Framework-Topology-Controlled Singlet Fission in Metal-Organic Frameworks.

Singlet fission (SF) has been explored as a viable route to improve photovoltaic performance by producing more excitons. Efficient SF is achieved through a high degree of interchromophoric coupling that facilitates electron superexchange to generate triplet pairs. However, strongly coupled chromophores often form excimers that can serve as an SF intermediate or a low-energy trap site. The succeeding decoherence process, however, requires an optimum electronic coupling to facilitate the isolation of triplet production from the initially prepared correlated triplet pair. Conformational flexibility and dielectric modulation can provide a means to tune the SF mechanism and efficiency by modulating the interchromophoric electronic interaction. Such a strategy cannot be easily adopted in densely stacked traditional organic solids. Here, we show that the assembly of the SF-active chromophores around well-defined pores of solution-stable metal-organic frameworks (MOFs) can be a great platform for a modular SF process. A series of three new MOFs, built out from 9,10-bis(ethynylenephenyl)anthracene-derived struts, show a topology-defined packing density and conformational flexibility of the anthracene core to dictate the SF mechanism. Various steady-state and transient spectroscopic data suggest that the initially prepared singlet population can prefer either an excimer-mediated SF or a direct SF (both through a virtual charge-transfer (CT) state). These solution-stable frameworks offer the tunability of the dielectric environment to facilitate the SF process by stabilizing the CT state. Given that MOFs are a great platform for various photophysical and photochemical developments, generating a large population of long-lived triplets can expand their utilities in various photon energy conversion schemes.

Deep learning combined with IAST to screen thermodynamically feasible MOFs for adsorption-based separation of multiple binary mixtures.

The structures of metal-organic frameworks (MOFs) can be tuned to reproducibly create adsorption properties that enable the use of these materials in fixed-adsorption beds for non-thermal separations. However, with millions of possible MOF structures, the challenge is to find the MOF with the best adsorption properties to separate a given mixture. Thus, computational, rather than experimental, screening is necessary to identify promising MOF structures that merit further examination, a process traditionally done using molecular simulation. However, even molecular simulation can become intractable when screening an expansive MOF database for their separation properties at more than a few composition, temperature, and pressure combinations. Here, we illustrate progress toward an alternative computational framework that can efficiently identify the highest-performing MOFs for separating various gas mixtures at a variety of conditions and at a fraction of the computational cost of molecular simulation. This framework uses a "multipurpose" multilayer perceptron (MLP) model that can predict single component adsorption of various small adsorbates, which, upon coupling with ideal adsorbed solution theory (IAST), can predict binary adsorption for mixtures such as Xe/Kr, CH4/CH6, N2/CH4, and Ar/Kr at multiple compositions and pressures. For this MLP+IAST framework to work with sufficient accuracy, we found it critical for the MLP to make accurate predictions at low pressures (0.01-0.1 bar). After training a model with this capability, we found that MOFs in the 95th and 90th percentiles of separation performance determined from MLP+IAST calculations were 65% and 87%, respectively, the same as MOFs in the simulation-predicted 95th percentile across several mixtures at diverse conditions (on average). After validating our MLP+IAST framework, we used a clustering algorithm to identify "privileged" MOFs that are high performing for multiple separations at multiple conditions. As an example, we focused on MOFs that were high performing for the industrially relevant separations 80/20 Xe/Kr at 1 bar and 80/20 N2/CH4 at 5 bars. Finally, we used the MOF free energies (calculated on our entire database) to identify privileged MOFs that were also likely synthetically accessible, at least from a thermodynamic perspective.

Improving Energy Transfer within Metal-Organic Frameworks by Aligning Linker Transition Dipoles along the Framework Axis.

Crystalline metal-organic frameworks (MOFs) can assemble chromophoric molecules into a wide range of spatial arrangements, which are controlled by the MOF topology. Like natural light-harvesting complexes (LHCs), the precise arrangement modulates interchromophoric interactions, in turn determining excitonic behavior and migration dynamics. To unveil the key factors that control efficient exciton displacements within MOFs, we first developed linkers with low electronic symmetry (as defined by large transition dipoles) and then assembled them into MOFs. These linkers possess extended conjugation along one molecular axis, engendering low optical bandgaps and improved oscillator strength for their lowest-energy transition (S0 → S1). This enhances absorption-emission spectral overlap and boosts the efficiency of Förster resonance energy transfer, which was observed experimentally by a sizable decrease in emission quantum yield (QY), accompanied by a faster population decay profile. We find that MOFs that orient these elongated linkers along their asymmetric pore channel, e.g., the hexagonal pores in an xly network, manifested >50% decrease in their emission QY with faster decay profiles relative to their corresponding solution dissolved linkers. This is due to an efficient migration of photogenerated excitons at the crystallite peripheral sites to internal sites, which was facilitated by polarized absorption-emission overlap among the parallelly aligned linkers. In contrast, symmetric MOFs, such as those with sqc-a topological net, orient elongated linkers along two perpendicular crystal axes, which hinders efficient exciton migration. The present study underscores that MOFs are promising to develop artificial LHCs, but that to achieve an efficient exciton displacement, appropriate topology-guided assembly is required to fully realize the true potential of linkers with low electronic symmetry.

Electronic effects due to organic linker-metal surface interactions: implications on screening of MOF-encapsulated catalysts.

MOF-encapsulated nanoparticles (NP@MOFs) are hybrid, heterogeneous catalysts, where the MOF could boost the activity and selectivity of the encapsulated NP for the reaction of choice by controlling reactant orientation. However, due to overwhelming combinatorics, methods to rapidly identify promising NP + MOF combinations for a given application are needed. Earlier work used a "surrogate" inert pore on top of NP-representative surfaces to generically capture MOF steric effects, hence enabling computational screening to focus on NP composition. However, the surrogate pore method neglects electronic effects of the MOF on the NP. Here, we use density functional theory to study how paradigmatic MOF linkers (imidazolate, carboxylate, and thiolate) impact the electronic structure of representative metal surfaces, and in turn the binding of small species, whose formation energies are commonly used in descriptor-based catalyst screening. We find that the coordinating moiety and functionalization of the linker modulates the shift in the metal d-band center and the electron transfer, which is correlated to experimentally measurable quantities such as C-O vibration frequencies. However, in the majority of cases, the effect of the linker on binding energies (for C*, O*, N*, H*, OH*, CH3* and CO*) was less than 10 kJ mol-1. Furthermore, scaling relationships between binding energies were only slightly affected by linker-originated electronic effects. Therefore, activity/selectivity "heat maps" derived from calculations under "generic" steric constrains could remain useful to screen the optimal NP composition of an NP@MOF catalyst. On the other hand, the placement of a given NP composition on the aforementioned heat maps is affected by the MOF. For an n-butane oxidation case study, we estimated that Ag3Pd-a promising NP composition for selective 1-butanol formation according to previous screenings using the surrogate pore method-has a ∼85% probability of retaining a selectivity for 1-butanol above 75% when encapsulated in a carboxylic MOF of suitable pore size.

Framework-Topology-Dependent Catalytic Activity of Zirconium-Based (Porphinato)zinc(II) MOFs.

Catalytic activity for acyl transfer from N-acetylimidazole (NAI) to different pyridylcarbinol (PC) regioisomers (2-PC, 3-PC, and 4-PC) is demonstrated for a set of topologically diverse, zirconium-based (porphinato)zinc metal-organic frameworks (MOFs). The MOFs studied are PCN-222, MOF-525, and NU-902, which are based on the csq, ftw, and scu topologies, respectively. The experimentally obtained reaction kinetics are discussed in light of molecular modeling results. The catalytic activity is shown to vary across the series of MOFs due to the different extent to which each topology facilitates reactant preconcentration and alignment of PC and NAI via coordination to framework porphyrin sites (orientation effects). Trends of experimental initial reaction rates with MOF topology and PC regioisomer are consistent with preconcentration effects, which depend on the number of porphyrin sites per volume of MOF, as well as with orientation effects, which depend on the number of porphyrin pairs per volume of MOF that bind PC and NAI in such a way that they are primed to form the required transition state. The present work shows how the proper alignment of catalytic linkers can enhance reaction rates in MOFs.

Application of Consistency Criteria To Calculate BET Areas of Micro- And Mesoporous Metal-Organic Frameworks.

Metal-organic frameworks (MOFs) can exhibit exceptionally high surface areas, which are experimentally estimated by applying the BET theory to measured nitrogen isotherms. The Brunauer, Emmett, and Teller (BET)-estimated nitrogen monolayer loading is thus converted to a "BET area," but the meaning of MOF BET areas remains under debate. Recent emphasis has been placed on the usage of four so-called "BET consistency criteria." Using these criteria and simulated nitrogen isotherms for perfect crystals, we calculated BET areas for graphene and 25 MOFs having different pore-size distributions. BET areas were compared with their corresponding geometrically calculated, nitrogen-accessible surface areas (NASAs). Analysis of simulation snapshots elucidated the contributions of "pore-filling" and "monolayer-formation" to the nitrogen adsorption loadings in different MOF pores, revealing the origin of inaccuracies in BET-calculated monolayer loadings, which largely explain discrepancies between BET areas and NASAs. We also find that even if all consistency criteria are satisfied, the BET calculation can significantly overestimate the true monolayer loading, especially in MOFs combining mesopores (d ≥ 20 Å) and large micropores (d = 10-20 Å), due to the overlap of pore-filling and monolayer-formation regimes of these two kinds of pores. While it is not always possible to satisfy all consistency criteria, it is critical to minimize the deviation from these criteria during BET range selection to consistently compare BET areas of different MOFs and for comparing simulated and experimental BET areas of a given MOF. To accurately assess the quality of a MOF sample, it is best to compare experimental BET areas with simulated BET areas rather than with calculated NASAs.

Ultraporous, Water Stable, and Breathing Zirconium-Based Metal-Organic Frameworks with ftw Topology.

"Breathing" metal-organic frameworks (MOFs) are an emerging class of soft porous crystals (SPCs) with potential for high working capacity for gas storage applications. However, most breathing MOFs have low stability and/or low surface area. Here we report a water-stable, high surface area, breathing MOF of ftw topology, NU-1105. While Zr6-oxo clusters as nodes introduce water stability in NU-1105, its high surface area and breathing character stem from its pyrene-based tetracarboxylate (Py-FP) linkers, in which the fluorene units (F) in the FP "arms" play a key role in promoting breathing behavior. During gas sorption studies, the "closed pore" (cp) ↔ "open pore" (op) transition of NU-1105 occurs at a propane pressure of ∼3 bar. At 1 bar, NU-1105 is in its cp form and adsorbs less propane than it would in its op form, highlighting improved working capacity. In situ powder X-ray diffraction during propane sorption was used to track the cp ↔ op transition, and molecular modeling was used to elucidate the structure of the op and cp forms of NU-1105. According to TD-DFT calculations, the proposed conformations of the Py-FP linkers in the op and cp forms are consistent with the measured excitation and emission spectra of the op and cp forms of NU-1105. Similar structural transitions are also observed in the porphyrinic MOF NU-1104 depending on the identity of the porphyrin core; we observed breathing behavior if the constituent Por-PTP linker is nonmetalated.

Ultrahigh surface area zirconium MOFs and insights into the applicability of the BET theory.

An isoreticular series of metal-organic frameworks (MOFs) with the ftw topology based on zirconium oxoclusters and tetracarboxylate linkers with a planar core (NU-1101 through NU-1104) has been synthesized employing a linker expansion approach. In this series, NU-1103 has a pore volume of 2.91 cc g(-1) and a geometrically calculated surface area of 5646 m(2) g(-1), which is the highest value reported to date for a zirconium-based MOF and among the largest that have been reported for any porous material. Successful activation of the MOFs was proven based on the agreement of pore volumes and BET areas obtained from simulated and experimental isotherms. Critical for practical applications, NU-1103 combines for the first time ultrahigh surface area and water stability, where this material retained complete structural integrity after soaking in water. Pressure range selection for the BET calculations on these materials was guided by the four so-called "consistency criteria". The experimental BET area of NU-1103 was 6550 m(2) g(-1). Insights obtained from molecular simulation suggest that, as a consequence of pore-filling contamination, the BET method overestimates the monolayer loading of NU-1103 by ∼16%.

A modelling approach for MOF-encapsulated metal catalysts and application to n-butane oxidation.

Metal nanoparticles (NP) encapsulated by metal-organic frameworks (MOFs) are novel composite materials that have shown promise as regioselective catalysts. The regioselectivity in these materials arises from steric constraints imposed by the porous MOF structure, which limit the way molecules approach and interact with the metal surface. Here we introduce a conceptually simple DFT approach to model reactions under such steric constraints. This approach is computationally efficient and accounts for the steric constraints imposed by a MOF pore in a general way. The adsorption of reactants, intermediates, and products associated with oxidation of n-butane to 1-butanol (and 2-butanol) on clean and oxygen-covered palladium surfaces is investigated with (and without) the constraints of a pore. Reaction energies are calculated, and we find that the thermodynamic favorability of the intermediate reactions is affected by the presence of steric constraints, oxygen coverage, and the exposed crystal surface of the metal. Based on these results, the Pd(111) surface with 0.25 ML oxygen coverage and steric constraints (which could be provided by a suitable MOF) seems promising to favor the desired sequence of reactions that would lead to the conversion of n-butane to 1-butanol.

Water-stable zirconium-based metal-organic framework material with high-surface area and gas-storage capacities.

We designed, synthesized, and characterized a new Zr-based metal-organic framework material, NU-1100, with a pore volume of 1.53 ccg(-1) and Brunauer-Emmett-Teller (BET) surface area of 4020 m(2) g(-1) ; to our knowledge, currently the highest published for Zr-based MOFs. CH4 /CO2 /H2 adsorption isotherms were obtained over a broad range of pressures and temperatures and are in excellent agreement with the computational predictions. The total hydrogen adsorption at 65 bar and 77 K is 0.092 g g(-1) , which corresponds to 43 g L(-1) . The volumetric and gravimetric methane-storage capacities at 65 bar and 298 K are approximately 180 vSTP /v and 0.27 g g(-1) , respectively.

Metal-Carbodithioate-Based 3D Semiconducting Metal-Organic Framework: Porous Optoelectronic Material for Energy Conversion.

Solar energy conversion requires the working compositions to generate photoinduced charges with high potential and the ability to deliver charges to the catalytic sites and/or external electrode. These two properties are typically at odds with each other and call for new molecular materials with sufficient conjugation to improve charge conductivity but not as much conjugation as to overly compromise the optical band gap. In this work, we developed a semiconducting metal-organic framework (MOF) prepared explicitly through metal-carbodithioate "(-CS2)nM" linkage chemistry, entailing augmented metal-linker electronic communication. The stronger ligand field and higher covalent character of metal-carbodithioate linkages─when combined with spirofluorene-derived organic struts and nickel(II) ion-based nodes─provided a stable, semiconducting 3D-porous MOF, Spiro-CS2Ni. This MOF lacks long-range ordering and is defined by a flexible structure with non-aggregated building units, as suggested by reverse Monte Carlo simulations of the pair distribution function obtained from total scattering experiments. The solvent-removed "closed pore" material recorded a Brunauer-Emmett-Teller area of ∼400 m2/g, where the "open pore" form possesses 90 wt % solvent-accessible porosity. Electrochemical measurements suggest that Spiro-CS2Ni possesses a band gap of 1.57 eV (σ = 10-7 S/cm at -1.3 V bias potential), which can be further improved by manipulating the d-electron configuration through an axial coordination (ligand/substrate), the latter of which indicates usefulness as an electrocatalyst and/or a photoelectrocatalyst (upon substrate binding). Transient-absorption spectroscopy reveals a long-lived photo-generated charge-transfer state (τCR = 6.5 µs) capable of chemical transformation under a biased voltage. Spiro-CS2Ni can endure a compelling range of pH (1-12 for weeks) and hours of electrochemical and photoelectrochemical conditions in the presence of water and organic acids. We believe this work provides crucial design principles for low-density, porous, light-energy-conversion materials.

Nanocatalyst structure as a template to define chirality of nascent single-walled carbon nanotubes.

Chirality is a crucial factor in a single-walled carbon nanotube (SWCNT) because it determines its optical and electronic properties. A chiral angle spanning from 0° to 30° results from twisting of the graphene sheet conforming the nanotube wall and is equivalently expressed by chiral indexes (n,m). However, lack of chirality control during SWCNT synthesis is an obstacle for a widespread use of these materials. Here we use first-principles density functional theory (DFT) and classical molecular dynamics (MD) simulations to propose and illustrate basic concepts supporting that the nanocatalyst structure may act as a template to control the chirality during nanotube synthesis. DFT optimizations of metal cluster (Co and Cu)∕cap systems for caps of various chiralities are used to show that an inverse template effect from the nascent carbon nanostructure over the catalyst may exist in floating catalysts; such effect determines a negligible chirality control. Classical MD simulations are used to investigate the influence of a strongly interacting substrate on the structure of a metal nanocatalyst and illustrate how such interaction may help preserve catalyst crystallinity. Finally, DFT optimizations of carbon structures on stepped (211) and (321) cobalt surfaces are used to demonstrate the template effect imparted by the nanocatalyst surface on the growing carbon structure at early stages of nucleation. It is found that depending on the step structure and type of building block (short chains, single atoms, or hexagonal rings), thermodynamics favor armchair or zigzag termination, which provides guidelines for a chirality controlled process based on tuning the catalyst structure and the type of precursor gas.

Adsorption Isotherm Predictions for Multiple Molecules in MOFs Using the Same Deep Learning Model.

Tailoring the structure and chemistry of metal-organic frameworks (MOFs) enables the manipulation of their adsorption properties to suit specific energy and environmental applications. As there are millions of possible MOFs (with tens of thousands already synthesized), molecular simulation has frequently been used to rapidly evaluate the adsorption performance of a large set of MOFs. This allows subsequent experiments to focus only on a small subset of the most promising MOFs. In many instances, however, even molecular simulation becomes prohibitively time-consuming, underscoring the need for alternative screening methods, such as machine learning, to precede molecular simulation efforts. In this study, as a proof of concept, we trained a neural network-specifically, a multilayer perceptron (MLP)-as the first example of a machine learning model capable of predicting full adsorption isotherms of different molecules not included in the training of the model. To achieve this, we trained our MLP on "alchemical" species, represented only by variables derived from their force-field parameters, to predict the loadings of real adsorbates. Alchemical species used for training were small, near-spherical, and nonpolar, enabling the prediction of analogous real molecules relevant for chemical separations such as argon, krypton, xenon, methane, ethane, and nitrogen. MOFs were also represented by simple descriptors (e.g., geometric properties and chemical moieties). The trained model was shown to make accurate adsorption predictions for these six adsorbates in both hypothetical and existing MOFs. The MLP presented here is not expected to be applied "as is" to more complex adsorbates with properties not considered during its training. However, our results illustrate a new philosophy of training that can be built upon with the goal of predicting adsorption isotherms in not only a database of MOFs but also a database of adsorbates and over a range of relevant operating conditions.

Balancing volumetric and gravimetric uptake in highly porous materials for clean energy.

A huge challenge facing scientists is the development of adsorbent materials that exhibit ultrahigh porosity but maintain balance between gravimetric and volumetric surface areas for the onboard storage of hydrogen and methane gas-alternatives to conventional fossil fuels. Here we report the simulation-motivated synthesis of ultraporous metal-organic frameworks (MOFs) based on metal trinuclear clusters, namely, NU-1501-M (M = Al or Fe). Relative to other ultraporous MOFs, NU-1501-Al exhibits concurrently a high gravimetric Brunauer-Emmett-Teller (BET) area of 7310 m2 g-1 and a volumetric BET area of 2060 m2 cm-3 while satisfying the four BET consistency criteria. The high porosity and surface area of this MOF yielded impressive gravimetric and volumetric storage performances for hydrogen and methane: NU-1501-Al surpasses the gravimetric methane storage U.S. Department of Energy target (0.5 g g-1) with an uptake of 0.66 g g-1 [262 cm3 (standard temperature and pressure, STP) cm-3] at 100 bar/270 K and a 5- to 100-bar working capacity of 0.60 g g-1 [238 cm3 (STP) cm-3] at 270 K; it also shows one of the best deliverable hydrogen capacities (14.0 weight %, 46.2 g liter-1) under a combined temperature and pressure swing (77 K/100 bar → 160 K/5 bar).

Growth of chiral single-walled carbon nanotube caps in the presence of a cobalt cluster.

Density functional theory is used to simulate nanotube growth by addition of a pair of carbon atoms to a composite chiral nanotube cap/cobalt cluster system, with caps corresponding to near-armchair (6, 5), (7, 5) and near-zigzag (9, 1) nanotubes. Two different carbon addition processes are evaluated: in the first, the new carbon atoms are located in the vicinity of the armchair site of the cap rim, and thus this process provides insight into the root-growth mechanism; in the second the carbon atoms are initially located under the cobalt cluster, and thus this process helps one to evaluate the dissolution of carbon inside the metal cluster. The geometric evolution and energetics of the system are used to explain features of the mechanism of nanotube growth. The root-growth reaction is shown to occur by displacement of a cobalt atom initially interacting with the armchair site while the added carbon atoms bond to each other forming a new hexagonal ring, whereas the carbon dissolution process shows formation of dimers inside the cluster only for the (6, 5) system. The energetics for both steps reveals that the dissolution stage is probably controlling the overall nanotube growth rate.

Modular Synthesis of Highly Porous Zr-MOFs Assembled from Simple Building Blocks for Oxygen Storage.

The last decade has witnessed significant advances in the scale-up synthesis of metal-organic frameworks (MOFs) using commercially available and affordable organic linkers. However, the synthesis of MOFs using elongated and/or multitopic linkers to access MOFs with large pore volume and/or various topologies can often be challenging due to multistep organic syntheses involved for linker preparation. In this report, a modular MOF synthesis strategy is developed by utilizing the coordination and covalent bonds formation in one-pot strategy where monoacid-based ligands reacted to form ditopic ligands, which then assembled into a three-dimensional MOF with Zr6 clusters. Chemical stability of the resulting materials was significantly enhanced through converting the imine bond into robust linkage via cycloaddition with phenylacetylene. Oxygen storage capacities of the MOFs were measured, and enhanced volumetric O2 uptake was observed for the stabilized MOF, NU-401-Q.

Molecular dynamics simulations of H2 adsorption in tetramethyl ammonium lithium phthalocyanine crystalline structures.

Tetramethyl ammonium lithium phthalocyanine is explored as a potential material for storage of molecular hydrogen. Density functional theory calculations are used to investigate the molecular structure and the dimer conformation. Additional scans performed to determine the interactions of a H2 molecule located at various distances from the molecular sites are used to generate a simple force field including dipole-induced-dipole interactions. This force field is employed in molecular dynamics simulations to calculate adsorption isotherms at various pressures. The regions of strongest adsorption are quantified as functions of temperature, pressure, and separation between molecules in the adsorbent phase, and compared to the regions of strongest binding energy as given by the proposed force field. It is found that the total adsorption could not be predicted only from the spatial distribution of the strongest binding energies; the available volume is the other contributing factor even if the volume includes regions of much lower binding energy. The results suggest that the complex anion is primarily involved in the adsorption process with molecular hydrogen, whereas the cation serves to provide access for hydrogen adsorption in both sides of the anion molecular plane, and spacing between the planes.

Molecular Simulation Insights on Xe/Kr Separation in a Set of Nanoporous Crystalline Membranes.

Separation of xenon and krypton is highly relevant to several applications such as spent nuclear fuel processing. Molecular simulation has been extensively used to understand the Kr/Xe separation performance of nanoporous materials for adsorption-based technologies but less frequently for membrane-based technologies. Motivated by recent experimental reports on krypton-selective membranes, herein, we present grand canonical Monte Carlo and biased molecular dynamics simulations (using adaptive biasing force) to elucidate the nature of adsorption- and diffusion-based Kr/Xe separation mechanisms in a set of nanoporous materials: SAPO-34, ZIF-8, UiO-66, and IRMOF-1. Xenon is found to preferentially adsorb on all materials, but diffusion selectivity for krypton is found to dominate the overall membrane separation selectivity. To increase adsorption selectivity for krypton, large pore cages are found to be desirable. To increase diffusion selectivity for krypton, stiff pore windows with a diameter smaller than xenon (but larger than krypton) are found to be desirable. No perfect molecular sieving was found, but the relatively rigid SAPO-34 was more effective at excluding xenon than the more flexible ZIF-8. Indeed, during xenon "window crossing," the SAPO-34 window opened to only 3.8 Å, while the ZIF-8 window opened to 4.1 Å, resulting in a lower free energy "diffusion" barrier for xenon in ZIF-8. Therefore, an ideal membrane material for Kr/Xe separation should be rigid and have large pore cages and small pore windows. Temperature was found to have opposite effects on adsorption and diffusion selectivity, but because of the dominance of diffusion selectivity, our simulations indicate that it is preferable to operate membranes for Kr/Xe separation at lower temperatures than at higher ones.

Molecular Building Block-Based Electronic Charges for High-Throughput Screening of Metal-Organic Frameworks for Adsorption Applications.

Metal-organic frameworks (MOFs) are porous crystalline materials with attractive properties for gas separation and storage. Their remarkable tunability makes it possible to create millions of MOF variations but creates the need for fast material screening to identify promising structures. Computational high-throughput screening (HTS) is a possible solution, but its usefulness is tied to accurate predictions of MOF adsorption properties. Accurate adsorption simulations often require an accurate description of electrostatic interactions, which depend on the electronic charges of the MOF atoms. HTS-compatible methods to assign charges to MOF atoms need to accurately reproduce electrostatic potentials (ESPs) and be computationally affordable, but current methods present an unsatisfactory trade-off between computational cost and accuracy. We illustrate a method to assign charges to MOF atoms based on ab initio calculations on MOF molecular building blocks. A library of building blocks with built-in charges is thus created and used by an automated MOF construction code to create hundreds of MOFs with charges "inherited" from the constituent building blocks. The molecular building block-based (MBBB) charges are similar to REPEAT charges-which are charges that reproduce ESPs obtained from ab initio calculations on crystallographic unit cells of nanoporous crystals-and thus similar predictions of adsorption loadings, heats of adsorption, and Henry's constants are obtained with either method. The presented results indicate that the MBBB method to assign charges to MOF atoms is suitable for use in computational high-throughput screening of MOFs for applications that involve adsorption of molecules such as carbon dioxide.

Understanding Volumetric and Gravimetric Hydrogen Adsorption Trade-off in Metal-Organic Frameworks.

Metal-organic frameworks (MOFs) are porous crystalline materials that are promising for adsorption-based, on-board storage of hydrogen in fuel-cell vehicles. Volumetric and gravimetric hydrogen capacities are the key factors that determine the size and weight of the MOF-filled tank required to store a certain amount of hydrogen for reasonable driving range. Therefore, they must be optimized so the tank is neither too large nor too heavy. Because the goals of maximizing MOF volumetric and gravimetric hydrogen adsorption loadings individually are incompatible, an in-depth understanding of the trade-off between MOF volumetric and gravimetric loadings is necessary to achieve the best compromise between these properties. Here we study, both experimentally and computationally, the trade-off between volumetric and gravimetric cryo-adsorbed hydrogen deliverable capacity by taking an isoreticular series of highly stable zirconium MOFs, NU-1101, NU-1102, and NU-1103 as a case study. These MOFs were studied under recently proposed operating conditions: 77 K/100 bar →160 K/5 bar. We found the difference between highest and lowest measured deliverable capacity in the MOF series to be ca. 40% gravimetrically, but only ca. 10% volumetrically. From our molecular simulation results, we found hydrogen "monolayer" adsorption to be proportional to the surface area, whereas hydrogen "pore filling" adsorption is proportional to the pore volume. Thus, we found that the higher variability in gravimetric deliverable capacity in contrast to the volumetric capacity, occurs due to the proportional relation between gravimetric surface area and pore volume in the NU-110x series in contrast to the inverse relation between volumetric surface area and void fraction. Additionally, we find better correlations with geometric surface areas than with BET areas. NU-1101 presents the highest measured volumetric performance with 46.6 g/L (9.1 wt %), whereas NU-1103 presents the highest gravimetric one with 12.6 wt % (43.2 g/L).