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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 1,261 records · Page 70
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Deuterium Permeation Through a Self-Supported Palladium-Silver Membrane in Helium Gas Mixtures

Palladium membranes and membrane reactors can separate and purify tritium from impurities in the plasma exhaust processing system for the fusion energy fuel cycle. Membranes can also act as a continuous separation method to remove tritium from helium streams in the breeder blanket tritium extraction system, such as from the purge gas of solid breeders. To investigate the potential of these membranes for these applications, we performed a deuterium permeation campaign with a self-supported palladium-silver (Pd-25Ag wt%) tube of 0.15 m length, 76 µ m wall thickness, and 3.0 mm inner diameter. A gas mixture of 3.95% D 2 and a balance of He was delivered to the inside of the tube and D permeated radially outwards through the membrane into a vacuum chamber. Permeation experiments were conducted at 300 ° C, 350 ° C, 400° C, and 450°C, from 100 to 1000 sccm total flow rate, and with total pressures of 90, 150, 190, and 250 kPa. Further, deuterium permeation was consistently lower than predicted from diffusion-limited permeation models, thus we developed a transport model that included gas-phase mass transfer and surface reactions to model experimental results. The dissociation constant was optimized to fit the developed model to experimental data.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2012

Thermal chemistry of copper(I)-N,N '-di-sec-butylacetamidinate on Cu(110) single-crystal surfaces

The surface chemistry of copper(I)-N,N'-di-sec-butylacetamidinate on Cu(110) single-crystal surfaces has been characterized under ultrahigh vacuum by temperature programmed desorption (TPD) and X-ray photoelectron spectroscopy. A series of thermal stepwise conversions were identified, starting with the partial dissociative adsorption of the copper acetamidinate dimers into a mixture of monomers and dimers on the surface. An early dissociation of a C-N bond leads to the production of N-sec-butylacetamidine, which is detected in TPD experiments in three temperature regimes, the last one centered around 480 K. Butene, and a small amount of butane, is also detected above approximately 500 K, and hydrogen production, an indication of dehydrogenation of surface fragments, is observed at 460, 550 and 670 K. In total, only about 10% of the initial copper(I)-N,N'-di-sec-butylacetamidinate adsorbed monolayer decomposes, and only about {approx}3% of carbon is left behind on the surface after heating to high temperatures. The implications of this surface chemistry to the design of chemical film growth processes using copper acetamidinates as precursors are discussed.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Charged Species Concentration in Combusting Mixtures Using Equilibrium Chemistry

Ionization in flames is of interest in the design and development of modern combustion devices. The identity and concentration of various charged species in reacting mixtures can play an important role in the diagnostics and control of such devices. Simplified chemistry computations that provide good estimates of ionic species in complex flow-fields can be used to model turbulent reacting flows in various combustion devices, greatly reducing the required computational resources for design and development studies. A critical assessment of the use of the equilibrium chemistry method to compute charged species concentration in combusting mixtures under various temperatures, pressures, and thermal disequilibrium conditions is presented. The use of equilibrium chemistry to compute charged species concentrations in propane-air mixtures performed by Calcote and King has been extended. A more accurate computational methodology that includes the effect of negative ions, chemi-ions (H 3 O + and CHO + ), and thermal nonequilibrium was investigated to evaluate the suitability of equilibrium computations for estimating charged species concentrations in reacting mixtures. The results show that equilibrium computations which include the effects of H 3 O + and elevated electron temperatures can indeed explain the levels of ion concentrations observed in laboratory flame experiments under lean and near-stoichiometric conditions. Furthermore, under engine-like conditions at higher temperatures and pressures, equilibrium computations can be used to obtain useful estimates of charged species concentrations in modern combustion devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Soil Oxygen Limits Microbial Phosphorus Utilization in Humid Tropical Forest Soils

Soil phosphorus (P) availability is of special interest in many humid tropical forests, especially those on highly weathered, iron (Fe)- and aluminum (Al)-rich soils where P often limits net primary productivity. Phosphorus cycling is partly dependent on the ability of microbes to compete for P with Fe and Al minerals, which strongly bind P. Soil P availability is also indirectly affected by soil redox conditions due to its effects on microbial activity and reductive dissolution of Fe oxides that may weaken Fe-O-P sorption strength. Here, we explored P sorption, soil Fe (II) concentrations, soil CO2 production, organic and inorganic P pools, and microbial biomass P in tropical soils that typically experience frequent low redox (valley soils), or fluctuating redox conditions (slope soils). Soils from both topographic positions were pre-incubated under oxic or anoxic headspaces and then amended with a mixture of P (as orthophosphate) and carbon (C, as acetate, to maintain microbial activity) and incubated in the dark for 24 h. Phosphorus sorption to the mineral phase occurred on a time scale of seconds to minutes in valley and slope soils, reflecting strong abiotic P sorption capacity. Valley soils were characterized by inherently higher Fe(II) concentrations and lower respiration rates. Under anoxic headspaces, Fe(II) concentrations increased 3-to 5-fold in the both soils. Soil respiration and microbial P utilization declined significantly in both soils under anoxic conditions, regardless of Fe(II) concentrations. Microbial P concentrations were highest when slope soils were incubated under an oxic headspace, despite the high P sorption under these conditions. Our results suggest that microbial P utilization is indirectly limited by low O2 availability and that microbes are able to effectively compete with minerals for P under Fe-oxidizing conditions. These results emphasize the central role of soil microorganisms in regulating P availability, even in the presence of strong abiotic sorption capacity.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS1976

Condensation of water vapor in rarefaction waves. I - Homogeneous nucleation

A detailed theoretical investigation has been made of the condensation of water vapor/carrier gas mixtures in the nonstationary rarefaction wave generated in a shock tube. It is assumed that condensation takes place by homogeneous nucleation. The equations of motion together with the nucleation rate and the droplet growth equations were solved numerically by the method of characteristics and Lax's method of implicit artificial viscosity. It is found that, for the case considered, the condensation wave formed by the collapse of the metastable nonequilibrium state is followed by a shock wave generated by the intersection of characteristics of the same family. The expansion is practically isentropic up to the onset of condensation. The condensation front accelerates in the x,t plane. The results of the computations for a chosen case of water vapor/nitrogen mixture are presented by plotting variations of pressure, nucleation rate, number density of critical clusters, and condensate mass-fraction along three particle paths. Some consideration is given to homogeneous condensation experiments conducted in a shock tube. Although a direct comparison of the present theoretical work and these experiments is not possible, several worthwhile interpretative features have resulted nevertheless.

Sislian, J. P.↗
NASA NTRS1981

Formation of peptides from amino acids by single or multiple additions of ATP to suspensions of nucleoproteinoid microparticles

The synthesis of peptides from individual amino acids or pairs of amino acids and ATP in the presence of catalysis by nucleoproteinoid microparticles is investigated. Experiments were performed with suspensions formed from the condensation of lysine-rich and acidic proteinoids with polyadenylic acid, to which were added glycine, phenylalanine, proline, lysine or glycine-phenylalanine mixtures, and ATP either at once or serially. Peptide yields are found to be greatest for equal amounts of acidic and basic proteinoids. The addition of imidazole is found to alter the preference of glycine-phenylalanine mixtures to form mixed heteropeptides rather than homopeptides. A rapid ATP decay in the peptide synthesis reaction is observed, and a greater yield is obtained for repeated small additions than for a single addition of ATP. The experimental system has properties similar to modern cells, and represents an organizational unit ready for the evolution of associated biochemical pathways.

Nakashima, T.↗
NASA NTRS1986

Fatigue of 1018 steel in hydrogen

Tests are performed at different hydrogen pressures and mechanical load parameter values (applied load, stress concentration factor, applied load frequency) to study enhanced fatigue crack growth in SAE 1018 steel. Oxygen was introduced as a hydrogen-oxygen gas mixture environment in order to compare the role of oxygen in crack inhibition with that previously reported for both static and cyclic loading of higher strength steels. In a number of experiments, a thin film of palladium was applied to the specimen surface to facilitate the study of steel-hydrogen interaction in the absence of any surface impedance to hydrogen entry. The kinetics of the diffusing atoms are found to be influenced by the stress field around the notch tip and the applied frequency. An increment in environmental effect occurred when applied load or stress concentration factor was increased.

Lo, S. H.↗
NASA NTRS1999

Effective Forces Between Colloidal Particles

Colloidal suspensions have proven to be excellent model systems for the study of condensed matter and its phase behavior. Many of the properties of colloidal suspensions can be investigated with a systematic variation of the characteristics of the systems and, in addition, the energy, length and time scales associated with them allow for experimental probing of otherwise inaccessible regimes. The latter property also makes colloidal systems vulnerable to external influences such as gravity. Experiments performed in micro-ravity by Chaikin and Russell have been invaluable in extracting the true behavior of the systems without an external field. Weitz and Pusey intend to use mixtures of colloidal particles with additives such as polymers to induce aggregation and form weak, tenuous, highly disordered fractal structures that would be stable in the absence of gravitational forces. When dispersed in a polarizable medium, colloidal particles can ionize, emitting counterions into the solution. The standard interaction potential in these charged colloidal suspensions was first obtained by Derjaguin, Landau, Verwey and Overbeek. The DLVO potential is obtained in the mean-field linearized Poisson-Boltzmann approximation and thus has limited applicability. For more precise calculations, we have used ab initio density functional theory. In our model, colloidal particles are charged hard spheres, the counterions are described by a continuum density field and the solvent is treated as a homogeneous medium with a specified dielectric constant. We calculate the effective forces between charged colloidal particles by integrating over the solvent and counterion degrees of freedom, taking into account the direct interactions between the particles as well as particle-counterion, counterion-counterion Coulomb, counterion entropic and correlation contributions. We obtain the effective interaction potential between charged colloidal particles in different configurations. We evaluate two- and three-body forces in the bulk as well as study the influence of soft walls. We qualitatively explain the effects of the walls on the forces and demonstrate that many-body effects are negligible in our system. With adjustments in the parameters, the DLVO pair-potential can describe the results quantitatively. Besides electrostatic interactions, entropic depletion effects that arise from (hard-core) exclusion play an important role in determining the behavior of multi-component colloidal suspensions. A standard theory for depletion forces is due to Asakura and Oosawa and is based on the ideal gas approximation. To go beyond this approximation, we have studied entropic forces in molecular dynamics simulations of systems of hard spheres (the effects of the solvent have been ignored). The effective depletion forces for these systems can be found either from equilibrium distribution functions or from direct momentum transfer calculations. Our results obtained by either method show qualitative differences from the Asakura-Oosawa forces, indicating a longer range, higher value at contact and most importantly a more complicated structure, comprising of several maxima and minima. Our calculations include the determination of effective forces between two spheres, a hard sphere and a wall, and the behavior of a hard sphere near a step-edge and a corner. We also demonstrate that such entropic forces do not necessarily satisfy pairwise additivity.

Tehver, Riina↗
NASA NTRS1999

Initial Observations on the Burning of an Ethanol Droplet in Microgravity

Combustion of liquid ethanol represents an important system both from fundamental and practical points of view, Ethanol is currently being used as an additive to gasoline in order to reduce carbon monoxide and particulate emissions as well as to improve the fuel octane rating. A detailed physical understanding of liquid ethanol combustion is therefore necessary to achieve an optimal performance of such fuel blends in practical conditions. Ethanol is also a relatively simple model compound suitable for investigation of important combustion characteristics typical of more complex fuels. In particular, ethanol has been proposed for studies of sooting behavior during droplet burning. The sooting nature of ethanol has pressure sensitivities similar to that of n-heptane, but shifted to a higher range of pressures (1-3 atm). Additionally, liquid ethanol is miscible with water produced during its combustion forming mixtures with azeotropic behavior, a phenomenon important for understanding multi-component, liquid fuel combustion. In this work, we present initial results obtained in a series of recent space-based experiments and develop a detailed model describing the burning of ethanol droplet in microgravity.

Kazakov, Andrei↗
NASA NTRS2002

Analytical/Operational Requirements for the In Situ Chemical Analysis of Cometary and Planetary Environments Using GC-IMS

Exobiology flight experiments require highly sensitive instrumentation for the in situ analysis of the volatile chemical species that occur in the atmospheres and surfaces of various bodies within the solar system. The complex mixtures encountered place a heavy burden on the analytical instrumentation to detect and identify all species present. The minimal resources available onboard for such missions mandate that the instruments provide maximum analytical capabilities with minimal requirements of volume, weight and consumables. The miniCIDEX instrument was developed for the chemical analysis of a cemetery environment. It combined a Gas Chromatograph (GC) with a helium based Ion Mobility Spectrometer (IMS) to fulfill the analytical requirements of a cemetery exobiology mission: universal response; ppb sensitivity; low mass, volume and consumable MiniCIDEX is now a candidate for the chemical analysis instrument of a Titan Aero-rover Mission. The complexity of the analyses will be similar to the comet application with a heavier emphasis on organic molecules. Because the Titan Aero-Rover will be a balloon powered rover, much more attention is placed on the total mass of the instrument package. The GC will likely be a Micro-Electro-Mechanical-System (MEMS) design, smaller than the initial miniCIDEX GC by a factor of ten (with a similar reduction in consumable use). Similar miniaturization of the helium-based IMS will be necessary while maintaining the analytical capabilities. The two mission applications, the analytical requirements, and the evolution of the IMS design to accommodate these requirements will be presented.

Kojiro, Daniel R.↗
NASA NTRS2023

Microstructural Changes and Pb Mobility During the Zircon to Reidite Transformation: Implications for Planetary Impact Chronology

Impact events modify and leave behind a complex history of rock metamorphism on terrestrial planets. Evidence for an impact event may be recorded in physical changes to minerals, such as mineral deformation and formation of high P-T polymorphs, but also in the form of chemical fingerprints, such as enhanced elemental diffusion and isotopic mixing. Here we explore laboratory shock-induced physical and chemical changes to zircon and feldspar, the former of which is of interest because its trace elements abundances and isotope ratios are used extensively in geochemistry and geochronology. To this end, a granular mixture of Bishop Tuff sanidine and Kuehl Lake zircon, both with well characterized Pb isotope compositions, was prepared and then shocked via a flat plate accelerator. The peak pressure of the experiment, as calculated by the impedance matching method, was ~24 GPa although a broader range of P-T conditions is anticipated due to starting sample porosity. Unshocked and shocked materials were characterized via scanning electron microscopy (SEM), electron backscatter diffraction (EBSD), and Raman spectroscopy. These methods show that the starting zircon material had abundant metamict regions, and the conversion of the feldspar to glass in the post-shock material. Analyses of the shocked product also yielded multiple occurrences of the high-pressure ZrSiO 4 polymorph reidite, with some domains up to 300 μm across. The possibility of U-Pb system disturbance was evaluated via laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) and secondary ion mass spectrometry (SIMS). The isotopic data reveal that disturbance of the U-Pb geochronometer in the reidite was minimal (<2% for the main U-Pb geochronometers). To better constrain the P-T conditions during the shock experiment, we complement impedance matching pressure calculations with iSALE2D impact simulations. The simulated results yield a range of P-T conditions experienced during the experiment and show that much of the sample may have reached >30 GPa, which is consistent with formation of reidite. In the recovered shocked material, we identified lamellae of reidite, some of which interlock with zircon lamellae. Reidite {112} twins were identified, which we interpret to have formed to reduce stress between the crystal structure of the host zircon and reidite. These two findings support the interpretation that shear transformation enabled the transition of zircon to reidite. The size and presence of reidite found here indicate that this phase is probably common in impact-shocked crustal rocks that experienced ~25 to ~35 GPa, especially when the target material has porosity. Additionally, shock loading of the zircon and transformation to reidite at these pressures in porous materials is unlikely to significantly disturb the U-Pb system in zircon and that the reidite inherits the primary U and Pb elemental and isotopic ratios from the zircon.

Bishop Tuff↗
DOE OSTI2025

A Fast Framework for Generating Radioactive Mixture Spectra and Its Application to Remote High-Performance Mixture Identification

Remote detection of radioactive materials in mixtures using handheld or portal detectors remains a challenge because of factors such as low concentration, environmental interference, sensor noise, and other complications. This work introduces a fast framework for generating realistic mixture spectra. Moreover, we present mixture isotope identification using data generated by the fast framework. Researchers have examined a range of conventional and recent algorithms within the fields of machine learning and deep learning. An application to uranium enrichment-level prediction has been included. Extensive simulation experiments validated the efficacy of the proposed framework.

GADRAS↗
DOE OSTI2016

CO oxidation on Pt(111) at near ambient pressures

The oxidation of CO on Pt(111) was investigated simultaneously by near ambient pressure X-ray photoelectron spectroscopy and online gas analysis. Different CO:O{sub 2} reaction mixtures at total pressures of up to 1 mbar were used in continuous flow mode to obtain an understanding of the surface chemistry. By temperature-programmed and by isothermal measurements, the onset temperature of the reaction was determined for the different reactant mixtures. Highest turnover frequencies were found for the stoichiometric mixture. At elevated temperatures, the reaction becomes diffusion-limited in both temperature-programmed and isothermal measurements. In the highly active regime, no adsorbates were detected on the surface; it is therefore concluded that the catalyst surface is in a metallic state, within the detection limits of the experiment, under the applied conditions. Minor bulk impurities such as silicon were observed to influence the reaction up to total inhibition by formation of non-platinum oxides.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Effectiveness of Sorbents to Reduce Mercury Methylation

Experiments were completed to assess the effectiveness of Biochar, ThiolSAMMS®, SediMite™, and Organoclay-199 to decrease methylmercury (MeHg) production by the known mercury methylator, Desulfovibrio desulfuricans ND132 (ND132), and to decrease aqueous (i.e., 0.2 μM filter passing) MeHg concentrations. Mercury (Hg) was introduced as Hg(II) or a preequilibrated Hg-DOM (dissolved organic matter) complex. Individual experiments tested the effect of sulfate concentration and Hg-sorbent equilibration time (up to 1 year). The sorbents provided little, if any, inhibition of total MeHg production, but decreased the percentage of MeHg that passed a 0.2 μm filter. Total MeHg produced was substantially greater than the calculated equilibrium aqueous inorganic Hg (Hgi), based on sorption isotherms, implying mercury assumed to be sorbed at the start of the assay was bioaccessible over the 24-h methylation timeframe. MeHg production increased when Hgi was introduced as an Hg:DOM complex, compared to Hg(II). Some of the increased MeHg production may be attributed to lower Hgi sorption with DOM present, but a substantial amount of sorbed Hg must have been accessible also. DOM also increased the filter-passing MeHg fraction, stressing the importance of Hg-DOM and MeHg-DOM interactions in experimental investigations. Sulfate concentrations did not affect Hg(II) methylation and could not explain the increased methylation seen with the Hg:DOM complex. Extended equilibration of Hg-sorbent mixtures for up to 1 year before the methylation assays did not affect the amount of MeHg produced for Biochar or SediMite treatments, but significantly lowered MeHg production for ThiolSAMMS. As a result, inclusion of DOM in these experiments presented the sorbents with a more environmentally relevant form of Hg and lowered sorbent effectiveness to decrease MeHg production and sorb produced MeHg.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

An experimental and chemical kinetic modeling study of 4-butoxyheptane combustion

Here, the combustion kinetics of a novel oxygenated bioblendstock for diesel, 4-butoxyheptane (4-BH), was investigated experimentally using a flow reactor and a heated, high-pressure shock tube. The flow reactor experiments employed oxygen as the oxidizer and helium as the diluent with oxidation conducted at atmospheric pressure and 10 bar for temperatures from 400 to 1000 K at 20-K intervals. The fuel, oxidizer, and diluent flow rates were varied at different temperatures to maintain a constant initial fuel mole fraction of 1000 ppm, with stoichiometric equivalence ratio, and a residence time of 2.0 s. The reacted gas was fed to two separate GC systems that could qualitatively and quantitatively detect product species. Additionally, real fuel-air ignition delay time (IDT) data were collected using a heated, high-pressure shock-tube facility. Fuel lean (φ = 0.5) and stoichiometric (φ = 1.0) mixtures were investigated at 10 atm as well as at 30 atm for the fuel lean case for temperatures between 847 and 1259 K. A detailed chemical kinetics mechanism was developed to model the product distribution from the flow reactor and IDTs from the shock tube. The proposed model was able to predict the double NTC behavior in flow reactor experiments reasonably well. Model predictions at low temperatures were observed to be highly sensitive to the rate constants of ketohydroperoxide (KHP) decomposition in the case of the OOH group in α position which were modeled based on existing literature studies on ethers. It was noted that in the absence of theoretical or experimental studies, the rate constants for KHP decomposition used in the literature were empirically set. Additional studies are required to address the gap in model prediction obtained in this study and to reduce the uncertainty in kinetics models for ether oxidation. Predicted product concentrations and IDTs showed some quantitative agreement with experimental data, but the overall reactivity of the IDTs is underpredicted. Additionally, significant deviation is observed for the IDT results at 10 atm for the stoichiometric case with minor deviations for the other cases. The reaction pathways to the missing products were then further analyzed theoretically through quantum-mechanical calculations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Role of Fe(II) Content in Olivine Carbonation in Wet Supercritical CO2

Basalt geologic reservoirs are targeted for carbon storage because they are abundant in divalent silicates such as olivine ((Mg,Fe)2SiO4) that can carbonate to permanently trap CO2. At reservoir conditions, CO2 is a supercritical fluid that contains dissolved H2O, which adsorbs to minerals as nanometer-thin films. In this study, the role of Fe(II) in the thin H2O film carbonation of olivine was investigated using in situ high pressure infrared spectroscopy and ab initio thermodynamic calculations. Experiments were performed at 50 °C and 90 bar in both scCO2 and scCO2 with 1% H2 at a relative humidity of 79% on synthetic forsterite, fayalite, and two Mg-Fe mixture olivines (MgxFe1-x)2SiO4 (x = 0.33 and 0.66). Carbonation rates and extents are lower with increasing concentrations of Fe(II) in the olivine, but the addition of 1% H2 increases carbonation in Fe(II)-rich olivines. These trends are explained according to the dependencies of olivine acidic solubilities, carbonate precipitation equilibria, and dissolution/growth kinetics on Fe(II) content, and by considering that Fe(II)-rich olivines can undergo competing oxidation reactions by O2 and H2O and Fe(III)-containing oxides. Given that CO2 injected into the subsurface will be relatively oxic, the oxidation of Fe(II)-rich olivines could impact their carbonation potential.

Wood, Cecelia E.↗
DOE OSTI2016

Solvents Polarity Governs Ion Interactions and Transport in a Solvated Room Temperature Ionic Liquid

We explore the influence of the solvent dipole moment on cation anion interactions and transport in 1-butyl-3-methyl-imidazolium bis-(trifluoromethylsulfonyl), [BMIM+][Tf2N ]. Free energy profiles derived from atomistic molecular dynamics (MD) simulations show a correlation of the cation anion separation and the equilibrium depth of the potential of mean force with the dipole moment of the solvent. Correlations of the ion diffusivity with the dipole moment and the concentration of the solvent were further demonstrated by classical MD simulations. Quasi-elastic neutron scattering experiments with deuterated solvents reveal a complex picture of nanophase separation into the ionic liquid-rich and solvent-rich phases. The experiment corroborates the trend of concentration- and dipole moment-dependent enhancement of ion mobility by the solvent, as suggested by the simulations. Despite the considerable structural complexity of ionic liquid solvent mixtures, we can rationalize and generalize the trends governing ionic transport in these complex electrolytes.

Osti, Naresh C↗
DOE OSTI2017

Ethylene oligomerization in metal–organic frameworks bearing nickel( ii ) 2,2'-bipyridine complexes

Here, the metal–organic frameworks Zr 6 O 4 (OH) 4 (bpydc) 6 ( 1 ; bpydc 2– = 2,2'-bipyridine-5,5'-dicarboxylate) and Zr 6 O 4 (OH) 4 (bpydc) 0.84 (bpdc) 5.16 ( 2 ; bpdc 21458983 = biphenyl-4,4'-dicarboxylate) were readily metalated with Ni(DME)Br 2 (DME = dimethoxyethane) to produce the corresponding metalated frameworks 1 (NiBr 2 ) 6 and 2 (NiBr 2 ) 0.84 . Both nickel( ii )-containing frameworks catalyze the oligomerization of ethylene in the presence of Et 2 AlCl. In these systems, the pore environment around the active nickel sites significantly influences their selectivity for formation of oligomers over polymer. Specifically, the single-crystal structure of 1 (NiBr 2 ) 5.64 reveals that surrounding metal–linker complexes enforce a steric environment on each nickel site that causes polymer formation to become favorable. Minimizing this steric congestion by isolating the nickel( ii ) bipyridine complexes in the mixed-linker framework 2 (NiBr 2 ) 0.84 markedly improves both the catalytic activity and selectivity for oligomers. Furthermore, both frameworks give product mixtures that are enriched in shorter olefins (C 4–10 ), leading to deviations from the expected Schulz–Flory distribution of oligomers. Although these deviations indicate possible pore confinement effects on selectivity, control experiments using the nickel-treated biphenyl framework Zr 6 O 4 (OH) 4 (bpdc) 6 (NiBr 2 ) 0.14 ( 3 (NiBr 2 ) 0.14 ) reveal that they likely arise at least in part from the presence of nickel species that are not ligated by bipyridine within 1 (NiBr 2 ) 5.64 and 2 (NiBr 2 ) 0.84 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗