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At least 37 records · Page 2

Understanding 2p core-level excitons of late transition metals by analysis of mixed-valence copper in a metal–organic framework

The L 2,3 -edge X-ray absorption spectra of late transition metals such as Cu, Ag, and Au exhibit absorption onsets lower in energy for higher oxidation states, which is at odds with the measured spectra of earlier transition metals. Time-dependent density functional theory calculations for Cu 2+ /Cu + reveal a larger 2p core-exciton binding energy for Cu 2+ , overshadowing shifts in single-particle excitation energies with respect to Cu + . Finally, we explore this phenomenon in a Cu + metal–organic framework with ~12% Cu 2+ defects and find that corrections with self-consistent excited-state total energy differences provide accurate XAS peak alignment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Association of nucleotides with homoionic clays

The binding of nucleotides to homoionic clays is studied as a possible mechanism for the concentration and catalysis of biological or prebiotic materials on the prebiotic earth. Samples of radioactively labeled adenosine and thymidine nucleotides were mixed in solutions with bentonite, kaolinite or Dowex-50 particles in which all exchangeable sites were occupied by Na, Mg, Ca, Mn, Fe, Cu or Zn ions. The binding of nucleotides to homoionic clays is observed, with adenosine nucleotides favored over thymidine, bentonite as the best absorber, and greater binding to clays homoionic in transition metal ions. Results indicate that the oligomerization of nucleotides may be possible by this mechanism, however difficulties in nucleotide variability and base pairing may arise due to the observed preference for purines at the adsorption sites.

Odom, D. G.↗

Spin pumping from antiferromagnetic insulator spin-orbit-proximitized by adjacent heavy metal: a first-principles Floquet-nonequilibrium Green function study

Motivated by the recent experiment on spin pumping from sub-THz radiation-driven uniaxial antiferromagnetic insulator (AFI) MnF 2 into heavy metal (HM) Pt hosting strong spin-orbit (SO) coupling, we compute and compare pumped spin currents in Cu/MnF 2 /Cu and Pt/MnF 2 /Cu heterostructures. Recent theories of spin pumping by AFI have relied on simplistic Hamiltonians (such as tight-binding) and the scattering approach to quantum transport yielding the so-called interfacial spin mixing conductance (SMC), but the concept of SMC ceases to be applicable when SO coupling is present directly at the interface. In contrast, we use a more general first-principles quantum transport approach which combines noncollinear density functional theory with Floquet-nonequilibrium Green's functions in order to take into account: SO-proximitized AFI as a new type of quantum material, different from isolated AFI and brought about by AFI hybridization with adjacent HM layer; strong SO coupling at the interface; and evanescent wavefunctions penetrating from Pt or Cu into AFI layer to make its interfacial region conducting rather than insulating as in the isolated AFI. The DC component of pumped spin current $I_\mathrm{DC}^{S_z}$ vs. precession cone angle $\theta_{\boldsymbol{l}}$ of the Néel vector l of AFI does not follow putative $I^{S_z}_\mathrm{DC} \propto \sin^2 \theta_{\boldsymbol{l}}$, except for very small angles $\theta_{\boldsymbol{l}} \lesssim 10^\circ$ for which we define an effective SMC from the prefactor and find that it doubles from MnF2/Cu to MnF2/Pt interface. In addition, the angular dependence $I^{S_z}_\mathrm{DC}(\theta_{\boldsymbol{l}})$ differs for opposite directions of precession of the Néel vector, leading to twice as large SMC for the right-handed than for the left-handed chirality of the precession mode.

36 MATERIALS SCIENCE↗

Interaction of Anisole on Alumina-Supported Ni and Mo Oxide Hydrodeoxygenation Catalysts

The conversion of biomass to transportation fuels and value-added chemicals is a promising method to reduce reliance on fossil fuels. Mo-based catalysts have been shown to be highly active in the hydrodeoxygenation of biomass-derived phenolic compounds. The catalyst active phase, surface species, and the effect of adding additional metals is not comprehensively understood. Here we compare the temperature-dependent adsorption behavior of the model compound anisole 2 on an alumina-supported mixed nickel molybdenum oxide catalyst with two reference catalysts of molybdenum oxide and nickel oxide. Raman spectroscopy showed that the catalysts contain significant amounts of molybdates and molybdoaluminates, in addition to NiMoO 4 in the nickel molybdenum catalyst and MoO 3 in the molybdenum-only catalyst. Using transmission infrared spectroscopy under a controlled environment, we find that anisole chemisorbed largely through the oxygen in the methoxy group to form surface-bound phenoxy and methoxy species on all the catalysts. Ambient pressure X-ray photoelectrons spectroscopy measurements of the catalysts in anisole vapor showed reduced Mo atoms are the binding sites. The surface interaction and removal temperature of these species varied with the metal composition. The MoO x component dominated the adsorption behavior in both MoO x and NiMoO x catalysts. The formation of new aromatics, including methylated rings, depended on Ni composition. Upon adding hydrogen to induce the hydrodeoxygenation of anisole, undesirable polynuclear aromatic species were quickly formed on the Mo-based catalysts. In conclusion, these results suggest that the molybdenum oxide controls the adsorption and reactivity of the surface species, with a cooperative effect by Ni.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effects of Radiation and Dietary Iron on Expression of Genes and Proteins Involved in Drug Metabolism

Liver function, especially the rate of metabolic enzyme activities, determines the concentration of circulating drugs and the duration of their efficacy. Most pharmaceuticals are metabolized by the liver, and clinically-used medication doses are given with normal liver function in mind. A drug overdose can result in the case of a liver that is damaged and removing pharmaceuticals from the circulation at a rate slower than normal. Alternatively, if liver function is elevated and removing drugs from the system more quickly than usual, it would be as if too little drug had been given for effective treatment. Because of the importance of the liver in drug metabolism, we want to understand any effects of spaceflight on the enzymes of the liver. Dietary factors and exposure to radiation are aspects of spaceflight that are potential oxidative stressors and both can be modeled in ground experiments. In this experiment, we examined the effects of high dietary iron and low dose gamma radiation (individually and combined) on the gene expression of enzymes involved in drug metabolism, redox homeostasis, and DNA repair. METHODS All procedures were approved by the JSC Animal Care and Use Committee. Male Sprague-Dawley rats were divided into 4 groups (n=8); control, high Fe diet (650 mg iron/kg), radiation (fractionated 3 Gy exposure from a Cs- 137 source) and combined high Fe diet + radiation exposure. Animals were euthanized 24h after the last treatment of radiation; livers were removed immediately and flash -frozen in liquid nitrogen. Expression of genes thought to be involved in redox homeostasis, drug metabolism and DNA damage repair was measured by RT-qPCR. Where possible, protein expression of the same genes was measured by western blotting. All data are expressed as % change in expression normalized to reference gene expression; comparisons were then made of each treatment group to the sham exposed/ normal diet control group. Data was considered significant at p< 0.5. RESULTS Among the redox homeostasis genes examined, metallothionein showed a significant down regulation in the radiation treated group (-3.85 fold) and a trend toward down regulation in the high Fe + rad group. Metallothionein is involved in the regulation of physiological metals and also has antioxidant activities. Among the drug metabolism genes examined, ATP binding cassette subfamily B (Abcb1b) gene expression increased more than 10-fold in both groups that received radiation treatments. This increased expression was also seen at the protein level. This ABC transporter carries many different compounds across cell membranes, including administered medications. The cytochrome P450 2E1 enzyme, a mixed-function oxidase that deactivates some medications and activates others, showed about a 2-fold increase in gene expression in both radiation-treated groups, with a trend toward increased expression at the protein level. Expression of epoxide hydrolase, which detoxifies polycyclic aromatic hydrocarbons, showed similar 2-fold increases. Among the DNA repair genes examined, expression of RAD51 was significantly down regulated (1.5 fold) in the radiation treated group. RAD51 is involved in repair of double-stranded DNA breaks. CONCLUSION This experiment used 2 different sources of physiological oxidative stress, administered separately and together, and examined their impacts on liver gene and protein expression. It is clear that significant changes occurred in expression of several genes and proteins in the radiation-treated animals. If the results from this ground analog of portions of the spaceflight environment hold true for the spaceflight environment itself, the physiological roles of the affected enzymes (drug transport and metabolism, redox homeostasis) could mean consequences in redox homeostasis or the pharmacokinetics of administered medications

Faust, K. M.↗

Tuning the Placement of Pt “Single Atoms” on a Mixed CeO 2 –TiO 2 Support

Defect sites on the oxide supports can be used to anchor and activate "single-atoms" catalysts (SACs). By engineering the anchoring sites for supporting SACs, one can alter their electronic and atomic structures which, in turn, define their activity, selectivity, and stability for catalytic reactions. To create and tune unique sites for Pt SACs on CeO 2 support, in this work, we synthesized a system consisting of CeO 2 decorated on TiO 2 nano-oxides for supporting the Pt SACs and investigated the effect of Pt weight loading. Here, a combination of multiple structural characterization methods including diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS) were employed to characterize the distribution of charge states of single atoms and evaluate the heterogeneity of their binding sites. We have found that the placement of Pt atoms can be tuned on a mixed oxide surface by changing the weight loading of Pt.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Selectivity Control in Catalytic Reductive Amination of Furfural to Furfurylamine on Supported Catalysts

Abstract Amines are widely used in the manufacture of pharmaceuticals, agricultural chemicals, polymers, and surfactants. However, amines are mostly produced via petrochemical means, which motivates amine production from renewable resources, such as biomass. However, biomass compounds present added challenges involving poor carbon balances. We show that furfural reacts homogeneously with ammonia to produce reactive primary imines, which form large side products and leads to significant carbon losses. The carbon balance is improved by mixing furfural with furfurylamine prior to reaction to form a secondary imine for use as the reaction substrate. While controlling the primary to secondary amine selectivity is a common challenge in reductive amination, supported metal catalysts, including Ni/SiO 2 , Co/SiO 2 , and Ru/SiO 2 optimize the primary amine yield to 90 to 94 % by using the secondary imine as the reaction substrate. A qualitative correlation between the primary to secondary amine selectivity with the nitrogen binding energy of metals is identified.

Gould, Nicholas S.↗

Ion-Specific Precipitation of Extractants Enables Rare-Earth Separation and Wastewater Remediation from Solvent Extraction of Critical Elements

The increasing demand for rare-earth elements (REEs) necessitates sustainable recovery strategies, particularly from secondary sources, such as electronic waste. Solvent extraction is the primary industrial method for REE separation; however, the unintentional dissolution of extractants into wastewater poses serious environmental risks, leading to organic contamination and process inefficiencies. Existing wastewater treatment methods struggle to remove these persistent pollutants, underscoring the need for innovative recovery approaches. Herein, we present a ligand-mediated precipitation strategy that simultaneously recovers REEs and removes dissolved extractants from solvent extraction wastewater. We show that residual extractants in the aqueous phase can selectively bind REEs, inducing their precipitation while leaving transition metals in solution. By integrating FTIR spectroscopy, EDS, XPS, EXAFS, and SAXS, we elucidate the mechanism of ion-specific precipitation and the local coordination environment of metal ions in the precipitate. Importantly, we demonstrate that the precipitated extractants can be efficiently recovered and reused, providing a closed-loop solution that enhances sustainability. Applying this method to leachates from samarium–cobalt (Sm–Co) and neodymium–iron–boron (NdFeB) mixed magnets, we achieve highly selective REE precipitation under mild conditions, demonstrating a scalable and cost-effective pathway for REE recovery, wastewater purification, and extractant recycling. In conclusion, by integrating element-specific ligand-mediated precipitation with extractant reuse, this work offers a transformative approach to REE separation that reduces the environmental impact while improving resource efficiency.

E-waste↗

Data from: Short-Term Inhibition and Long-Term Enhancement of IrreversibleTrace Metal Binding to Goethite in Multi-Metal Systems

These files include the data used in all figures from the following paper: Short-Term Inhibition and Long-Term Enhancement of Irreversible Trace Metal Binding to Goethite in Multi-Metal Systems Below is a brief description of each of the figures and associated data. Fig 1. Ni adsorption isotherms to goethite in the presence and absence of Zn and Cd Fig 2. % of Ni, Zn, and Cd exchanged as a function of time in isotope exchange experiments conducted after 2 days, 30 days, and 60 days aging. Fig. 3. This shows the % of Ni, Cd, and Zn in single metal and mixed metal systems that is non-exchangeable, both in units of % non-exchangeable and in micromoles of metal per gram of goethite. Fig. 4. Particle size distributions of Ni-Zn and Ni-Cd systems after aging. Fig 5. Ni and Zn XANES fits for Ni-Cd and Ni-Zn systems after 30 and 60 days aging. Linear combination fits were performed between freshly adsorbed and incorporated phases (synthesized as Ni- or Zn-substituted goethite) to determine the proportions of each. Figure S1. Dissolved Metal Concentrations at the Start of Isotope Exchange Figure S2. Reactor pH with Aging Figure S3. Dissolved Cd and Ni Concentrations during Isotope Exchange Figure S4. Dissolved Zn and Ni Concentrations during Isotope Exchange Figure S5. Tracer Mole Fractions in Ni-Zn Isotope Exchange Experiments Figure S6. Tracer Mole Fractions in Ni-Cd Isotope Exchange Experiments

58 GEOSCIENCES↗

Local Coordination Environment of Lanthanides Adsorbed onto Cr- and Zr-based Metal–Organic Frameworks

Separating individual lanthanide (Ln) elements in aqueous mixtures is challenging. Ion-selective capture by porous materials, such as metal–organic frameworks (MOFs), is a promising approach. To design ion-selective MOFs, molecular details of the Ln adsorption complexes within the MOFs must be understood. We determine the local coordination environment of lanthanides Nd(III), Gd(III), and Lu(III) adsorbed onto Cr(III)-based terephthalate MOF (Cr-MIL-101) and Zr(IV)-based Universitet in Oslo MOFs (UiO-66 and UiO-68) and their derivatives. In the Cr(III)- and Zr(IV)-based MOFs, Ln adsorb as inner-sphere complexes at the metal oxo clusters, regardless of whether the organic linkers are decorated with amino groups. Missing linkers result in favorable Ln binding sites at oxo clusters; however, Ln can coordinate to metal sites even with linkers in place. Further, MOF functionalization with phosphonate groups led to Ln chemisorption onto these groups, which out-compete metal cluster sites. Ln form monodentate and bidentate and mononuclear and binuclear surface complexes. We conclude that MOFs for ion-selective Ln capture can be designed by a combination of (1) maximizing metal-lanthanide interactions via shared O atoms at the metal oxo cluster sites, where mixed oxo clusters can lead to ion-selective Ln adsorption, and (2) functionalizing MOFs with Ln-selective groups capable of out-completing the metal oxo cluster sites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Photocatalytic Hydrogen Evolution by a De Novo Designed Metalloprotein that Undergoes Ni–Mediated Oligomerization Shift

De novo metalloprotein design involves the construction of proteins guided by specific repeat patterns of polar and apolar residues, which, upon self-assembly, provide a suitable environment to bind metals and produce artificial metalloenzymes. While a wide range of functionalities have been realized in de novo designed metalloproteins, the functional repertoire of such constructs towards alternative energy-relevant catalysis is currently limited. Here we show the application of de novo approach to design a functional H 2 evolving protein. The design involved the assembly of an amphiphilic peptide featuring cysteines at tandem a/d sites of each helix. Intriguingly, upon Ni II addition, the oligomers shift from a major trimeric assembly to a mix of dimers and trimers. The metalloprotein produced H 2 photocatalytically with a bell-shape pH dependence, having a maximum activity at pH 5.5. Transient absorption spectroscopy is used to determine the timescales of electron transfer as a function of pH. Selective outer sphere mutations are made to probe how the local environment tunes activity. Finally, a preferential enhancement of activity is observed via steric modulation above the Ni II site, towards the N-termini, compared to below the Ni II site towards the C-termini.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nd, SbNd and Sb 3 Nd 4 and their interactions with the cladding alloy HT9

Lanthanide fission products, such as neodymium, formed during the irradiation of metallic fuels are known to cause deleterious effects from chemical interactions occurring at the fuel-cladding interface; a phenomenon known as fuel-cladding chemical interaction (FCCI). The use of fuel-based additives that bind with the lanthanide elements within the fuel meat, alleviating their interactions at the fuel-cladding interface, is one potential method proposed to mitigate the FCCI phenomenon and extend the burnup potential of such metallic fuel systems. In this study, antimony (Sb) is evaluated as one such additive, and neodymium (Nd) is used to represent the lanthanides. A Sb-Nd alloy is fabricated, which consists of two intermetallic phases, SbNd and Sb 3 Nd 4 . Isothermal diffusion couple experiments are carried out at 675 °C for 24 h between Nd and the Fe-12Cr based HT9 cladding alloy. The results are compared against similar diffusion couple experiments carried out between the Sb-Nd alloy and also HT9. Inter-diffusion between Nd/HT9 diffusion couple is characterized and the phases Fe 17 Nd 5 and Fe 17 Nd 2 were found to form whereas no interactions were observed in the Sb-Nd/HT9 diffusion couple. The lack of compound forming tendencies between Fe, the primary alloying constituent of HT9, and SbNd is elucidated through density functional theory (DFT) calculations on enthalpy of mixing, aligning well with the experimental observations. Lastly, the strong binding of Nd with Sb appears to be favorable, alleviating Nd interactions with HT9 constituent elements.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Ambient pressure x-ray photoelectron spectroscopy study of water formation and adsorption under two-dimensional silica and aluminosilicate layers on Pd(111)

Ambient pressure x-ray photoelectron spectroscopy (AP-XPS) supported by density functional theory (DFT) calculations was used to characterize the interaction of water with two-dimensional (2D) silica and aluminosilicate bilayers on Pd(111). Starting with oxygen adsorbed at the SiO2/Pd interface, exposure to water caused the SiO 2 -derived XPS peaks to shift to higher binding energy and the removal of an O 1s feature associated with interfacial adsorbed oxygen. These observations were attributed to the formation of a mixed water–hydroxyl interface, which eliminates the interfacial dipolar layer, and its associated electrostatic potential, created by adsorbed oxygen. Interfacial oxygen also reacted with H 2 to produce adsorbed water which also caused an upward binding energy shift of the SiO 2 peaks. Spectra recorded under 0.5 Torr water revealed additional water adsorption and a further shift of the overlayer peaks to higher binding energy. Incorporating Al into the 2D material caused the bilayer peaks to shift to lower binding energy which could be explained by electron donation from the metal to the bilayer. Although the stronger interaction between the bilayer and Pd substrate should restrict interfacial adsorption and reaction, similar trends were observed for water and hydrogen exposure to interfacial adsorbed oxygen. Less water adsorption was observed at the aluminosilicate interface which is a consequence of Al strengthening the bond to the metal substrate. The results reveal how the sensitivity of XPS to interfacial dipoles can be exploited to distinguish reactions taking place in confined spaces under 2D layers and how tuning the composition of the 2D layer can impact such reactions.

Density functional theory↗

Titanium-, Nitrogen-Doped Carbon Flowers Catalyze Electrochemical Nitrate Reduction Reaction to Ammonia

An emerging design heuristic for electrochemical nitrate reduction (NO 3 RR) catalysts is synthesizing electron-deficient sites to facilitate binding of electron-rich NO 3 – . However, this rule has rarely been applied to metal-, nitrogen-doped carbon (MNC) catalysts. Titanium (Ti), with low electronegativity and high NO 3 RR reactivity, is a compelling MNC candidate. To date, atomically dispersed TiN x motifs have eluded synthesis due to the strong oxophilicity of Ti. Here, in this work, we leverage nitrogen-rich carbon flowers (CF) to overcome synthetic challenges and produce Ti-, N-doped carbon flower (TiCF) catalysts. Advanced materials characterization demonstrates that TiCF catalysts are a mixed phase material with 3/4 of Ti atoms in TiO 2 -like nanoparticles and 1/4 of Ti atoms in novel, atomically dispersed TiN x sites. TiCF achieves 61 ± 7% NH 3 -selectivity at −0.70 V vs RHE and 14 ± 5 mA/cm 2 to NH 3 formation (| j NH 3 |) at −0.85 V vs RHE in (0.1 M NaOH + 0.1 M NaNO 3 + 0.45 M Na 2 SO 4 ) electrolyte. Control studies show both CF morphology and Ti sites are essential for high NO 3 RR activity. Density functional theory calculations attribute the NO3RR reactivity to TiN x , which facilitates multiple bond formation with surface intermediates to promote favorable NH3 synthesis pathways. Thus, TiCF exhibits 60× higher | j NH 3 | values than bulk Ti and NH 3 yield rates (>0.06 mmol NH 3 /h/cm 2 ) that are competitive with state-of-the-art MNC catalysts (e.g., FeNC, CuNC). TiCF introduces a new class of Ti electrocatalysts, advancing the MNC design space and sustainable NH 3 production.

ammonia↗

Photophysics and Carrier Dynamics of Lasing in Quasi-2D Lead Halide Perovskites

Quasi-2D perovskites have recently been extensively studied due to their narrow-bandwidth-tunable emission, solution processability, and applicability as optical gain media. Quasi-2D perovskites are composed of inorganic perovskite crystal layers encapsulated with a bulky organic ligand such as phenylethylammonium, endowing the perovskite with a quantum-well structure and improved stability. In this article, we explore the photophysics of a quasi-2D metal halide perovskite as a promising light-harvesting and emitting medium. We find it exhibits high optical absorption (~10 5 cm -1 ) and an optically pumped amplified spontaneous emission threshold at 623 μJ/cm 2 . We study charge transfer processes in the complex mixed quantum wells of these perovskites through transient absorption and time-resolved photoluminescence measurements and develop a phenomenological model that incorporates optical gain for lasing. Further, while both free carriers and excitons are observed, we show surprisingly that photoluminescence is dominated by excitons despite the relatively small binding energy (~16 meV) of the low-energy band edge. Additionally, we extract the rates of exciton relaxation pathways, revealing a relatively large radiative term of 4.6 x 10 8 s -1 as well as an exciton-exciton annihilation term of 3.6 x 10 -13 cm 3 s -1 that is 3 orders of magnitude smaller than in similar quasi-2D perovskites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Robust Chemiresistive Behavior in Conductive Polymer/MOF Composites

Metal-organic frameworks (MOFs) are promising materials for gas sensing but are often limited to single-use detection. A hybridization strategy is demonstrated synergistically deploying conductive MOFs (cMOFs) and conductive polymers (cPs) as two complementary mixed ionic-electronic conductors in high-performing stand-alone chemiresistors. This work presents significant improvement in i) sensor recovery kinetics, ii) cycling stability, and iii) dynamic range at room temperature. The effect of hybridization across well-studied cMOFs is demonstrated based on 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP) and 2,3,6,7,10,11-hexaiminotriphenylene (HITP) ligands with varied metal nodes (Co, Cu, Ni). A comprehensive mechanistic study is conducted to relate energy band alignments at the heterojunctions between the MOFs and the polymer with sensing thermodynamics and binding kinetics. The findings reveal that hole enrichment of the cMOF component upon hybridization leads to selective enhancement in desorption kinetics, enabling significantly improved sensor recovery at room temperature, and thus long-term response retention. This mechanism is further supported by density functional theory calculations on sorbate–analyte interactions. It is also found that alloying cPs and cMOFs enables facile thin film co-processing and device integration, potentially unlocking the use of these hybrid conductors in diverse electronic applications.

36 MATERIALS SCIENCE↗

Application of a mixed metal oxide catalyst to a metallic substrate

A method for applying a mixed metal oxide catalyst to a metallic substrate for the creation of a robust, high temperature catalyst system for use in decomposing propellants, particularly hydrogen peroxide propellants, for use in propulsion systems. The method begins by forming a prepared substrate material consisting of a metallic inner substrate and a bound layer of a noble metal intermediate. Alternatively, a bound ceramic coating, or frit, may be introduced between the metallic inner substrate and noble metal intermediate when the metallic substrate is oxidation resistant. A high-activity catalyst slurry is applied to the surface of the prepared substrate and dried to remove the organic solvent. The catalyst layer is then heat treated to bind the catalyst layer to the surface. The bound catalyst layer is then activated using an activation treatment and calcinations to form the high-activity catalyst system.

Sevener, Kathleen M.↗

Purification of Propylene and Ethylene by a Robust Metal–Organic Framework Mediated by Host–Guest Interactions

Industrial purification of propylene and ethylene requires cryogenic distillation and selective hydrogenation over palladium catalysts to remove propane, ethane and/or trace amounts of acetylene. Here, we report the excellent separation of equimolar mixtures of propylene/propane and ethylene/ethane, and of a 1/100 mixture of acetylene/ethylene by a highly robust microporous material, MFM-520, under dynamic conditions. In situ synchrotron single crystal X-ray diffraction, inelastic neutron scattering and analysis of adsorption thermodynamic parameters reveal that a series of synergistic host-guest interactions involving hydrogen bonding and π&ctdot;π stacking interactions underpin the cooperative binding of alkenes within the pore. Notably, the optimal pore geometry of the material enables selective accommodation of acetylene. The practical potential of this porous material has been demonstrated by fabricating mixed-matrix membranes comprising MFM-520, Matrimid and PIM-1, and these exhibit not only a high permeability for propylene (≈1984 Barrer), but also a separation factor of 7.8 for an equimolar mixture of propylene/propane at 298 K.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗