Effect of Polymorphism on the Sorption Properties of a Flexible Square-Lattice Topology Coordination Network.

The stimulus-responsive behavior of coordination networks (CNs), which switch between closed (nonporous) and open (porous) phases, is of interest because of its potential utility in gas storage and separation. Herein, we report two polymorphs of a new square-lattice (sql) topology CN, X-sql-1-Cu, of formula [Cu(Imibz)2]n (HImibz = {[4-(1H-imidazol-1-yl)phenylimino]methyl}benzoic acid), isolated from the as-synthesized CN X-sql-1-Cu-(MeOH)2·2MeOH, which subsequently transformed to a narrow pore solvate, X-sql-1-Cu-A·MeOH, upon mild activation (drying in air or heating at 333 K under nitrogen). X-sql-1-Cu-A·MeOH contains MeOH in cavities, which was removed through exposure to vacuum for 2 h, yielding the nonporous (closed) phase X-sql-1-Cu-A. In contrast, a more dense polymorph, X-sql-1-Cu-B, was obtained by exposing X-sql-1-Cu-(MeOH)2·2MeOH directly to vacuum for 2 h. Gas sorption studies conducted on X-sql-1-Cu-A and X-sql-1-Cu-B revealed different switching behaviors to two open phases (X-sql-1-Cu·CO2 and X-sql-1-Cu·C2H2), with different gate-opening threshold pressures for CO2 at 195 K and C2H2 at 278 K. Coincident CO2 sorption and in situ powder X-ray diffraction studies at 195 K revealed that X-sql-1-Cu-A transformed to X-sql-1-Cu-B after the first sorption cycle and that the CO2-induced switching transformation was thereafter reversible. The results presented herein provide insights into the relationship between two polymorphs of a CN and the effect of polymorphism upon gas sorption properties. To the best of our knowledge, whereas sql networks such as X-sql-1-Cu are widely studied in terms of their structural and sorption properties, this study represents only the second example of an in-depth study of the sorption properties of polymorphic sql networks.

Resolving Multielement Semiconductor Nanocrystals at the Atomic Level: Complete Deciphering of Domains and Order in Complex CuαZnßSnγSeδ (CZTSe) Tetrapods.

Semiconductor nanocrystals (NCs) with high elemental and structural complexity can be engineered to tailor for electronic, photovoltaic, thermoelectric, and battery applications etc. However, this greater complexity causes ambiguity in the atomic structure understanding. This in turn hinders the mechanistic studies of nucleation and growth, the theoretical calculations of functional properties, and the capability to extend functional design across complementary semiconductor nanocrystals. Herein, we successfully deciphered the atomic arrangements of 4 different nanocrystal domains in CuαZnßSnγSeδ (CZTSe) nanocrystals using crucial zone axis analysis on multiple crystals in different orientations. The results show that the essence of crystallographic progression from binary to multielemental semiconductors is actually the change of theoretical periodicity. This transition is caused by decreased symmetry in the crystal instead of previously assumed crystal deformation. We further reveal that these highly complex crystalline entities have highly ordered element arrangements as opposed to the previous understanding that their elemental orderings are random.

Crystal Engineering of a New Hexafluorogermanate Pillared Hybrid Ultramicroporous Material Delivers Enhanced Acetylene Selectivity.

Hybrid ultramicroporous materials (HUMs), metal-organic platforms that incorporate inorganic pillars, are a promising class of porous solids. A key area of interest for such materials is gas separation, where HUMs have already established benchmark performances. Thanks to their ready compositional modularity, we report the design and synthesis of a new HUM, GEFSIX-21-Cu, incorporating the ligand pypz (4-(3,5-dimethyl-1H-pyrazol-4-yl)pyridine, 21) and GeF62- pillaring anions. GEFSIX-21-Cu delivers on two fronts: first, it displays an exceptionally high C2H2 adsorption capacity (≥5 mmol g-1) which is paired with low uptake of CO2 (<2 mmol g-1), and, second, a low enthalpy of adsorption for C2H2 (ca. 32 kJ mol-1). This combination is rarely seen in the C2H2 selective physisorbents reported thus far, and not observed in related isostructural HUMs featuring pypz and other pillaring anions. Dynamic column breakthrough experiments for 1:1 and 2:1 C2H2/CO2 mixtures revealed GEFSIX-21-Cu to selectively separate C2H2 from CO2, yielding ≥99.99% CO2 effluent purities. Temperature-programmed desorption experiments revealed full sorbent regeneration in <35 min at 60 °C, reinforcing HUMs as potentially technologically relevant materials for strategic gas separations.

Highly Selective p-Xylene Separation from Mixtures of C8 Aromatics by a Nonporous Molecular Apohost.

High and increasing production of separation of C8 aromatic isomers demands the development of purification methods that are efficient, scalable, and inexpensive, especially for p-xylene, PX, the largest volume C8 commodity. Herein, we report that 4-(1H-1,2,4-triazol-1-yl)-phenyl-1H-benzo[de]isoquinoline-1,3(2H)-dione (TPBD), a molecular compound that can be prepared and scaled up via solid-state synthesis, exhibits exceptional PX selectivity over each of the other C8 isomers, o-xylene (OX), m-xylene (MX), and ethylbenzene (EB). The apohost or α form of TPBD was found to exhibit conformational polymorphism in the solid state enabled by rotation of its triazole and benzene rings. TPBD-αI and TPBD-αII are nonporous polymorphs that transformed to the same PX inclusion compound, TPBD-PX, upon contact with liquid PX. TPBD enabled highly selective capture of PX, as established by competitive slurry experiments involving various molar ratios in binary, ternary, and quaternary mixtures of C8 aromatics. Binary selectivity values for PX as determined by 1H NMR spectroscopy and gas chromatography ranged from 22.4 to 108.4, setting new benchmarks for both PX/MX (70.3) and PX/EB (59.9) selectivity as well as close to benchmark selectivity for PX/OX (108.4). To our knowledge, TPBD is the first material of any class to exhibit such high across-the-board PX selectivity from quaternary mixtures of C8 aromatics under ambient conditions. Crystallographic and computational studies provide structural insight into the PX binding site in TPBD-PX, whereas thermal stability and capture kinetics were determined by variable-temperature powder X-ray diffraction and slurry tests, respectively. That TPBD offers benchmark PX selectivity and facile recyclability makes it a prototypal molecular compound for PX purification or capture under ambient conditions.

Anticancer Potential of Dendritic Poly(aryl ether)-Substituted Polypyridyl Ligand-Based Ruthenium(II) Coordination Entities.

This paper studies the anticancer potency of dendritic poly(aryl ether)-substituted polypyridyl ligand-based ruthenium(II) coordination entities. The dendritic coordination entities were successfully designed, synthesized, and characterized by different spectral methods such as Fourier transform infrared (FTIR), 1H and 13C- NMR, and mass spectrometry. Further, to understand the structure and solvation behavior of the coordination entities, we performed all-atom molecular dynamics (MD) simulations. The behavior, configuration, and size of the coordination entities in DMSO and water were studied by calculating the radius of gyration (Rg) and solvent-accessible surface area (SASA). The MTT assay was used to assess the in vitro cytotoxicity of all of the coordination entities against cancerous A549 (lung cancer cells), MDA MB 231 (breast cancer cells), and HepG2 (liver cancer cells) and was found to be good with comparable IC50 values with respect to the standard drug cisplatin. The coordination entities exhibited dose dependence, and the highest activity was shown against HepG2 cell lines in comparison to the other cancer cell lines. In addition, fluorescence staining studies, such as AO/EB, DAPI, and cell death analysis by PI staining, were performed on the coordination entities to understand the apoptosis mechanism. Furthermore, reactive oxygen species (ROS) and mitochondrial membrane potential (MMP) assays confirmed apoptosis in cancer cells via the mitochondrial pathway. The DNA fragmentation assay was done followed by molecular docking analysis with DNA executed to strengthen and support the experimental observations.

Shape-Memory Effect Enabled by Ligand Substitution and CO2 Affinity in a Flexible SIFSIX Coordination Network.

We report that linker ligand substitution involving just one atom induces a shape-memory effect in a flexible coordination network. Specifically, whereas SIFSIX-23-Cu, [Cu(SiF6 )(L)2 ]n , (L=1,4-bis(1-imidazolyl)benzene, SiF6 2- =SIFSIX) has been previously reported to exhibit reversible switching between closed and open phases, the activated phase of SIFSIX-23-CuN , [Cu(SiF6 )(LN )2 ]n (LN =2,5-bis(1-imidazolyl)pyridine), transformed to a kinetically stable porous phase with strong affinity for CO2 . As-synthesized SIFSIX-23-CuN , α, transformed to less open, γ, and closed, ß, phases during activation. ß did not adsorb N2 (77 K), rather it reverted to α induced by CO2 at 195, 273 and 298 K. CO2 desorption resulted in α', a shape-memory phase which subsequently exhibited type-I isotherms for N2 (77 K) and CO2 as well as strong performance for separation of CO2 /N2 (15/85) at 298 K and 1 bar driven by strong binding (Qst =45-51 kJ/mol) and excellent CO2 /N2 selectivity (up to 700). Interestingly, α' reverted to ß after re-solvation/desolvation. Molecular simulations and density functional theory (DFT) calculations provide insight into the properties of SIFSIX-23-CuN .

Hf-Based MOF for Rapid and Selective Sensing of a Nerve Agent Simulant and an Aminophenol: Insights from Experiments and Theory.

The metal-organic framework (MOF) Hf-DUT-52 was prepared with diamino functionality by the solvothermal method. This material displayed fluorometric sensing ability toward a nerve agent simulant (diethyl chlorophosphate (DCP)) and 3-diethylaminophenol (3-DEAP). It is the first-ever reported fluorescent MOF sensor for DCP and 3-DEAP. Apart from a fast response (<5 s), the sensor had a very low detection limit for both DCP and DEAP (limit of detection (LOD) values for DCP and 3-DEAP sensing were 9 and 125 nM, respectively). The obtained detection limit is the second lowest among all of the reported optical sensors for DCP. The sensor also displayed its capability to identify the presence of trace amount of DCP in various natural water specimens with good selectivity. Moreover, MOF@cotton composites were developed for visual, on-site, nanomolar-level detection of both targeted analytes. Furthermore, a MOF@PVA thin film was fabricated and successfully utilized for the detection of highly volatile and deadly poisonous DCP in the vapor phase. The sensor was also recyclable for up to five cycles without losing appreciable efficiency. Density functional theory (DFT)-based periodic and cluster calculations were performed to shed light on the sensing ability of the MOF by studying the interactions of DCP and DEAP with the MOF. Our theoretical results reveal the importance of linker defects and water chemisorption on the adsorption/complexation of the analytes at uncoordinated Hf sites.

Role of decomposition products in the oxidation of cyclohexene using a manganese(III) complex.

Metal complexes are extensively explored as catalysts for oxidation reactions; molecular-based mechanisms are usually proposed for such reactions. However, the roles of the decomposition products of these materials in the catalytic process have yet to be considered for these reactions. Herein, the cyclohexene oxidation in the presence of manganese(III) 5,10,15,20-tetra(4-pyridyl)-21H,23H-porphine chloride tetrakis(methochloride) (1) in a heterogeneous system via loading the complex on an SBA-15 substrate is performed as a study case. A molecular-based mechanism is usually suggested for such a metal complex. Herein, 1 was selected and investigated under the oxidation reaction by iodosylbenzene or (diacetoxyiodo)benzene (PhI(OAc)2). In addition to 1, at least one of the decomposition products of 1 formed during the oxidation reaction could be considered a candidate to catalyze the reaction. First-principles calculations show that Mn dissolution is energetically feasible in the presence of iodosylbenzene and trace amounts of water.

Highly Productive C3H4/C3H6 Trace Separation by a Packing Polymorph of a Layered Hybrid Ultramicroporous Material.

Ultramicroporous materials can be highly effective at trace gas separations when they offer a high density of selective binding sites. Herein, we report that sql-NbOFFIVE-bpe-Cu, a new variant of a previously reported ultramicroporous square lattice, sql, topology material, sql-SIFSIX-bpe-Zn, can exist in two polymorphs. These polymorphs, sql-NbOFFIVE-bpe-Cu-AA (AA) and sql-NbOFFIVE-bpe-Cu-AB (AB), exhibit AAAA and ABAB packing of the sql layers, respectively. Whereas NbOFFIVE-bpe-Cu-AA (AA) is isostructural with sql-SIFSIX-bpe-Zn, each exhibiting intrinsic 1D channels, sql-NbOFFIVE-bpe-Cu-AB (AB) has two types of channels, the intrinsic channels and extrinsic channels between the sql networks. Gas and temperature induced transformations of the two polymorphs of sql-NbOFFIVE-bpe-Cu were investigated by pure gas sorption, single-crystal X-ray diffraction (SCXRD), variable temperature powder X-ray diffraction (VT-PXRD), and synchrotron PXRD. We observed that the extrinsic pore structure of AB resulted in properties with potential for selective C3H4/C3H6 separation. Subsequent dynamic gas breakthrough measurements revealed exceptional experimental C3H4/C3H6 selectivity (270) and a new benchmark for productivity (118 mmol g-1) of polymer grade C3H6 (purity >99.99%) from a 1:99 C3H4/C3H6 mixture. Structural analysis, gas sorption studies, and gas adsorption kinetics enabled us to determine that a binding "sweet spot" for C3H4 in the extrinsic pores is behind the benchmark separation performance. Density-functional theory (DFT) calculations and Canonical Monte Carlo (CMC) simulations provided further insight into the binding sites of C3H4 and C3H6 molecules within these two hybrid ultramicroporous materials, HUMs. These results highlight, to our knowledge for the first time, how pore engineering through the study of packing polymorphism in layered materials can dramatically change the separation performance of a physisorbent.

One Atom Can Make All the Difference: Gas-Induced Phase Transformations in Bisimidazole-Linked Diamondoid Coordination Networks.

Coordination networks (CNs) that undergo gas-induced transformation from closed (nonporous) to open (porous) structures are of potential utility in gas storage applications, but their development is hindered by limited control over their switching mechanisms and pressures. In this work, we report two CNs, [Co(bimpy)(bdc)]n (X-dia-4-Co) and [Co(bimbz)(bdc)]n (X-dia-5-Co) (H2bdc = 1,4-benzendicarboxylic acid; bimpy = 2,5-bis(1H-imidazole-1-yl)pyridine; bimbz = 1,4-bis(1H-imidazole-1-yl)benzene), that both undergo transformation from closed to isostructural open phases involving at least a 27% increase in cell volume. Although X-dia-4-Co and X-dia-5-Co only differ from one another by one atom in their N-donor linkers (bimpy = pyridine, and bimbz = benzene), this results in different pore chemistry and switching mechanisms. Specifically, X-dia-4-Co exhibited a gradual phase transformation with a steady increase in the uptake when exposed to CO2, whereas X-dia-5-Co exhibited a sharp step (type F-IV isotherm) at P/P0 ≈ 0.008 or P ≈ 3 bar (195 or 298 K, respectively). Single-crystal X-ray diffraction, in situ powder XRD, in situ IR, and modeling (density functional theory calculations, and canonical Monte Carlo simulations) studies provide insights into the nature of the switching mechanisms and enable attribution of pronounced differences in sorption properties to the changed pore chemistry.

A Robust Molecular Porous Material for C2 H2 /CO2 Separation.

A molecular porous material, MPM-2, comprised of cationic [Ni2 (AlF6 )(pzH)8 (H2 O)2 ] and anionic [Ni2 Al2 F11 (pzH)8 (H2 O)2 ] complexes that generate a charge-assisted hydrogen-bonded network with pcu topology is reported. The packing in MPM-2 is sustained by multiple interionic hydrogen bonding interactions that afford ultramicroporous channels between dense layers of anionic units. MPM-2 is found to exhibit excellent stability in water (>1 year). Unlike most hydrogen-bonded organic frameworks which typically show poor stability in organic solvents, MPM-2 exhibited excellent stability with respect to various organic solvents for at least two days. MPM-2 is found to be permanently porous with gas sorption isotherms at 298 K revealing a strong affinity for C2 H2 over CO2 thanks to a high (ΔQst )AC [Qst (C2 H2 ) - Qst (CO2 )] of 13.7 kJ mol-1 at low coverage. Dynamic column breakthrough experiments on MPM-2 demonstrated the separation of C2 H2 from a 1:1 C2 H2 /CO2 mixture at 298 K with effluent CO2 purity of 99.995% and C2 H2 purity of >95% after temperature-programmed desorption. C-H···F interactions between C2 H2 molecules and F atoms of AlF6 3- are found to enable high selectivity toward C2 H2 , as determined by density functional theory simulations.

Modeling Polyzwitterion-Based Drug Delivery Platforms: A Perspective of the Current State-of-the-Art and Beyond.

Drug delivery platforms are anticipated to have biocompatible and bioinert surfaces. PEGylation of drug carriers is the most approved method since it improves water solubility and colloid stability and decreases the drug vehicles' interactions with blood components. Although this approach extends their biocompatibility, biorecognition mechanisms prevent them from biodistribution and thus efficient drug transfer. Recent studies have shown (poly)zwitterions to be alternatives for PEG with superior biocompatibility. (Poly)zwitterions are super hydrophilic, mainly stimuli-responsive, easy to functionalize and they display an extremely low protein adsorption and long biodistribution time. These unique characteristics make them already promising candidates as drug delivery carriers. Furthermore, since they have highly dense charged groups with opposite signs, (poly)zwitterions are intensely hydrated under physiological conditions. This exceptional hydration potential makes them ideal for the design of therapeutic vehicles with antifouling capability, i.e., preventing undesired sorption of biologics from the human body in the drug delivery vehicle. Therefore, (poly)zwitterionic materials have been broadly applied in stimuli-responsive "intelligent" drug delivery systems as well as tumor-targeting carriers because of their excellent biocompatibility, low cytotoxicity, insignificant immunogenicity, high stability, and long circulation time. To tailor (poly)zwitterionic drug vehicles, an interpretation of the structural and stimuli-responsive behavior of this type of polymer is essential. To this end, a direct study of molecular-level interactions, orientations, configurations, and physicochemical properties of (poly)zwitterions is required, which can be achieved via molecular modeling, which has become an influential tool for discovering new materials and understanding diverse material phenomena. As the essential bridge between science and engineering, molecular simulations enable the fundamental understanding of the encapsulation and release behavior of intelligent drug-loaded (poly)zwitterion nanoparticles and can help us to systematically design their next generations. When combined with experiments, modeling can make quantitative predictions. This perspective article aims to illustrate key recent developments in (poly)zwitterion-based drug delivery systems. We summarize how to use predictive multiscale molecular modeling techniques to successfully boost the development of intelligent multifunctional (poly)zwitterions-based systems.

Enhanced Photocatalytic Hydrogen Evolution from Water Splitting on Ta2O5/SrZrO3 Heterostructures Decorated with CuxO/RuO2 Cocatalysts.

Photocatalytic H2 generation by water splitting is a promising alternative for producing renewable fuels. This work synthesized a new type of Ta2O5/SrZrO3 heterostructure with Ru and Cu (RuO2/CuxO/Ta2O5/SrZrO3) using solid-state chemistry methods to achieve a high H2 production of 5164 µmol g-1 h-1 under simulated solar light, 39 times higher than that produced using SrZrO3. The heterostructure performance is compared with other Ta2O5/SrZrO3 heterostructure compositions loaded with RuO2, CuxO, or Pt. CuxO is used to showcase the usage of less costly cocatalysts to produce H2. The photocatalytic activity toward H2 by the RuO2/CuxO/Ta2O5/SrZrO3 heterostructure remains the highest, followed by RuO2/Ta2O5/SrZrO3 > CuxO/Ta2O5/SrZrO3 > Pt/Ta2O5/SrZrO3 > Ta2O5/SrZrO3 > SrZrO3. Band gap tunability and high optical absorbance in the visible region are more prominent for the heterostructures containing cocatalysts (RuO2 or CuxO) and are even higher for the binary catalyst (RuO2/CuxO). The presence of the binary catalyst is observed to impact the charge carrier transport in Ta2O5/SrZrO3, improving the solar to hydrogen conversion efficiency. The results represent a valuable contribution to the design of SrZrO3-based heterostructures for photocatalytic H2 production by solar water splitting.

Elucidation of Structure-Activity Relations in Proton Electroreduction at Pd Surfaces: Theoretical and Experimental Study.

The structure-activity relationship is a cornerstone topic in catalysis, which lays the foundation for the design and functionalization of catalytic materials. Of particular interest is the catalysis of the hydrogen evolution reaction (HER) by palladium (Pd), which is envisioned to play a major role in realizing a hydrogen-based economy. Interestingly, experimentalists observed excess heat generation in such systems, which became known as the debated "cold fusion" phenomenon. Despite the considerable attention on this report, more fundamental knowledge, such as the impact of the formation of bulk Pd hydrides on the nature of active sites and the HER activity, remains largely unexplored. In this work, classical electrochemical experiments performed on model Pd(hkl) surfaces, "noise" electrochemical scanning tunneling microscopy (n-EC-STM), and density functional theory are combined to elucidate the nature of active sites for the HER. Results reveal an activity trend following Pd(111) > Pd(110) > Pd(100) and that the formation of subsurface hydride layers causes morphological changes and strain, which affect the HER activity and the nature of active sites. These findings provide significant insights into the role of subsurface hydride formation on the structure-activity relations toward the design of efficient Pd-based nanocatalysts for the HER.

Surprisingly Low Reactivity of Layered Manganese Oxide toward Water Oxidation in Fe/Ni-Free Electrolyte under Alkaline Conditions.

So far, many studies on the oxygen-evolution reaction (OER) by Mn oxides have been focused on activity; however, the identification of the best performing active site and corresponding catalytic cycles is also of critical importance. Herein, the real intrinsic activity of layered Mn oxide toward OER in Fe/Ni-free KOH is studied for the first time. At pH ≈ 14, the onset of OER for layered Mn oxide in the presence of Fe/Ni-free KOH happens at 1.72 V (vs reversible hydrogen electrode (RHE)). In the presence of Fe ions, a 190 mV decrease in the overpotential of OER was recorded for layered Mn oxide as well as a significant decrease (from 172.8 to 49 mV/decade) in the Tafel slope. Furthermore, we find that both Ni and Fe ions increase OER remarkably in the presence of layered Mn oxide, but that pure layered Mn oxide is not an efficient catalyst for OER without Ni and Fe under alkaline conditions. Thus, pure layered Mn oxide and electrolytes are critical factors in finding the real intrinsic activity of layered Mn oxide for OER. Our results call into question the high efficiency of layered Mn oxides toward OER under alkaline conditions and also elucidate the significant role of Ni and Fe impurities in the electrolyte in the presence of layered Mn oxide toward OER under alkaline conditions. Overall, a computational model supports the conclusions from the experimental structural and electrochemical characterizations. In particular, substitutional doping with Fe decreases the thermodynamic OER overpotential up to 310 mV. Besides, the thermodynamic OER onset potential calculated for the Fe-free structures is higher than 1.7 V (vs RHE) and, thus, not in the stability range of Mn oxides.

The First Sulfate-Pillared Hybrid Ultramicroporous Material, SOFOUR-1-Zn, and Its Acetylene Capture Properties.

Hybrid ultramicroporous materials, HUMs, are comprised of metal cations linked by combinations of inorganic and organic ligands. Their modular nature makes them amenable to crystal engineering studies, which have thus far afforded four HUM platforms (as classified by the inorganic linkers). HUMs are of practical interest because of their benchmark gas separation performance for several industrial gas mixtures. We report herein design and gram-scale synthesis of the prototypal sulfate-linked HUM, the fsc topology coordination network ([Zn(tepb)(SO4 )]n ), SOFOUR-1-Zn, tepb=(tetra(4-pyridyl)benzene). Alignment of the sulfate anions enables strong binding to C2 H2 via O⋅⋅⋅HC interactions but weak CO2 binding, affording a new benchmark for the difference between C2 H2 and CO2 heats of sorption at low loading (ΔQst =24 kJ mol-1 ). Dynamic column breakthrough studies afforded fuel-grade C2 H2 from trace (1 : 99) or 1 : 1 C2 H2 /CO2 mixtures, outperforming its SiF6 2- analogue, SIFSIX-22-Zn.

Breaking the trade-off between selectivity and adsorption capacity for gas separation.

The trade-off between selectivity and adsorption capacity with porous materials is a major roadblock to reducing the energy footprint of gas separation technologies. To address this matter, we report herein a systematic crystal engineering study of C2H2 removal from CO2 in a family of hybrid ultramicroporous materials (HUMs). The HUMs are composed of the same organic linker ligand, 4-(3,5-dimethyl-1H-pyrazol-4-yl)pyridine, pypz, three inorganic pillar ligands, and two metal cations, thereby affording six isostructural pcu topology HUMs. All six HUMs exhibited strong binding sites for C2H2 and weaker affinity for CO2. The tuning of pore size and chemistry enabled by crystal engineering resulted in benchmark C2H2/CO2 separation performance. Fixed-bed dynamic column breakthrough experiments for an equimolar (v/v = 1:1) C2H2/CO2 binary gas mixture revealed that one sorbent, SIFSIX-21-Ni, was the first C2H2 selective sorbent that combines exceptional separation selectivity (27.7) with high adsorption capacity (4 mmol·g-1).

High Working Capacity Acetylene Storage at Ambient Temperature Enabled by a Switching Adsorbent Layered Material.

Unlike most gases, acetylene storage is a challenge because of its inherent pressure sensitivity. Herein, a square lattice (sql) coordination network [Cu(4,4'-bipyridine)2(BF4)2]n (sql-1-Cu-BF4) is investigated with respect to its C2H2 sorption behavior from 189 to 298 K. The C2H2 sorption studies revealed that sql-1-Cu-BF4 exhibits multistep isotherms that are temperature-dependent and consistent with the transformation from "closed" (nonporous) to four "open" (porous) phases induced by the C2H2 uptake. The Clausius-Clapeyron equation was used to calculate the performance of sql-1-Cu-BF4 for C2H2 storage at pressures >1 bar, which revealed that its volumetric working capacity at 288 K is slightly superior to acetone (174 vs 170 cm3 cm-3) over a safer pressure range (1-3.5 vs 1-15 bar). Molecular simulations provided insights into the observed switching phenomena, revealing that the layer expansion of sql-1-Cu-BF4 occurs via intercalation and inclusion of C2H2. These results indicate that switching adsorbent layered materials offer promise for utility in the context of C2H2 storage and delivery.

Oxygen-Evolution Reaction by a Palladium Foil in the Presence of Iron.

Herein, we investigate the oxygen-evolution reaction (OER) and electrochemistry of a Pd foil in the presence of iron under alkaline conditions (pH ≈ 13). As a source of iron, K2FeO4 is employed, which is soluble under alkaline conditions in contrast to many other Fe salts. Immediately after reacting with the Pd foil, [FeO4]2- causes a significant increase in OER and changes in the electrochemistry of Pd. In the absence of this Fe source and under OER, Pd(IV) is stable, and hole accumulation occurs, while in the presence of Fe this accumulation of stored charges can be used for OER. A Density Functional Theory (DFT) based thermodynamic model suggests an oxygen bridge vacancy as an active site on the surface of PdO2 and an OER overpotential of 0.42 V. A substitution of Pd with Fe at this active site reduces the calculated OER overpotential to 0.35 V. The 70 mV decrease in overpotential is in good agreement with the experimentally measured decrease of 60 mV in the onset potential. In the presence of small amounts of Fe salt, our results point toward the Fe doping of PdO2 rather than extra framework FeOx (Fe(OH)3, FeO(OH), and KFeO2) species on top of PdO2 as the active OER sites.