Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “ALKANE”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 397 records · Page 22
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Creating values from wastes: Producing biofuels from waste cooking oil via a tandem vapor-phase hydrotreating process

Here, this study is focused on producing biofuels from waste oils via a tandem vapor-phase hydrotreating process in a pressurized two-stage fixed bed reactor over a bifunctional Ni/Al 2 O 3 -SiO 2 catalyst under 0.25 MPa H 2 . A 100% hydrodeoxygenation efficiency both in liquid and gas products was observed, yielding 83.9 wt% C 5 -C 19 n-alkanes which corresponds to a 7.4-fold increase compared with that obtained from non-catalytic conversion. The hydrodeoxygenation mechanism of waste cooking oil in the catalytic tandem hydrotreating process induced by Ni/Al 2 O 3 -SiO 2 was proposed. The hydropyrolysis temperature in the first reactor, hydrogenation temperature in the second reactor, reaction pressure, catalyst to waste cooking oil mass ratio, and gas hourly space velocity (GHSV) was optimized at 550 °C, 300 °C, 0.25 MPa, 3, and 56 s -1 , respectively. The application potential of this cascade vapor-phase hydrotreating process was evaluated by employing different waste oils such as palm kernel oil, woody oil (swida wilsoniana), soapstock, and waste lubricating oil as feedstock, giving C 5 to C 19 n-alkane yields ranging from 21.6 to 87.5 wt%. This work provides a novel and promising approach to upcycle waste oils into upgraded biofuels compared with conventional catalytic pyrolysis.

09 BIOMASS FUELS↗
DOE OSTI2018

Phytoremediation of sewage sludge contaminated by trace elements and organic compounds

Highlights: • Sewage sludge reclamation by poplar, willow, eucalyptus and sunflower was evaluated. • A species-specific response in trace element (TE) extraction was observed. • Sunflower was the best candidate for As, Cu, and Zn phytoextraction. • Eucalyptus seems a promising candidate for Pb and Cr phytoextraction. • All species were able to decrease organic pollutant concentration. Phytoremediation is a green technique being increasingly used worldwide for various purposes including the treatment of municipal sewage sludge (MSS). Most plants proposed for this technique have high nutrient demands, and fertilization is often required to maintain soil fertility and nutrient balance while remediating the substrate. In this context, MSS could be a valuable source of nutrients (especially N and P) and water for plant growth. The aim of this study was to determine the capacity willow (Salix matsudana, cv Levante), poplar (Populus deltoides × Populus nigra, cv Orion), eucalyptus (Eucalyptus camaldulensis) and sunflower (Helianthus annuus) to clean MSS, which is slightly contaminated by trace elements (TEs) and organic pollutants, and to assess their physiological response to this medium. In particular, we aimed to evaluate the TE accumulation by different species as well as the decrease of TEs and organic pollutants in the sludge after one cropping cycle and the effect of MSS on plant growth and physiology. Since MSS did not show any detrimental effect on the biomass yield of any of the species tested, it was found to be a suitable growing medium for these species. TE phytoextraction rates depended on the species, with eucalyptus showing the highest accumulation for Cr, whereas sunflower exhibited the best performance for As, Cu and Zn. At the end of the trial, some TEs (i.e. Cr, Pb and Zn), n-alkanes and PCBs showed a significant concentration decrease in the sludge for all tested species. The highest Cr decrease was observed in pots with eucalyptus (57.4%) and sunflower (53.4%), whereas sunflower showed the highest Cu decrease (44.2%), followed by eucalyptus (41.2%), poplar (16.2%) and willow (14%). A significant decrease (41.1%) of Pb in the eucalyptus was observed. Zn showed a high decrease rate with sunflower (59.5%) and poplar (52%) and to a lesser degree with willow (35.3%) and eucalyptus (25.4%). The highest decrease in n-alkanes concentration in the sludge was found in willow (98.3%) and sunflower (97.3%), whereas eucalyptus has the lowest PCBs concentration (91.8%) in the sludge compared to the beginning of the trial. These results suggest new strategies (e.g. crop rotation and intercropping) to be adopted for a better management of this phytotechnology.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Kinetics of low-temperature methane activation on IrO 2 (1 1 0): Role of local surface hydroxide species

The ability of the IrO 2 (1 1 0) surface to promote CH 4 activation at low temperatures (~150 K) suggests possibilities for developing IrO 2 -based catalysts to selectively convert light alkanes to high-value chemicals. In this study, we present experimental results and microkinetic simulations, based on density functional theory (DFT) calculations, of temperature programmed reaction spectra (TPRS) obtained for CH 4 σ-complexes adsorbed on IrO 2 (1 1 0), and focus on clarifying how surface OH groups modify the branching between CH 4 desorption, activation and subsequent reactions during TPRS. Our DFT results predict that surface OH groups strongly destabilize CH 4 σ-complexes on IrO 2 (1 1 0) in addition to deactivating surface O-atoms that are needed to achieve CH 4 activation at low temperature. We demonstrate that a microkinetic model that incorporates the influence of surface OH groups on the CH 4 binding and reactivity reproduces experimental TPRS results which show that adsorbed CH 4 σ-complexes preferentially dissociate at low CH 4 coverage, but that an increasing fraction of the adsorbed CH 4 desorbs at low temperature (~120 K) with increasing initial CH 4 or H coverage. The simulations reveal that low-temperature CH4 desorption during TPRS arises primarily from CH 4 σ-complexes that are kinetically-trapped between adjacent surface OH groups, and are thus destabilized and unable to access reactive O-atoms. In addition, when the effect of adjacent OH groups is incorporated we find that the PBE-D3 functional incorporating dispersion provides CH 4 binding energies that agree more closely with that obtained from the TPRS experiments. Overall, our results demonstrate that the local effect of adjacent OH groups must be incorporated into any microkinetic models to properly capture the selectivity between extensive and partial oxidation in alkane conversion on IrO 2 (1 1 0) under reaction conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Synthesis and characterization of mangenese(III) porphyrin supported on imidazole modified chloromethylated MIL-101(Cr): A heterogeneous and reusable catalyst for oxidation of hydrocarbons with sodium periodate

In the present work, chloromethylated MIL-101(Cr) modified with imidazole, Im-MIL-101, was applied as a support for immobilizing of tetraphenylporphyrinatomangenese(III) chloride. The imidazole-bound MIL-101, Im-MIL-101, not only used as support for immobilization of manganese porphyrin but also applied as a heterogeneous axial base. The Mn(TPP)Cl@Im-MIL-101 catalyst was characterized by UV–vis, FT-IR, X-ray diffraction (XRD), N{sub 2} adsorption, field emission scanning electron microscopy (FE-SEM), energy dispersive X-ray (EDX), elemental analysis and inductively coupled plasma (ICP) methods. The catalytic activity of this new catalytic system was investigated in the alkene epoxidation and alkane hydroxylation using NaIO{sub 4} as an oxidant in CH{sub 3}CN/H{sub 2}O at room temperature. This heterogeneous catalyst is highly efficient, stable and reusable in the oxidation of hydrocarbons. - Highlights: • MIL-101 was modified by covalent post synthetic modification. • Mn(TPP)Cl was anchored to imidazole modified MIL-101 by covalent attachment. • A heterogeneous catalyst was prepared. • The catalyst was used for epoxidation of alkenes and hydroxylation of alkanes. • The catalyst was reusable.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

On the prediction of pressure effects for the combination kinetics of two alkyl radicals with the geometric mean rule

Here, alkyl combination reactions, along with their reverse alkane unimolecular decomposition reactions, are widely present in pyrolysis and combustion systems. These reactions occur mainly at temperatures at which their rate coefficients depend on pressure, and only a few studies have explored this dependence for large size alkyls. The accurate calculation of these kinetic data is limited by the size of the alkyl fragments involved, since the theoretical methods used are computationally expensive. Therefore, little reliable data is available for the modeling of real fuels alkane decomposition kinetics. In this paper, we propose an alternative approach that allows an accurate estimation of pressure-dependent kinetic rates for the combination of long-chain alkyl radicals, based on tabulated reaction models. The rates of combination of linear alkyls radicals forming ethane to pentane were calculated using the CASPT2-F12/cc-pVDZ-F12 level within VRC-TST theory combined with master-equation simulations. The computed high-pressure limit rate coefficients showed that n-propyl could be a minimum-size representative structure for larger n-alkyl chain, but this approach fails to capture the pressure dependence of the reaction that remains size-dependent for larger alkyls. The Geometric Mean Rule (GMR), a simple rule that links the self and cross-reactions of three alkyl radicals, is used to address this issue. Our theoretical calculations show for the first time that the GMR applies not only at the high-pressure limit, but also for every pressure explored. The GMR is shown to be accurate, with a maximum 22 % deviation in the falloff region for the estimation of rates for small alkyl combinations. Using this method, we propose a tabulated reaction rate rule for the combination of alkyl radicals up to C5+C5. The use of computed rate coefficients with the GMR approximation opens ways to develop pressure-dependent reaction rate rules for large n-alkyl combinations, based on accurate and computationally expensive theoretical calculations on smaller alkyl fragments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Mechanistic Interpretations and Insights for the Oxidative Dehydrogenation of Propane via CO 2 over Cr 2 O 3 /Al 2 O 3 Catalysts

Oxidative dehydrogenation (ODH) of alkanes using carbon dioxide as a soft oxidant has recently emerged as a potentially attractive alternative to steam cracking for the production of light olefins. To elucidate reaction pathways and their dependence on the operating conditions, CO 2 -assisted propane dehydrogenation over a redox-active Cr 2 O 3 /Al 2 O 3 catalyst was examined in a packed bed reactor as a function of temperature, Cr 2 O 3 /CO 2 feed ratio, and residence time. Previous ODH studies have largely focused on CO 2 -rich conditions with the aim of preventing coke formation. However, at T = 600 °C the present study finds that the use of propane-rich conditions (1 ≤ C 3 H 8 /CO 2 ≤ 2.5) maximizes propylene production and selectivity while maintaining catalyst stability. In this work, it is postulated that the selective Mars van Krevelen dehydrogenation process is optimized at these ratios. Excess CO 2 apparently promotes nonselective dehydrogenation and dry reforming pathways that generate additional CO, adversely impacting catalyst stability via the Bouduard reaction. This hypothesis is supported by complementary investigations of the reverse water gas shift reaction and thermodynamic analysis. The findings and methodology presented here are likely applicable to related ODH processes with other alkanes and redox-active catalysts.

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

Probing the Transformation of Boron Nitride Catalysts under Oxidative Dehydrogenation Conditions

Hexagonal boron nitride (h-BN) and boron nitride nanotubes (BNNTs) were recently reported as highly selective catalysts for the oxidative dehydrogenation (ODH) of alkanes to olefins in the gas phase. Previous studies revealed a substantial increase in surface oxygen content after exposure to ODH conditions (heating to ca. 500 °C under a flow of alkane and oxygen); however, the complexity of these materials has thus far precluded an in-depth understanding of the oxygenated surface species. In this contribution, we combine advanced NMR spectroscopy experiments with scanning electron microscopy (SEM) and soft X-ray absorption spectroscopy (XAS) to characterize the molecular structure of the oxygen functionalized phase that arises on h-BN and BNNTs following catalytic testing for ODH of propane. The pristine BN materials are readily oxidized and hydrolyzed under ODH reaction conditions to yield a phase consisting of three coordinate boron sites with variable numbers of hydroxyl and bridging oxide groups which is denoted B(OH) x O 3-x (where x = 0-3). Evidence for this robust oxide phase revises previous literature hypotheses of hydroxylated BN edges as the active component on h-BN.

03 NATURAL GAS↗
DOE OSTI2014

Molecular dynamics simulation of diffusion coefficients and structural properties of some alkylbenzenes in supercritical carbon dioxide at infinite dilution

The binary infinite dilute diffusion coefficients, D{sub 12}{sup ∞}, of some alkylbenzenes (Ph-C{sub n}, from Ph-H to Ph-C{sub 12}) from 313 K to 333 K at 15 MPa in supercritical carbon dioxide (scCO{sub 2}) have been studied by molecular dynamics (MD) simulation. The MD values agree well with the experimental ones, which indicate MD simulation technique is a powerful way to predict and obtain diffusion coefficients of solutes in supercritical fluids. Besides, the local structures of Ph-C{sub n}/CO{sub 2} fluids are further investigated by calculating radial distribution functions and coordination numbers. It qualitatively convinces that the first solvation shell of Ph-C{sub n} in scCO{sub 2} is significantly influenced by the structure of Ph-C{sub n} solute. Meanwhile, the mean end-to-end distance, the mean radius of gyration and dihedral angle distribution are calculated to gain an insight into the structural properties of Ph-C{sub n} in scCO{sub 2}. The abnormal trends of radial distribution functions and coordination numbers can be reasonably explained in term of molecular flexibility. Moreover, the computed results of dihedral angle clarify that flexibility of long-chain Ph-C{sub n} is the result of internal rotation of C-C single bond (σ{sub c-c}) in alkyl chain. It is interesting that compared with n-alkane, because of the existence of benzene ring, the flexibility of alkyl chain in Ph-C{sub n} with same carbon atom number is significantly reduced, as a result, the carbon chain dependence of diffusion behaviors for long-chain n-alkane (n ≥ 5) and long-chain Ph-C{sub n} (n ≥ 4) in scCO{sub 2} are different.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Negative differential resistance devices by using N-doped graphene nanoribbons

Recently, extensive efforts have been devoted to the investigations of negative differential resistance (NDR) behavior in graphene. Here, by performing fully self-consistent density functional theory calculations combined with non-equilibrium Green's function technique, we investigate the transport properties of three molecules from conjugated molecule, one-dimension alkane chain, and single molecule magnet, which are sandwiched between two N-doped zigzag and armchair graphene nanoribbons (GNRs). We observe robust NDR effect in all examined molecular junctions including benzene, alkane, and planar four-coordinated Fe complex. Through the analyses of the calculated electronic structures and the bias-dependent transmission coefficients, we find that the narrow density of states of N-doped GNRs and the bias-dependent effective coupling between the discrete frontier molecular orbitals and the subbands of N-doped GNRs are responsible for the observed NDR phenomenon. These theoretical findings imply that N-doped GNRs hold great potential for building NDR devices based on various molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Derivation of coarse-grained potentials via multistate iterative Boltzmann inversion

In this work, an extension is proposed to the standard iterative Boltzmann inversion (IBI) method used to derive coarse-grained potentials. It is shown that the inclusion of target data from multiple states yields a less state-dependent potential, and is thus better suited to simulate systems over a range of thermodynamic states than the standard IBI method. The inclusion of target data from multiple states forces the algorithm to sample regions of potential phase space that match the radial distribution function at multiple state points, thus producing a derived potential that is more representative of the underlying interactions. It is shown that the algorithm is able to converge to the true potential for a system where the underlying potential is known. It is also shown that potentials derived via the proposed method better predict the behavior of n-alkane chains than those derived via the standard IBI method. Additionally, through the examination of alkane monolayers, it is shown that the relative weight given to each state in the fitting procedure can impact bulk system properties, allowing the potentials to be further tuned in order to match the properties of reference atomistic and/or experimental systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Multibody correlations in the hydrophobic solvation of glycine peptides

Protein collapse during folding is often assumed to be driven by a hydrophobic solvation energy (ΔG{sub vdw}) that scales linearly with solvent-accessible surface area (A). In a previous study, we argued that ΔG{sub vdw}, as well as its attractive (ΔG{sub att}) and repulsive (ΔG{sub rep}) components, was not simply a linear function of A. We found that the surface tensions, γ{sub rep}, γ{sub att}, and γ{sub vdw}, gotten from ΔG{sub rep}, ΔG{sub att}, and ΔG{sub vdw} against A for four configurations of deca-alanine differed from those obtained for a set of alkanes. In the present study, we extend our analysis to fifty decaglycine structures and atomic decompositions. We find that different configurations of decaglycine generate different estimates of γ{sub rep}. Additionally, we considered the reconstruction of the solvation free energy from scaling the free energy of solvation of each atom type, free in solution. The free energy of the isolated atoms, scaled by the inverse surface area the atom would expose in the molecule does not reproduce the γ{sub rep} for the intact decaglycines. Finally, γ{sub att} for the decaglycine conformations is much larger in magnitude than those for deca-alanine or the alkanes, leading to large negative values of γ{sub vdw} (−74 and −56 cal/mol/Å{sup 2} for CHARMM27 and AMBER ff12sb force fields, respectively). These findings imply that ΔG{sub vdw} favors extended rather than compact structures for decaglycine. We find that ΔG{sub rep} and ΔG{sub vdw} have complicated dependencies on multibody correlations between solute atoms, on the geometry of the molecular surface, and on the chemical identities of the atoms.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Adsorption of a metalorganic complex at a metal surface: A density functional theory study vs. model description

A modification of the electronic and magnetic structure of a metalorganic complex by chemisorption at a metallic surface is addressed. The density functional theory (DFT) is applied to investigate a simplified form of a copper-dioxolene complex in a free state and connected to Au(111) surface with alkanethiol linkers. A systematic study of the dependence of the system electronic structure on the linker length is performed. It is found that the electronic structure of the complex is well preserved during the adsorption process. The magnetic moment of the Cu-dioxolene functional group is shown to be strictly correlated with the amount of the charge residing at the complex. On the basis of the DFT results, a model Hamiltonian of the adsorbed metalorganic system is proposed. The model is an extension of the Sandorfy's model of the alkanes and includes explicitly Coulomb interaction between electrons both within the alkane's backbone and the end group. We show that the latter feature is necessary to understand the evolution of the system's properties with the length of the linkers. The advantage of this approach is that it not only reproduces the main results of our DFT analysis but also provides a simple common basis to analyse a wide class of metal complexes bound to metal surfaces with alkanethiol linkers.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Designer Metal–Organic Frameworks for Size–Exclusion–Based Hydrocarbon Separations: Progress and Challenges

The separation of hydrocarbons is of primary importance in the petrochemical industry but remains a challenging process. Hydrocarbon separations have traditionally relied predominantly on costly and energy intensive heat-driven procedures such as low temperature distillations. Adsorptive separation based on porous solids represents an alternative technology that is potentially more energy efficient for the separation of some hydrocarbons. Great efforts have been made recently not only on the development of adsorbents with optimal separation performance but also towards the subsequent implementation of adsorption-based separation technology. Emerging as a relatively new class of multifunctional porous materials, metal-organic frameworks hold substantial promise as adsorbents for highly efficient separation of hydrocarbons. This is because of their exceptional and intrinsic porosity tunability which enables size-exclusion based separations that render the highest possible separation selectivity. In this review, we highlight the recent advances in the development of MOFs for separation of selected groups of hydrocarbons, including methane/C2 hydrocarbons, normal alkanes, alkane isomers, alkane/alkene/alkyne, and C8 alkylaromatics, with a particular focus on separations based on size-exclusion mechanism. Insights into tailor-made structures, material design strategies, and structure-property relations will be elucidated. In addition, the existing challenges and possible future directions of this important research field will be discussed.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Effects of surface species and homogeneous reactions on rates and selectivity in ethane oxidation on oxide catalysts

Selective alkane oxidations on metal oxide catalysts involve complex mechanisms with multiple reactions in series and parallel, different types of reduced and oxidized surface species, and potential contributions from gas-phase reactions. We report kinetics and thermodynamics of elementary steps involved in C 2 H 6 -O 2 reactions on SiO 2 -supported small vanadium oxide domains are determined using density functional theory. These surface reactions together with gas-phase mechanisms are incorporated in kinetic simulations to determine how surface and gaseous reactions interact and contribute to rates and selectivity. The results show that gas-phase reactions within pore volumes in contact with the catalyst contribute significantly to C 2 H 6 activation rates, even at conditions where gas-phase reactions in empty volumes without catalyst are negligible. The majority of C 2 H 6 activations occur on the surface, via H abstraction by vanadium oxo species present at terminal lattice oxygens. The gas-phase activations via H-abstraction by OH radicals also exhibit significant contributions. The reduced centers formed by reactions at vanadium oxo species are re-oxidized rapidly and, therefore, are present in very small concentrations at reaction conditions. The re-oxidation steps lead to the formation of HO 2 radicals and surface peroxo species that are also rapidly consumed and are present in small concentrations. The peroxo species preferentially convert C 2 H 4 to its epoxide product and influence selectivity even at low concentrations. The gas-phase reactions decrease the concentrations of peroxo species and improve selectivity slightly. The effects of reaction conditions and catalyst site density provide further insights into how factors beyond conversions at lattice oxygens influence rates and selectivity in alkane oxidation reactions of significant industrial importance.

42 ENGINEERING↗
DOE OSTI2015

Propane σ‐Complexes on PdO(101): Spectroscopic Evidence of the Selective Coordination and Activation of Primary CH Bonds

Abstract Achieving selective CH bond cleavage is critical for developing catalytic processes that transform small alkanes to value‐added products. The present study clarifies the molecular‐level origin for an exceptionally strong preference for propane to dissociate on the crystalline PdO(101) surface via primary CH bond cleavage. Using reflection absorption infrared spectroscopy (RAIRS) and density functional theory (DFT) calculations, we show that adsorbed propane σ‐complexes preferentially adopt geometries on PdO(101) in which only primary CH bonds datively interact with the surface Pd atoms at low propane coverages and are thus activated under typical catalytic reaction conditions. We show that a propane molecule achieves maximum stability on PdO(101) by adopting a bidentate geometry in which a HPd dative bond forms at each CH 3 group. These results demonstrate that structural registry between the molecule and surface can strongly influence the selectivity of a metal oxide surface in activating alkane CH bonds.

Zhang, Feng↗
DOE OSTI2017

Uncatalyzed, Regioselective Oxidation of Saturated Hydrocarbons in an Ambient Corona Discharge

Abstract Atmospheric pressure chemical ionization (APCI) in air or in nitrogen with just traces of oxygen is shown to yield regioselective oxidation, dehydrogenation, and fragmentation of alkanes. Ozone is produced from ambient oxygen in situ and is responsible for the observed ion chemistry, which includes partial oxidation to ketones and C−C cleavage to give aldehydes. The mechanism of oxidation is explored and relationships between ionic species produced from individual alkanes are established. Unusually, dehydrogenation occurs by water loss. Competitive incorporation into the hydrocarbon chain of nitrogen versus oxygen as a mode of ionization is also demonstrated.

Ayrton, Stephen T.↗
DOE OSTI2020

Overcoming Fundamental Limitations in Adsorbent Design: Alkene Adsorption by Non‐porous Copper(I) Complexes

Abstract Purifying alkenes from alkanes requires cryogenic distillation. This consumes energy equivalent to countries of ca. 5 million people. Replacing distillation with adsorption processes would significantly increase energy efficiency. Trade‐offs between kinetics, selectivity, capacity, and heat of adsorption have prevented production of an optimal adsorbent. We report adsorbents that overcome these trade‐offs. [Cu‐Br] 3 and [Cu‐H] 3 are air‐stable trinuclear complexes that undergo reversible solid‐state inter‐molecular rearrangements to produce dinuclear [Cu‐Br⋅(alkene)] 2 and [Cu‐H⋅(alkene)] 2 . The reversible solid‐state rearrangement, confirmed in situ using powder X‐ray diffraction, allows adsorbent design trade‐offs to be overcome, coupling low heat of adsorption (−10 to −17 kJ mol −1 alkene ), high alkene:alkane selectivity (47; 29), and uptake capacity (>2.5 mol alkene mol −1 Cu3 ). Most remarkably, [Cu‐H] 3 displays fast uptake and regenerates capacity within 10 minutes.

Parasar, Devaborniny↗
DOE OSTI2022

Temperature‐Programmed Separation of Hexane Isomers by a Porous Calcium Chloranilate Metal‐Organic Framework

Abstract The full separation of alkane isomers as a function of different degrees of branching remains a daunting challenge due to its stringent requirement with respect to pore dimensions of the adsorbents. In this work, we report a novel microporous coordination network built on calcium (II) and chloranilate. The compound has a flexible framework and exhibits temperature‐dependent adsorption behavior toward hexane isomers. At 30 °C, it accommodates substantial amounts of linear and monobranched hexanes but fully excludes their dibranched isomer, and at elevated temperatures such as 150 °C, it acts as a splitter for linear and branched alkanes. Its capability of efficient discrimination of hexane isomers as a function of branching is verified by experimental breakthrough measurements. Ab initio calculations have uncovered the underlying selective size‐exclusion separation mechanism.

Lin, Yuhan↗