynamics of pyrazine ring rotation in a series of pillared square grid frameworks, namely SIFSIX-3-M (M = Fe, Ni). It was found that the rotation of pyrazine ring is influenced by the variation of metal cation, temperature and the guest molecule. The Fe-analogue, [Fe(pz)2(SiF6)2] (pz= Pyrazine), , showed no pronounced ring rotation and exhibited a high affinity toward Xe gas over Kr as exemplified by the sharp Xe uptake at low loading (~0.1 bar) and its high isosteric heat of adsorption (Qst~ 27.4 kJmol-1) compared to the current benchmark materials. The Ni analogue, on the contrary, showed a two-regime adsorption isotherm for Xe with a temperature-dependent inflection point. However, this behavior is not observed with the other gases such as CO2, N2, and Kr which showed one-step adsorption isotherms without any inflection. Using molecular models and simulations, we hypothesize that the inflection point is due to a disordered to ordered transition of the rotational configurations of the pz rings in SIFSIX-3-Ni. These results further support the impact of tuning the pore size and chemistry on the adsorption behavior of porous materials.
Elsaidi, Sameh K.↗
Noria: A Highly Xe‐Selective Nanoporous Organic Solid
Abstract Separation of xenon and krypton is of industrial and environmental concern; the existing technologies use cryogenic distillation. Thus, a cost‐effective, alternative technology for the separation of Xe and Kr and their capture from air is of significant importance. Herein, we report the selective Xe uptake in a crystalline porous organic oligomeric molecule, noria, and its structural analogue, PgC‐noria, under ambient conditions. The selectivity of noria towards Xe arises from its tailored pore size and small cavities, which allows a directed non‐bonding interaction of Xe atoms with a large number of carbon atoms of the noria molecular wheel in a confined space.
Patil, Rahul S.↗
Metal–organic framework with optimally selective xenon adsorption and separation
Nuclear energy is considered among the most viable alternatives to our current fossil fuel based energy economy.1 The mass-deployment of nuclear energy as an emissions-free source requires the reprocessing of used nuclear fuel to mitigate the waste.2 One of the major concerns with reprocessing used nuclear fuel is the release of volatile radionuclides such as Xe and Kr. The most mature process for removing these radionuclides is energy- and capital-intensive cryogenic distillation. Alternatively, porous materials such as metal-organic frameworks (MOFs) have demonstrated the ability to selectively adsorb Xe and Kr at ambient conditions.3-8 High-throughput computational screening of large databases of porous materials has identified a calcium-based nanoporous MOF, SBMOF-1, as the most selective for Xe over Kr.9,10 Here, we affirm this prediction and report that SBMOF-1 exhibits by far the highest Xe adsorption capacity and a remarkable Xe/Kr selectivity under relevant nuclear reprocessing conditions. The exceptional selectivity of SBMOF-1 is attributed to its pore size tailored to Xe and its dense wall of atoms that constructs a binding site with a high affinity for Xe, as evident by single crystal X-ray diffraction and molecular simulation.
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
Computer-Aided Search for Materials to Store Natural Gas for Vehicles
Most cars use gasoline as a fuel. But cars can run on other fuels, such as natural gas (NG), the same gas that is used for cooking and for heating our homes. NG is cheaper and possibly better for the environment than gasoline. However, gasoline is much more dense than NG since gasoline is a liquid and NG is a gas. So, to run a car on NG, we need to increase its density so that we can fit enough NG in the fuel tank to drive a similar distance as with a tank of gasoline. Researchers around the world are working on synthesizing materials that act as sponges that adsorb NG. By putting these sponge-like materials inside of the fuel tank, we can increase the density of NG to efficiently store it onboard the vehicle. In our study, we show that how computers can be used to search for the most promising sponge-like materials to store NG.
03 NATURAL GAS↗
What Are the Best Materials To Separate a Xenon/Krypton Mixture?
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membrane, carbon capture, materials and chemistry ↗
The materials genome in action: identifying the performance limits for methane storage
Analogous to the way the Human Genome Project advanced an array of biological sciences by mapping the human genome, the Materials Genome Initiative aims to enhance our understanding of the fundamentals of materials science by providing the information we need to accelerate the development of new materials. This approach is particularly applicable to recently developed classes of nanoporous materials, such as metal–organic frameworks (MOFs), which are synthesized from a limited set of molecular building blocks that can be combined to generate a very large number of different structures. In this Perspective, we describe how a materials genome approach can be used to search for high-performance adsorbent materials to store natural gas in a vehicular fuel tank. Drawing upon recent reports of large databases of existing and predicted nanoporous materials generated in silico , we have collected and compared on a consistent basis the methane uptake in over 650 000 materials based on the results of molecular simulation. The data that we have collected provide candidate structures for synthesis, reveal relationships between structural characteristics and performance, and suggest that it may be difficult to reach the current Advanced Research Project Agency-Energy (ARPA-E) target for natural gas storage.
03 NATURAL GAS↗
Kinetically tuned dimensional augmentation as a versatile synthetic route towards robust metal–organic frameworks
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membrane, carbon capture, materials and chemistry ↗
Optimizing nanoporous materials for gas storage
In this work, we address the question of which thermodynamic factors determine the deliverable capacity of methane in nanoporous materials. The deliverable capacity is one of the key factors that determines the performance of a material for methane storage in automotive fuel tanks. To obtain insights in how the molecular characteristics of a material are related to this deliverable capacity, we developed several statistical thermodynamic models. The predictions of these models are compared with the classical thermodynamics approach of Bhatia and Myers [Bhatia and Myers Langmuir, 2005, 22, 1688] and with the results of molecular simulations in which we screen the IZA zeolite structures and a hypothetical zeolite database of over 100,000 structures. Both the simulations and our models do not support the rule of thumb that, for methane storage, one should aim for an optimal heat of adsorption of 18.8 kJ/mol -1 . Instead, our models show that one can identify an optimal heat of adsorption, but that this optimal heat of adsorption depends on the structure of the material. The different models we have developed are aimed to provide guidelines on how this optimal heat of adsorption is related to the molecular structure of the material.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Modeling Methane Adsorption in Interpenetrating Porous Polymer Networks
Porous polymer networks (PPNs) are a class of porous materials of particular interest in a variety of energy-related applications because of their stability, high surface areas, and gas uptake capacities. Computationally derived structures for five recently synthesized PPN frameworks, PPN-2, -3, -4, -5, and -6, were generated for various topologies, optimized using semiempirical electronic structure methods, and evaluated using classical grand canonical Monte Carlo simulations. We show that a key factor in modeling the methane uptake performance of these materials is whether, and how, these material frameworks interpenetrate and demonstrate a computational approach for predicting the presence, degree, and nature of interpenetration in PPNs that enables the reproduction of experimental adsorption data.
Martin, RL↗