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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 955 records · Page 53
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Accelerated Steam Methane Reforming by Dynamically Applied Charges

Catalyst design has traditionally focused on tuning active site properties to optimally bind reaction intermediates and balance the kinetic requirements of multiple competing chemical processes, as necessitated by the Sabatier principle. It has recently been proposed that for reactions following certain potential energy landscapes, the activity limit imposed by the Sabatier principle may be overcome by using programmed oscillations of surface electron density at the timescales of surface reactions (i.e., “catalytic resonance”). Here, we use a combination of density functional theory (DFT) simulations and transient kinetic models (TKMs) to simulate the kinetics of steam methane reforming (SMR) on Ru(211) surfaces under statically and dynamically applied charges. DFT-calculated binding energies of SMR intermediates and transition states exhibit strong sensitivity to positively applied charges and follow unique scaling relationships that deviate from linear periodic trends across transition metals. Our simulations demonstrate that applying a small positive charge to Ru dramatically enhances the steady-state turnover frequency (TOF) of SMR by up to 5 orders of magnitude above the TOF observed over neutral Ru. Thus, statically charging Ru catalysts may be an effective strategy to lower the temperature requirements for SMR. Dynamic square-wave oscillations in charge resulted in SMR catalytic resonance with an onset frequency f ∼ 106 Hz and the corresponding average TOFs exceeding the statically charged Ru surface by an additional 15%. Here, based on sensitivity analyses performed for the two end points of oscillation, we propose that dynamic TOF improvement beyond the Sabatier maximum can be expected when the system oscillates between two kinetic regimes that are uniquely controlled by distinct elementary steps.

Catalysts↗
DOE OSTI2021

Origin of Chirality Induced Spin Selectivity in Photoinduced Electron Transfer

Here we propose a mechanism by which spin-polarization can be generated dynamically in chiral molecular systems undergoing photoinduced electron transfer. The proposed mechanism explains how spin-polarization emerges in systems where charge transport is dominated by incoherent hopping, mediated by spin-orbit and electronic exchange couplings through an intermediate charge transfer state. We derive a simple expression for the spin-polarization that predicts a nonmonotonic temperature dependence, consistent with recent experiments, and a maximum spin-polarization that is independent of the magnitude of the spin-orbit coupling. We validate this theory using approximate quantum master equations and the numerically exact hierarchical equations of motion. The proposed mechanism of chirality induced spin selectivity should apply to many chiral systems, and the ideas presented here have implications for the study of spin transport at temperatures relevant to biology and provide simple principles for the molecular control of spins in fluctuating environments.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2023

Extraordinary Magnetic Response of an Anisotropic 2D Antiferromagnet via Site Dilution

A prominent characteristic of 2D magnetic systems is the enhanced spin fluctuations, which reduce the ordering temperature. We report that a magnetic field of only 1000th of the Heisenberg superexchange interaction can induce a crossover, which for practical purposes is the effective ordering transition, at temperatures about 6 times the Néel transition in a site-diluted two-dimensional anisotropic quantum antiferromagnet. Such a strong magnetic response is enabled because the system directly enters the antiferromagnetically ordered state from the isotropic disordered state, skipping the intermediate anisotropic stage. The underlying mechanism is achieved on a pseudospin-half square lattice realized in the [(SrIrO3)1/(SrTiO3)2] superlattice thin film that is designed to linearly couple the staggered magnetization to external magnetic fields by virtue of the rotational symmetry-preserving Dzyaloshinskii–Moriya interaction. Furthermore, our model analysis shows that the skipping of the anisotropic regime despite finite anisotropy is due to the enhanced isotropic fluctuations under moderate dilution.

2D antiferromagnet↗
DOE OSTI2023

Modeling the Effect of Surface Platinum–Tin Alloys on Propane Dehydrogenation on Platinum–Tin Catalysts

Uncertainty analysis, reported experimental literature data, and density functional theory were synthesized to model the effect of surface tin coverage on platinum-based catalysts for nonoxidative propane dehydrogenation to propylene. Here, this study tests four different platinum–tin skin surface models as potential catalytic sites, Pt 3 Sn/Pt(100), PtSn/Pt(100), Pt 3 Sn/Pt(111), and Pt 2 Sn/Pt(211), and compares them to the corresponding pure Pt surface sites using an uncertainty analysis methodology that uses BEEF-vdW with its ensembles (BMwE) to generate the uncertainty for the energies of the intermediates and transition states. One experimental data set with two experimental observations, selectivity to propylene and turnover frequency of propylene, was used as a calibration data set to evaluate the impact of the experimental data on informing the models. This study finds that the prior model for Pt 3 Sn/Pt(100) is the most active and Pt 2 Sn/Pt(211) is the most selective toward propylene. Active sites on the (100) facet have the highest probability of being responsible for C 1 and C 2 product formations (C–C bond cleavage). Increasing the Sn coverage on the (100) surface facet to a PtSn/Pt(100) active site leads to a significantly reduced rate and might explain the experimentally observed higher selectivity of Sn-doped catalysts relative to pure Pt catalysts. Next, this study finds that for all surfaces, except PtSn/Pt(100), the rate-controlling steps are the initial dehydrogenation steps alongside some partially rate-controlling second dehydrogenation steps. For PtSn/Pt(100), only the initial terminal dehydrogenation step to CH 3 CH 2 CH 2 * and second dehydrogenation steps are rate-controlling. Next, the calibrated models for all surfaces were found to be selective toward propylene production and model the reported turnover frequency successfully. Nevertheless, Pt 2 Sn/Pt(211) emerges as the active site with some (minor) evidence as the main active site based on Jeffreys’ scale interpretation of Bayes factors. This observation agrees with prior studies that also found step sites to be most likely the most relevant active sites for pure Pt catalysts. Overall, the results indicate that tin, in addition to affecting the binding strength of the adsorbed species, prevents deeper dehydrogenation (reducing coking) and cracking reactions through increasing activation barriers for unwanted side reactions.

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

Tunable riboregulator switches for post-transcriptional control of gene expression

The most straightforward approach to altering the flux through a particular metabolic step is to increase or decrease the concentration of the enzyme catalyst. Until recently engineering strategies for altering gene expression have focused on transcription control using strong inducible promoters or by using one of several strategies to knock down or knock out a wasteful gene. Recently, synthetic riboregulators have been developed for translational regulation of gene expression. We report a new modular synthetic riboregulator class that has the potential to finely tune protein expression and independently control the concentration of each enzyme in an engineered metabolic pathway. Our design includes a cis-repressor at the 5’ end of the mRNA that forms a stem-loop helix occluding the ribosome binding site and blocking translation. An activating-RNA, expressed in trans, frees the RBS turning on translation. The overall architecture of the riboregulators is designed using Watson-Crick base-pairing stability followed by directed evolution on a portion of each trans-activator to fine tune translation. We report a cis-repressor that can completely shut off translation of antibiotic resistance reporters and a trans-activator that restores translation. We have shown it is possible to use riboregulators to achieve translational control of gene expression over a wide dynamic range. Using a bioluminescent reporter system, we demonstrated an ON/OFF ratio >300. We have demonstrated that a targeting sequence can be changed to develop riboregulators that can independently regulate translation of many genes with minimal cross-talk. In a SELEX experiment, we demonstrated that by subtly altering the sequence of the trans-activator, it is possible to alter the equilibrium between repressed and activated states and achieve intermediate translational control.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Evolution from Tunneling to Hopping Mediated Triplet Energy Transfer from Quantum Dots to Molecules

Efficient energy transfer is particularly important for multiexcitonic processes like singlet fission and photon upconversion. Observation of the transition from short-range tunneling to long-range hopping during triplet exciton transfer from CdSe nanocrystals to anthracene is reported here. This is firmly supported by steady- state photon upconversion measurements, a direct proxy for the efficiency of triplet energy transfer (TET), as well as transient absorption measurements. When phenylene bridges are initially inserted between a CdSe nanocrystal donor and anthracene acceptor, the rate of TET decreases exponentially, commensurate with a decrease in the photon upconversion quantum efficiency from 11.6% to 4.51% to 0.284%, as expected from a tunneling mechanism. However, as the rigid bridge is increased in length to 4 and 5 phenylene units, photon upconversion quantum efficiencies increase again to 0.468% and 0.413%, 1.5–1.6 fold higher than that with 3 phenylene units (using the convention where the maximum upconversion quantum efficiency is 100%). This suggests a transition from exciton tunneling to hopping, resulting in relatively efficient and distance-independent TET beyond the traditional 1 nm Dexter distance. Transient absorption spectroscopy is used to confirm triplet energy transfer from CdSe to transmitter, and the formation of a bridge triplet state as an intermediate for the hopping mechanism. Lastly, this first observation of the tunneling-to-hopping transition for long-range triplet energy transfer between nanocrystal light absorbers and molecular acceptors suggests that these hybrid materials should further be explored in the context of artificial photosynthesis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Bimolecular Reductive Elimination of Ethane from Pyridine(diimine) Iron Methyl Complexes: Mechanism, Electronic Structure, and Entry into [2+2] Cycloaddition Catalysis

The application of bimolecular reductive elimination to the activation of iron catalysts for alkene–diene cycloaddition is described. Key to this approach was the synthesis, characterization, electronic structure determination, and ultimately solution stability of a family of pyridine(diimine) iron methyl complexes with diverse steric properties and electronic ground states. Both the aryl-substituted, ( Me PDI)FeCH 3 and ( Et PDI)FeCH 3 ( R PDI = 2,6-(2,6-R 2 -C 6 H 3 N=CMe) 2 C 5 H 3 N), and the alkyl-substituted examples, ( Cy APDI)FeCH 3 ( Cy APDI = 2,6-(C 6 H 11 N=CMe) 2 C 5 H 3 N), have molecular structures significantly distorted from planarity and S = 3/2 ground states. The related N-arylated derivative bearing 2,6-di-isopropyl aryl substituents, ( iPr PDI)FeCH 3 , has an idealized planar geometry and exhibits spin crossover behavior from S = 1/2 to S = 3/2 states. At 23 °C under an N 2 atmosphere, both ( Me PDI)FeCH 3 and ( Et PDI)FeCH 3 underwent reductive elimination of ethane to form the iron dinitrogen precatalysts, [( Me PDI)Fe(N 2 )] 2 (μ-N 2 ) and [( Et PDI)Fe(N 2 )] 2 (μ-N 2 ), respectively, while ( iPr PDI)FeCH 3 proved inert to C–C bond formation. By contrast, addition of butadiene to all three iron methyl complexes induced ethane formation and generated the corresponding iron butadiene complexes, ( R PDI)Fe(η 4 -C 4 H 6 ) (R = Me, Et, i Pr), known precatalysts for the [2+2] cycloaddition of olefins and dienes. Kinetic, crossover experiments, and structural studies were combined with magnetic measurements and Mössbauer spectroscopy to elucidate the electronic and steric features of the iron complexes that enable this unusual reductive elimination and precatalyst activation pathway. Furthermore, transmetalation of methyl groups between iron centers was fast at ambient temperature and independent of steric environment or spin state, while the intermediate dimer underwent the sterically controlled rate-determining reaction with either N 2 or butadiene to access a catalytically active iron compound.

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

Direct Evidence for a Sequential Electron Transfer–Proton Transfer Mechanism in the PCET Reduction of a Metal Hydroxide Catalyst

Here, the proton-coupled electron transfer (PCET) mechanism for the reaction M ox -OH + e − + H + → M red -OH 2 was de-termined through kinetic resolution of the independent electron transfer (ET) and proton transfer (PT) steps. The reaction of interest was triggered by visible light excitation of [Ru II (tpy)(bpy′)H 2 O] 2+ , Ru II -OH 2 , where tpy is 2,2′:6′,2″-terpyridine and bpy′ is 4,4′-diaminopropylsilatrane-2,2′-bipyridine, anchored to In 2 O 3 :Sn (ITO) thin films in aqueous solutions. Interfacial kinetics for the PCET reduction reaction were quantified by nanosecond transient absorption spectroscopy as a function of solution pH and applied potential. Data acquired from pH = 5-10 revealed a stepwise electron-transfer proton-transfer (ET-PT) mechanism, while kinetic measurements made below the pK a (Ru III -OH/OH 2 ) = 1.3 were used to study the analogous interfacial reaction where electron transfer was the only mechanistic step. Analysis of this data with a recently reported multi-channel kinetic model was used to construct a PCET zone diagram and supported the assignment of an ET-PT mechanism from pH = 5-10. Ultimately, this study represents a unique example amongst M ox -OH/M red -OH 2 reactivity where the protona-tion and oxidation state of the intermediate was kinetically and spectrally resolved to firmly establish the PCET mechanism.

Charge transfer↗
DOE OSTI2024

Can the Rate of a Catalytic Turnover Be Altered by Ligands in the Absence of Direct Binding Interactions?

Second sphere coordination effects ubiquitous in enzymatic catalysis occur through direct interactions, either covalent or non-covalent, with reaction intermediates and transition states. Here, we present herein evidence of indirect second sphere coordination effects in which ligation of water/alkanols far removed from the primary coordination sphere of the active site nevertheless alter energetic landscapes within catalytic redox cycles in the absence of direct physicochemical interactions with surface species mediating catalytic turnovers. Density functional theory, in situ X-ray absorption and infrared spectroscopy, and a wide array of steady-state and transient CO oxidation rate data suggest that the presence of peripheral water renders oxidation half-cycles within two-electron redox cycles over μ m -oxo-bridged trimers in MIL-100(M) more kinetically demanding. Communication between ligated water and the active site appears to occur through the Fe-O-Fe backbone, as inferred from spin density variations on the central μ m -oxygen 'junction'. Evidence is provided for the generality of these second sphere effects in that they influence different types of redox half-cycles or metals, and can be amplified or attenuated through choice of coordinating ligand. Specifically in the case of MIL-100(M) materials, the Cr isostructure can be made to kinetically mimic the Fe variant by disproportionately hindering oxidation half-cycles relative to the reduction half-cycles. Kinetic and spectroscopic inferences presented here significantly expand both the conceptual definition of second sphere effects as well as the palette of synthetic levers available for tuning catalytic redox performance through chemical ligation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Mechanism of Tyrosine-Driven Deprotonation in Photosystem II Revealed by Multiscale Simulations

Photosystem II (PSII) drives light-induced water oxidation via stepwise redox transitions of its oxygen-evolving complex (OEC), a Mn 4 Ca cluster advancing through five intermediate S-states (S 0 –S 4 ). The S 2 → S 3 transition involves a redox event in which a Mn ion donates an electron to the redox-active tyrosine YZ, coupled to deprotonation of an OEC-bound water ligand─yet the underlying coupling mechanism remains unresolved. Time-resolved serial femtosecond crystallography (TR-SFX) has revealed transient electron density shifts near the redox-active tyrosine Y Z , interpreted as sequential oxidation and reduction, with reduction initiating ∼1 μs after excitation and substantially progressed by 30 μs. However, this interpretation conflicts with kinetics from photothermal beam deflection (PBD), time-resolved X-ray absorption spectroscopy (TR-XAS), and electron paramagnetic resonance (EPR), which place electron transfer at 190–400 μs and proton transfer around 30 μs. Here, we reconcile these discrepancies using quantum mechanics/molecular mechanics (QM/MM) and molecular dynamics (MD) simulations. We show that oxidation of P680 and Y Z breaks the symmetry of the nearby hydrogen bonds involving water molecule W4, displacing Y Z and replicating the TR-SFX features of Y Z and Q165 observed at 1 μs. This local perturbation propagates through a hydrogen-bond network, transmitting the electrostatic signal from Y Z to the E65-E312 dyad and triggering redox-coupled deprotonation via the Cl1 channel. By 30 μs, the hydrogen-bond symmetry is restored through deprotonation of W2 (or alternatively W1), reproducing the disappearance of TR-SFX density differences around Y Z and Q165 without requiring Y Z reduction. Our proposed mechanism also gives molecular insights into the O6* density, assigning it to water reorganization rather than a discrete Ca-bound hydroxide species. Here, our results reveal a detailed atomistic mechanism linking Y Z oxidation to long-range proton release and suggest a functional role for the nearby Cl – ion in proton transfer. More broadly, this study underscores the importance of hydrogen-bond dynamics in mediating redox-driven proton transport and demonstrates how integrative simulations can resolve mechanistic ambiguities.

Deprotonation↗
DOE OSTI2018

Pb-Activated Amine-Assisted Photocatalytic Hydrogen Evolution Reaction on Organic–Inorganic Perovskites

We report here the reaction mechanism for explicit aqueous solvent quantum mechanics (QM) studies determining the energetics and reaction barriers for the photocatalytic hydrogen evolution reaction (HER) on CH 3 NH 3 PbI 3 surface. We find that both the lead (Pb) atoms and the surface organic molecules play essential roles, leading to a two-step Pb-activated amine-assisted (PbAAA) reaction mechanism involving an intermediate lead hydride state. Both H of H 2 product are extracted from surface organic molecules, while two protons from the solution migrate along water chains via the Grotthuss mechanism to replace the H in organic molecule. We obtain a reaction barrier of 1.08 eV for photochemical generation of H 2 on CH 3 NH 3 PbI 3 compared to 2.61 eV for the dark reaction. We expect this HER mechanism can also apply to the other organic perovskites, but the energy barriers and reaction rates may depend on the basicity of electrolyte and intrinsic structures of perovskites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

A Universal Model of Cation Effects in Electrocatalysis

Electrolyte cations are conventionally viewed as inert spectators in electrocatalysis. However, a wealth of observations show that catalytic rates are often highly sensitive to cation identity. Despite their prevalence, these cation effects have resisted a unified mechanistic explanation, with different physical phenomena implicated across reaction chemistries, catalyst compositions, and choice of solvent. In this perspective, we describe a general framework for understanding cation effects in electrocatalysis based on electrostatics. We argue that cations influence reaction rates by modifying the strength of the electric field present at the catalyst surface, which alters the energetics of adsorbed intermediates and transition states according to their dipole moments and polarizabilities. The magnitude of this field depends on how cations arrange at the electrode surface, controlled by their size, shape, solvation, and packing efficiency. Cations that can arrange more densely result in a steeper potential drop at the electrode surface and consequently a stronger electric field. Our model further identifies two criteria for observing cation effects: (1) the operating potential must be negative of the electrode’s potential of zero total charge, ensuring that cations accumulate at the interface, and (2) the energetics of the kinetically relevant elementary step must be field sensitive. This framework reconciles previously inconsistent trends, including why cation effects appear only for some catalysts, why reaction selectivity is sensitive to cation identity, and why activity can increase with cation size on certain metals but decrease on others. Supported by kinetic measurements, spectroscopy, and atomistic simulations, the model provides both conceptual value for building intuition about catalysis at charged interfaces and predictive value for anticipating trends for new reactions, catalysts, and electrolytes. We conclude by highlighting the importance of electric fields across electrochemical, thermochemical, and biological catalysis and propose that considering the electrostatic environment around active sites offers new opportunities for improving activity and selectivity.

cation effects↗
DOE OSTI2016

Structure of photosystem II and substrate binding at room temperature

Light-induced oxidation of water by photosystem II (PS II) in plants, algae and cyanobacteria has generated most of the dioxygen in the atmosphere. PS II, a membrane-bound multi-subunit pigment protein complex, couples the one-electron photochemistry at the reaction centre with the four-electron redox chemistry of water oxidation at the Mn 4 CaO 5 cluster in the oxygen-evolving complex (OEC). Under illumination, the OEC cycles through five intermediate S-states (S 0 to S 4), in which S 1 is the dark-stable state and S 3 is the last semi-stable state before O-O bond formation and O 2 evolution. A detailed understanding of the O-O bond formation mechanism remains a challenge, and will require elucidation of both the structures of the OEC in the different S-states and the binding of the two substrate waters to the catalytic site. Here we report the use of femtosecond pulses from an X-ray free electron laser (XFEL) to obtain damage-free, room temperature structures of dark-adapted (S 1), two-flash illuminated (2F; S 3 -enriched), and ammonia-bound two-flash illuminated (2F-NH 3; S 3 -enriched) PS II. Although the recent 1.95 Å resolution structure of PS II at cryogenic temperature using an XFEL provided a damage-free view of the S 1 state, measurements at room temperature are required to study the structural landscape of proteins under functional conditions, and also for in situ advancement of the S-states. To investigate the water-binding site(s), ammonia, a water analogue, has been used as a marker, as it binds to the Mn 4 CaO 5 cluster in the S 2 and S 3 states. Since the ammonia-bound OEC is active, the ammonia-binding Mn site is not a substrate water site. This approach, together with a comparison of the native dark and 2F states, is used to discriminate between proposed O-O bond formation mechanisms.

Young, Iris D.↗
DOE OSTI2017

Strongly Coupled Magnetic and Electronic Transitions in Multivalent Strontium Cobaltites

Here, the topotactic phase transition in SrCoO x (x = 2.5–3.0) makes it possible to reversibly transit between the two distinct phases, i.e. the brownmillerite SrCoO 2.5 that is a room-temperature antiferromagnetic insulator (AFM-I) and the perovskite SrCoO 3 that is a ferromagnetic metal (FM-M), owing to their multiple valence states. For the intermediate x values, the two distinct phases are expected to strongly compete with each other. With oxidation of SrCoO 2.5 , however, it has been conjectured that the magnetic transition is decoupled to the electronic phase transition, i.e., the AFM-to-FM transition occurs before the insulator-to-metal transition (IMT), which is still controversial. Here, we bridge the gap between the two-phase transitions by density-functional theory calculations combined with optical spectroscopy. We confirm that the IMT actually occurs concomitantly with the FM transition near the oxygen content x = 2.75. Strong charge-spin coupling drives the concurrent IMT and AFM-to-FM transition, which fosters the near room-T magnetic transition characteristic. Ultimately, our study demonstrates that SrCoO x is an intriguingly rare candidate for inducing coupled magnetic and electronic transition via fast and reversible redox reactions.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Transition between protein-like and polymer-like dynamic behavior: Internal friction in unfolded apomyoglobin depends on denaturing conditions

Equilibrium dynamics of different folding intermediates and denatured states is strongly connected to the exploration of the conformational space on the nanosecond time scale and might have implications in understanding protein folding. For the first time, the same protein system apomyoglobin has been investigated using neutron spin-echo spectroscopy in different states: native-like, partially folded (molten globule) and completely unfolded, following two different unfolding paths: using acid or guanidinium chloride (GdmCl). While the internal dynamics of the native-like state can be understood using normal mode analysis based on high resolution structural information of myoglobin, for the unfolded and even for the molten globule states, models from polymer science are employed. The Zimm model accurately describes the slowly-relaxing, expanded GdmCl-denaturated state, ignoring the individuality of the different aminoacid side chain. The dynamics of the acid unfolded and molten globule state are similar in the framework of the Zimm model with internal friction, where the chains still interact and hinder each other: the first Zimm relaxation time is as large as the internal friction time. Transient formation of secondary structure elements in the acid unfolded and presence of α-helices in the molten globule state lead to internal friction to a similar extent.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Superconducting phase transitions in disordered NbTiN films

Suppression of superconductivity in disordered systems is a fundamental problem of condensed matter physics. Here we investigate superconducting niobium-titanium-nitride (Nb 1-x Ti x N) thin films grown by the atomic layer deposition (ALD) with slightly different growth process parameters. We observe a smooth crossover from the disorder-driven superconductor-normal metal transition (SMT) to the superconductor-insulator transition (SIT) via the intermediate Bose metal state detected by the low-temperature saturation of the temperature dependence of the sheet resistance. We demonstrate that the SIT via the intervening Bose metal state occurs if the sheet resistance of the film in the maximum, R max prior to the superconducting drop of R(T), exceeds R q = h/4e 2 .

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2016

Using degrees of rate control to improve selective n-butane oxidation over model MOF-encapsulated catalysts: sterically-constrained Ag 3 Pd(111)

Metal nanoparticles encapsulated within metal organic frameworks (MOFs) offer steric restrictions near the catalytic metal that can improve selectivity, much like in enzymes. A microkinetic model is developed for the regio-selective oxidation of n -butane to 1-butanol with O 2 over a model for MOF-encapsulated bimetallic nanoparticles. The model consists of a Ag 3 Pd(111) surface decorated with a 2-atom-thick ring of (immobile) helium atoms which creates an artificial pore of similar size to that in common MOFs, which sterically constrains the adsorbed reaction intermediates. The kinetic parameters are based on energies calculated using density functional theory (DFT). The microkinetic model was analysed at 423 K to determine the dominant pathways and which species (adsorbed intermediates and transition states in the reaction mechanism) have energies that most sensitively affect the reaction rates to the different products, using degree-of-rate-control (DRC) analysis. This analysis revealed that activation of the C–H bond is assisted by adsorbed oxygen atoms, O*. Unfortunately, O* also abstracts H from adsorbed 1-butanol and butoxy as well, leading to butanal as the only significant product. This suggested to (1) add water to produce more OH*, thus inhibiting these undesired steps which produce OH*, and (2) eliminate most of the O 2 pressure to reduce the O* coverage, thus also inhibiting these steps. Combined with increasing butane pressure, this dramatically improved the 1-butanol selectivity (from 0 to 95%) and the rate (to 2 molecules per site per s). Moreover, 40% less O 2 was consumed per oxygen atom in the products. Under these conditions, a terminal H in butane is directly eliminated to the Pd site, and the resulting adsorbed butyl combines with OH* to give the desired 1-butanol. These results demonstrate that DRC analysis provides a powerful approach for optimizing catalytic process conditions, and that highly selectivity oxidation can sometimes be achieved by using a mixture of O 2 and H 2 O as the oxidant. This was further demonstrated by DRC analysis of a second microkinetic model based on a related but hypothetical catalyst, where the activation energies for two of the steps were modified.

catalysis (heterogeneous), materials and chemistry↗