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At least 595 records · Page 33

Advanced Supported Liquid Membranes for Carbon Dioxide Control in Cabin Applications

The development of new, robust, life support systems is critical to NASA's continued progress in space exploration. One vital function is maintaining the carbon dioxide (CO2) concentration in the cabin at levels that do not impair the health or performance of the crew. The CO2 removal assembly (CDRA) is the current CO2 control technology on-board the International Space Station (ISS). Although the CDRA has met the needs of the ISS to date, the repeated cycling of the molecular sieve sorbent causes it to break down into small particles that clog filters or generate dust in the cabin. This reduces reliability and increases maintenance requirements. Another approach that has potential advantages over the current system is a membrane that separates CO2 from air. In this approach, cabin air contacts one side of the membrane while other side of the membrane is maintained at low pressure to create a driving force for CO2 transport across the membrane. In this application, the primary power requirement is for the pump that creates the low pressure and then pumps the CO2 to the oxygen recovery system. For such a membrane to be practical, it must have high CO2 permeation rate and excellent selectivity for CO2 over air. Unfortunately, conventional gas separation membranes do not have adequate CO2 permeability and selectivity to meet the needs of this application. However, the required performance could be obtained with a supported liquid membrane (SLM), which consists of a microporous material filled with a liquid that selectively reacts with CO2 over air. In a recently completed Phase II SBIR project, Reaction Systems, Inc. fabricated an SLM that is very close to meeting permeability and selectivity objectives for use in the advanced space suit portable life support system. This paper describes work carried out to evaluate its potential for use in spacecraft cabin application.

Wickham, David T.↗

Advanced Supported Liquid Membranes for Carbon Dioxide Control in Cabin Applications

The development of new, robust, life support systems is critical to NASA's continued progress in space exploration. One vital function is maintaining the carbon dioxide (CO2) concentration in the cabin at levels that do not impair the health or performance of the crew. The carbon dioxide removal assembly (CDRA) is the current CO2 control technology on-board the International Space Station (ISS). Although the CDRA has met the needs of the ISS to date, the repeated cycling of the molecular sieve sorbent causes it to break down into small particles that clog filters or generate dust in the cabin. This reduces reliability and increases maintenance requirements. Another approach that has potential advantages over the current system is a membrane that separates CO2 from air. In this approach, cabin air contacts one side of the membrane while other side of the membrane is maintained at low pressure to create a driving force for CO2 transport across the membrane. In this application, the primary power requirement is for the pump that creates the low pressure and then pumps the CO2 to the oxygen recovery system. For such a membrane to be practical, it must have high CO2 permeation rate and excellent selectivity for CO2 over air. Unfortunately, conventional gas separation membranes do not have adequate CO2 permeability and selectivity to meet the needs of this application. However, the required performance could be obtained with a supported liquid membrane (SLM), which consists of a microporous material filled with a liquid that selectively reacts with CO2 over air. In a recently completed Phase II SBIR project, Reaction Systems, Inc. fabricated an SLM that is very close to meeting permeability and selectivity objectives for use in the Portable Life Support System (PLSS). This paper describes work carried out to evaluate its potential for use in the cabin.

Wickham, David T.↗

Disentangling jet modification in jet simulations and in Z+jet data

The selection of jets in heavy-ion collisions based on their p T after jet quenching is known to bias towards jets that lost little energy in the quark-gluon plasma. In this work, we study and quantify the impact of this selection bias on jet substructure observables so as to isolate effects caused by the modification of the substructure of jets by quenching. We do so at first in a simplified Monte Carlo study in which it is possible to identify the same jet before and after quenching. We show explicitly that jets selected based on their quenched (i.e. observable) p T have substantially smaller fractional energy loss than those selected based on the p T that they would have had in the absence of any quenching. This selection bias has a large impact on jet structure and substructure observables. As an example, we consider the angular separation ΔR of the hardest splitting in each jet, and find that the ΔR distribution of the (biased) sample of jets selected based upon their quenched p T is almost unmodified by quenching. In contrast, quenching causes dramatic modifications to the ΔR distribution of a sample of jets selected based upon their unquenched p T , with a significant enhancement at larger ΔR coming from the soft particles originating from the wake of the jet in the quark-gluon plasma. The jets which contribute to this enhancement are those which have lost the most energy and which were, therefore, left out of the sample selected after quenching. In a more realistic study, we then show that the same qualitative effects can all be observed in Z+jet events. Selecting jets in such events based on either the jet p T or the Z-boson p T provides an experimentally accessible way to quantify the effects of selection biases in jet observables and separate them from the modification of jet substructure caused by quenching. Selecting Z+jet events based upon the jet p T yields a ΔR distribution that appears almost unmodified whereas selecting Z+jet events based upon the Z-boson p T reveals a significant modification to the ΔR-distribution caused by quenching, once again arising from the wakes of those jets that lose more energy.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Precise Pore Engineering of fcu–Type Y–MOFs for One–Step C 2 H 4 Purification from Ternary C 2 H 6 /C 2 H 4 /C 2 H 2 Mixtures

The purification of C 2 H 4 from C 2 H 6 /C 2 H 4 /C 2 H 2 mixtures is of great significance in the chemical industry for C 2 H 4 production but remains a daunting task. Guided by powerful reticular chemistry principles, herein a systematic study is carried out to engineer pore dimensions and pore functionality of fcu-type Y-based metal–organic frameworks (Y-MOFs) through the construction of a series of eight new structures using linear dicarboxylate linkers with different length and functional groups. This study illustrates how delicate changes in pore size and pore surface chemistry can effectively influence the adsorption preference of C 2 H 6 , C 2 H 4 , and C 2 H 2 by the MOFs. Importantly, clear relations between pore size/pore surface polarity and C 2 adsorption selectivities of this series of MOFs are established. In particular, HIAM-326 built on a linker decorated with trifluoromethoxy group shows notably preferential adsorption of C 2 H 6 and C 2 H 2 over C 2 H 4 , with balanced C 2 H 2 /C 2 H 4 and C 2 H 6 /C 2 H 4 selectivities. Furthermore, this endows the compound with the capability of one-step purification of C 2 H 4 from C 2 H 6 /C 2 H 4 /C 2 H 2 ternary mixtures, which is validated by breakthrough measurements where high purity C 2 H 4 (99.9%+) can be obtained directly from the separation column. Its adsorption thermodynamics and underlying selective adsorption mechanisms are further revealed by ab initio calculations.

36 MATERIALS SCIENCE↗

Connecting Current and Future Dual Active Galactic Nucleus Searches to LISA and Pulsar Timing Array Gravitational-wave Detections

Abstract Dual active galactic nuclei (DAGN) mark the observable stage of massive black hole (MBH) pairing during galaxy mergers and are the progenitors of the MBH binaries that generate low-frequency gravitational waves. Using the large-volume ASTRID cosmological simulation, we construct mock DAGN catalogs tailored to the selection functions of current (COSMOS-Web and DESI) and forthcoming (Nancy Grace Roman Space Telescope (Roman) and Lynx X-ray Observatory (Lynx)) surveys, enabling direct comparisons between simulations and observations. With realistic observational selections, ASTRID reproduces the observed dual fractions, projected separations, and host-galaxy properties across redshifts. We predict a substantial population of small-separation (<5 kpc) duals that remain inaccessible to current surveys, demonstrating that the apparent paucity of subkiloparsec systems in COSMOS-Web is primarily a consequence of observational selection rather than an intrinsic absence. Following each simulated dual to coalescence, we show that DAGN are effective tracers of MBH mergers: ∼30%–70% merge within ≲1 Gyr, and 20%–60% of these mergers produce gravitational-wave signals detectable by the Laser Interferometer Space Antenna (LISA). Duals observable with Roman and Lynx are the progenitors of ∼10%–50% of low-redshift LISA sources and contribute ∼30% of the PTA-band stochastic gravitational-wave background. We further identify massive green-valley galaxies hosting moderate-luminosity active galactic nuclei (AGN), together with massive star-forming galaxies containing bright quasars at z > 1, as the environments most likely to host imminent MBH binaries. These results establish a unified cosmological framework connecting DAGN demographics, MBH binary evolution, and gravitational-wave sources, while identifying high-priority targets for coordinated electromagnetic and multimessenger observations in the coming decade.

Chen, Nianyi [Max-Planck-Institut für Astrophysik;↗

Molecularly engineering polymeric membranes for H 2 / CO 2 separation at 100–300 °C

Over the last two decades, polymers with superior H 2 /CO 2 separation properties at 100–300 °C have gathered significant interest for H 2 purification and CO 2 capture. This timely review presents various strategies adopted to molecularly engineer polymers for this application. We first elucidate the Robeson's upper bound at elevated temperatures for H 2 /CO 2 separation and the advantages of high-temperature operation (such as improved solubility selectivity and absence of CO 2 plasticization), compared with conventional membrane gas separations at ~35 °C. Second, we describe commercially relevant membranes for the separation and highlight materials with free volumes tuned to discriminate H 2 and CO 2 , including functional polymers (such as polybenzimidazole) and engineered polymers by cross-linking, blending, thermal treatment, thermal rearrangement, and carbonization. Third, we succinctly discuss mixed matrix materials containing size-sieving or H 2 -sorptive nanofillers with attractive H 2 /CO 2 separation properties.

42 ENGINEERING↗

Identifying High-Performance Metal–Organic Frameworks for Low-Temperature Oxygen Recovery from Helium by Computational Screening

Metal–organic frameworks (MOFs) are an important class of porous crystalline materials for applications ranging from gas adsorption and separation to catalysis. There are thousands of potential MOFs available for separation applications. Here, we developed a computational approach to screen MOFs for the separation of oxygen–helium mixtures at low temperatures (100–200 K), conditions that were motivated by issues associated with propulsion in space-based settings. We used detailed molecular simulations for a small number of MOFs to develop screening methods that were then used to estimate the optimum temperatures for separations using pressure swing adsorption for 2932 MOFs from the CoRE MOF database and the swing capacity and oxygen–helium selectivity at these temperatures. We used the stability of the best-performing structures in the presence of moisture as a means to provide a short list of high-performance materials. In addition to identifying specific materials for oxygen–helium separations, this approach could prove useful for selecting adsorbents for other gas separations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electrophoresis tests on STS-3 and ground control experiments - A basis for future biological sample selections

Static zone electrophoresis is an electrokinetic method of separating macromolecules and small particles. However, its application for the isolation of biological cells and concentrated protein solutions is limited by sedimentation and convection. Microgravity eliminates or reduces sedimentation, floatation, and density-driven convection arising from either Joule heating or concentration differences. The advantages of such an environment were first demonstrated in space during the Apollo 14 and 16 missions. In 1975 the Electrophoresis Technology Experiment (MA-011) was conducted during the Apollo-Soyuz Test Project flight. In 1979 a project was initiated to repeat the separations of human kidney cells. One of the major objectives of the Electrophoresis Equipment Verification Tests (EEVT) on STS-3 was to repeat and thereby validate the first successful electrophoretic separation of human kidney cells. Attention is given to the EEVT apparatus, the preflight electrophoresis, and inflight operational results.

Morrison, D. R.↗

Generation of Optical Combs in a WGM Resonator from a Bichromatic Pump

Optical combs generated by a monolithic resonator with Kerrmedium can be used in a number of applications, including orbital clocks and frequency standards of extremely high accuracy, such as astronomy, molecular spectroscopy, and the like. The main difficulty of this approach is the relatively high pump power that has to be used in such devices, causing undesired thermorefractive effects, as well as stimulated Raman scattering, and limiting the optical comb quality and utility. In order to overcome this problem, this innovation uses a different approach to excitation of the nonlinear oscillations in a Kerr-nonlinear whispering gallery mode (WGM) resonator and generation of the optical comb. By coupling to the resonator two optical pump frequencies instead of just one, the efficiency of the comb source can be increased considerably. It therefore can operate in a lowerpower regime where the undesirable effects are not present. This process does not have a power threshold; therefore, the new optical component can easily be made strong enough to generate further components, making the optical comb spread in a cascade fashion. Additionally, the comb spacing can be made in an arbitrary number of the resonator free spectral ranges (FSR). The experimental setup for this innovation used a fluorite resonator with OMEGA= 13.56 GHz. This material has very low dispersion at the wavelength of 1.5 microns, so the resonator spectrum around this wavelength is highly equidistant. Light was coupled in and out of the resonator using two optical fibers polished at the optimal coupling angle. The gap between the resonator and the fibers, affecting the light coupling and the resonator loading, was controlled by piezo positioners. The light from the input fiber that did not go into the resonator reflected off of its rim, and was collected by a photodetector. This enabled observation and measurement of the (absorption) spectrum of the resonator. The input fiber combined light from two lasers centered at around 1,560 nanometers. Both laser frequencies were simultaneously scanned around the selected WGMs of the same family. However, they were separated by one, two, three, or ten FSRs. This was achieved by fine-tuning each laser frequency offset until the selected resonances overlap on the oscilloscope screen. The resonator quality factor Q = 7 x 10(exp 7) was relatively low to increase the linewidth and, therefore, the duty cycle of both lasers simultaneously coupled into their WGMs. The optical spectrum analyzer (OSA) connected to the output fiber was continuously acquiring data, asynchronously with the laser scan. The instrument was set to retain the peak power values; therefore, a trace recorded for a sufficiently long period of time reflected the situation with both lasers maximally coupled to the WGMs.

Strekalov, Dmitry V.↗

Carbon molecular-sieve membranes developed from a Tröger’s base polymer and possessing superior gas-separation performance

Carbon molecular-sieve membranes possess tremendous practical advantages over unary polymer membranes by providing high gas-separation performance levels, coupled with excellent mechanical and chemical stability. Improving their overall effectiveness greatly expands the competitiveness of this class of membranes. In the present study, carbon membranes are fabricated from a Tröger’s base polymer as the precursor. Further, by optimizing the carbonization conditions, the gas-separation performance of the resultant membranes are significantly enhanced. Under optimized conditions, a H 2 permeability of up to 1135 Barrer is achieved, with a corresponding H 2 /CH 4 selectivity of 1170 and a CO 2 /CH 4 selectivity of 238. While increasing the operating temperature slightly reduces the selectivity, it still remains in the high-separation region. Overall, the measured separation performance levels for H 2 -related separations, i.e., H 2 /CH 4 , H 2 /N 2 and H 2 /CO 2 , all substantially exceed the Robeson upper bound. Moreover, the CO 2 /CH 4 separation efficacy also lies above the 2019 upper bound, indicating that the carbon membranes developed in the present work are versatile and promising for many different gas-separation applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electrochromatographic separation of proteins

We have developed a modified electrochromatography system which minimizes Joule heating at electric field strengths up to 125 V/cm. A non-linear equilibrium model is described which incorporates electrophoretic mobility, hydrodynamic flow velocity, and an electrically induced concentration polarization at the surface of the stationary phase. This model is able to provide useful estimates of protein retention time and velocity in a column packed with Sephadex gel and subjected to an electric field. A correlation of electrophoretic mobility of peptide and proteins with respect to their charge, molecular mass, and asymmetry enables the selection of solute target molecules for electrochromatographic separations. Good separation of protein mixtures have been obtained.

NASA Discipline Life Support Systems↗

Characterizing the target selection pipeline for the Dark Energy Spectroscopic Instrument Bright Galaxy Survey

ABSTRACT We present the steps taken to produce a reliable and complete input galaxy catalogue for the Dark Energy Spectroscopic Instrument (DESI) Bright Galaxy Survey (BGS) using the photometric Legacy Survey DR8 DECam. We analyse some of the main issues faced in the selection of targets for the DESI BGS, such as star–galaxy separation, contamination by fragmented stars and bright galaxies. Our pipeline utilizes a new way to select BGS galaxies using Gaia photometry and we implement geometrical and photometric masks that reduce the number of spurious objects. The resulting catalogue is cross-matched with the Galaxy And Mass Assembly (GAMA) survey to assess the completeness of the galaxy catalogue and the performance of the target selection. We also validate the clustering of the sources in our BGS catalogue by comparing with mock catalogues and the Sloan Digital Sky Survey (SDSS) data. Finally, the robustness of the BGS selection criteria is assessed by quantifying the dependence of the target galaxy density on imaging and other properties. The largest systematic correlation we find is a 7 per cent suppression of the target density in regions of high stellar density.

79 ASTRONOMY AND ASTROPHYSICS↗

Adaptive Conformer Sampling for Property Prediction Using the Conductor-like Screening Model for Real Solvents

The valorization of lignocellulose-derived bioproducts requires effective separation from excessive water. Liquid–liquid extraction is a promising low-energy separation technology, but effective extraction requires solvent selection based on the thermodynamic properties of the bioproduct and solvent components. We propose a computational framework for predicting such properties by developing an adaptive conformer selection approach for use with COSMO-RS (conductor-like screening model for real solvents) calculations. In this framework, molecular dynamics simulations are used to generate many molecular structures (conformers) at representative temperatures in varying solvent environments. Conformers are then clustered based on structural metrics in a low-dimensional space and selected using a mixed-integer quadratic programming problem to iteratively insert a sampled conformer. At each iteration, we determine bioproduct properties using COSMO-RS. Here, we demonstrate the capability of the proposed framework on representative bioproducts to show convergence of the adaptive sampling toward experimentally measured properties with fewer calculations than required by random conformer sampling, enabling the improved screening of solvent systems for liquid-phase separation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

3D Printing of Functional Hydrogel Devices for Screenings of Membrane Permeability and Selectivity

Developing a fundamental understanding of the effects of varying ligand chemistries on mass transport rates is key to designing membranes with solute-specific selectivity. While permeation cells offer a robust method to characterize membrane performance, they are limited to assessing a single membrane chemistry or salt solution per test. As a result, investigating the effects of varying ligand chemistries on membrane performance can be a tedious process, involving both the preparation of multiple samples and numerous, time-consuming permeation tests. This study uses digital light processing (DLP) 3D printing to fabricate a millifluidic flow-based permeation device made from a hydrogel active ester network that can be easily functionalized with ion-selective ligands. Without the need for bonding or assembly steps, ligands can be introduced and tested in the permeation device by simply injecting a small volume of a ligand solution. Various salt concentrations and molecular species can be cycled through a single device by switching the solution feeding into the salt reservoir, thereby reducing the number of samples needed for permeability and selectivity screenings. This research sets the groundwork for formulation development and postprocessing methods to 3D-print functional millifluidic devices capable of assessing solute selectivity in membranes and polymer adsorbents for aqueous separations. In this work, comparable salt permeability trends were observed with both 3D-printed devices and traditional assays. Devices were functionalized with an imidazole ligand to investigate salt permeability and selectivity of monovalent and divalent salts. Measurements showed increasing permeability for monovalent salts (NaCl) relative to divalent salts (MgCl 2 , CuCl 2 ) in functionalized membranes, with higher monovalent/divalent selectivity at increasing imidazole grafting densities. Here, the methods and findings described here represent a step toward developing higher-throughput methods with 3D-printed devices for screening the effects of ligand chemistry on mass transport rates in membrane materials.

36 MATERIALS SCIENCE↗

CO2 Acquisition Membrane (CAM)

The objective of CAM is to develop, test, and analyze thin film membrane materials for separation and purification of carbon dioxide (CO2) from mixtures of gases, such as those found in the Martian atmosphere. The membranes are targeted toward In Situ Resource Utilization (ISRU) applications that will operate in extraterrestrial environments and support future unmanned and human space missions. A primary application is the Sabatier Electrolysis process that uses Mars atmosphere CO2 as raw material for producing water, oxygen, and methane for rocket fuel and habitat support. Other applications include use as an inlet filter to collect and concentrate Mars atmospheric argon and nitrogen gases for habitat pressurization, and to remove CO2 from breathing gases in Closed Environment Life Support Systems (CELSS). CAM membrane materials include crystalline faujasite (FAU) zeolite and rubbery polymers such as silicone rubber (PDMS) that have been shown in the literature and via molecular simulation to favor adsorption and permeation of CO2 over nitrogen and argon. Pure gas permeation tests using commercial PDMS membranes have shown that both CO2 permeance and the separation factor relative to other gases increase as the temperature decreases, and low (Delta)P(Sub CO2) favors higher separation factors. The ideal CO2/N2 separation factor increases from 7.5 to 17.5 as temperature decreases from 22 C to -30 C. For gas mixtures containing CO2, N2, and Ar, plasticization decreased the separation factors from 4.5 to 6 over the same temperature range. We currently synthesize and test our own Na(+) FAU zeolite membranes using standard formulations and secondary growth methods on porous alumina. Preliminary tests with a Na(+) FAU membrane at 22 C show a He/SF6 ideal separation factor of 62, exceeding the Knudsen diffusion selectivity by an order of magnitude. This shows that the membrane is relatively free from large defects and associated non-selective (viscous flow) transport mechanisms. The Membrane Test Facility (MTF) has been developed to measure membrane permeance over a wide range of temperature and pressure. The facility uses two volume compartments separated by the membrane that are instrumented to measure temperature, delta pressure across the membrane, and gas composition. A thermal shroud supports and encloses the membrane, and provides temperature control. Methods were developed to determine membrane permeance using the first order decay of the pressure difference between the sealed compartments, using the total pressure for pure gases, and partial pressure of each species in gas mixtures. The technique provides an end-to-end measurement of gas permeance that includes concentration polarization effects. Experiments have shown that in addition to membrane permeance properties, the geometry and design of associated structures play an important role in how membrane systems will function on Mars.

Mason, Larry W.↗

Tuning gas separation performance of polyimide membranes with macrocyclic crown ether units

Membrane-based gas separation is an energy-efficient alternative to conventional thermally-driven separation processes. However, polymer membranes face the permeability-selectivity trade-off challenge, which stems from the broad size distribution of free volume voids. Here, this study reports a molecular design strategy to address this challenge through incorporating macrocyclic crown ether (CE) moieties into the backbone of Matrimid® polyimide, a commercial gas separation membrane. A series of CE-containing Matrimid®-like copolyimides were synthesized with systematically varied CE molar contents ranging from 3 to 20%. These copolyimides formed ductile, defect-free thin films suitable for membrane fabrication. Gas permeation tests revealed a non-monotonic relationship between permeability/selectivity and CE content. Notably, the copolyimide with only 5% CE demonstrated a 61% increase in CO 2 /CH 4 selectivity and a 13% increase in CO 2 permeability relative to pristine Matrimid®. Higher CE contents did not yield further performance improvements, which is likely due to the competing effects of chain packing disruption and π–π interactions among CE moieties at high content. This hypothesis was supported by wide-angle X-ray scattering (WAXS) analysis, density measurements, and fractional free volume calculations. These findings highlight the potential of macrocyclic crown ether incorporation strategies in fine tuning the microstructure of commercial polyimide gas separation membranes to surpass the traditional permeability-selectivity trade-off.

CO2 separation↗

Pyrazine-Fused Porous Graphitic Framework-Based Mixed Matrix Membranes for Enhanced Gas Separations

Membrane-based separations can mitigate the capital- and energy-intensive challenges associated with traditional thermally driven processes. To further push the boundary of gas separations, mixed matrix membranes (MMMs) have been extensively exploited; however, identifying an optimal nanofiller to boost the separation performance of MMMs beyond Robeson permeability-selectivity upper bounds remains an ongoing challenge. In this study, a new class of MMMs based on pyrazine-fused crystalline porous graphitic frameworks (PGFs) is reported. At a loading of 6 wt % PGFs, the MMMs surpass the current H 2 /CH 4 Robeson upper bound, ideally suited for applications such as H 2 regeneration. In addition, the fabricated MMMs exhibit appealing CO 2 separation performance, closely approaching the current Robeson upper bounds for CO 2 separation. Compared with the pristine polymeric membranes, the PGF-based MMMs display a record-high enhancement of gas permeability over 120% while maintaining intrinsic gas selectivities. Highlighting the crucial role of the crystallinity of nanofillers, this study demonstrates a facile and effective approach in formulating high-performance MMMs, complementing state-of-the-art membrane formation processes. The design principles open the door to energy-efficient separations of gas mixtures with enhanced productivity compatible with the current membrane manufacturing.

36 MATERIALS SCIENCE↗

An Exceptionally Stable Metal–Organic Framework Constructed from Chelate-Based Metal–Organic Polyhedra

In this paper, we report the rational design and synthesis of a new, water-stable metal-organic framework (MOF), Fe-HAF-1, constructed from supramolecular, Fe3+-hydroxamate-based polyhedra with mononuclear metal nodes. Owing to its chelate-based con-struction, Fe-HAF-1 displays exceptional chemical stability in organic and aqueous solvents over a wide pH range (pH 1-14), including in the presence of 5 M NaOH. Despite the charge-neutrality of the Fe 3+ -tris(hydroxamate) centers, Fe-HAF-1 crystals are negatively charged above pH 4. This unex-pected property is attributed to the formation of defects during crystallization that results in uncoordinated hydroxamate ligands or hydroxide-coordinated Fe centers. The anionic na-ture of Fe-HAF-1 crystals enables selective adsorption of pos-itively charged ions in aqueous solution, resulting in efficient separation of organic dyes and other charged species in a size-selective fashion. Fe-HAF-1 presents a new addition to a small group of chelate-based MOFs and provides a rare framework whose 3D connectivity is exclusively formed by metal-hydroxamate coordination.

36 MATERIALS SCIENCE↗