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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 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Interaction of methanol with a layered α-Sn(IV) phosphate on its surface: A solid-state NMR study

Here, a layered crystalline phosphate, α-Sn(HPO 4 ) 2 ·H 2 O, treated with CD 3 OD was characterized by the 31 P, 119 Sn, 1 H and 2 H solid-state NMR techniques. The 2 H solid-echo MAS NMR spectra of the product have unexpectedly revealed deuterated hydronium ions on the surface of this material instead of intercalated methanol. According to the 13 C NMR and GC–MS studies, these ions are formed by water molecules following a dehydration of the methanol-d 4 to yield deuterated dimethyl ether.

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

Maximum Impact of Ionic Strength on Acid‐Catalyzed Reaction Rates Induced by a Zeolite Microporous Environment

Abstract The intracrystalline ionic environment in microporous zeolite can remarkably modify the excess chemical potential of adsorbed reactants and transition states, thereby influencing the catalytic turnover rates. However, a limit of the rate enhancement for aqueous‐phase dehydration of alcohols appears to exist for zeolites with high ionic strength. The origin of such limitation has been hypothesized to be caused by the spatial constraints in the pores via, e.g., size exclusion effects. It is demonstrated here that the increase in turnover rate as well as the formation of a maximum and the rate drop are intrinsic consequences of the increasingly dense ionic environment in zeolite. The molecularly sized confines of zeolite create a unique ionic environment that monotonically favors the formation of alcohol‐hydronium ion complexes in the micropores. The zeolite microporous environment determines the kinetics of catalytic steps and tailors the impact of ionic strength on catalytic rates.

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

Diameter-dependent multiple proton jumps dictate hydronium and hydroxide transport in carbon nanotubes

Nanofluidic channels impose extreme confinement on water, giving rise to unusual transport phenomena of the liquid. However, how the transport of hydroxide and hydronium ions is influenced by such confinement is still not fully understood. This study employs machine learning-accelerated simulations, based on the SCAN density functional, to investigate proton transfer dynamics in CNTs of varying diameters (0.8 nm to 2.8 nm). The extreme confinement of water inside a 0.8 nm CNT not only enhances the probability of multiple consecutive proton jumps, but also reverses the relative diffusion coefficient of hydronium and hydroxide ions in bulk water. In CNTs with diameters larger than 0.8 nm, hydronium diffuses slightly faster than in bulk water, whereas hydroxide diffusion slows because of its localization near CNT walls, hindering multiple proton jumps. This work highlights the significant impact of nanoscale confinement on proton transfer dynamics, with implications for designing nanoscale systems with controlled proton transport.

Chemistry↗
DOE OSTI2025

Product ion distributions using H 3 O + proton-transfer-reaction time-of-flight mass spectrometry (PTR-ToF-MS): mechanisms, transmission effects, and instrument-to-instrument variability

Abstract. Proton-transfer-reaction mass spectrometry (PTR-MS) using hydronium ion (H3O+) ionization is widely used for the measurement of volatile organic compounds (VOCs) both indoors and outdoors. H3O+ ionization, as well as the associated chemistry in an ion–molecule reactor, is known to generate product ion distributions (PIDs) that include other product ions besides the proton-transfer product. We present a method, using gas-chromatography pre-separation, for quantifying PIDs from PTR-MS measurements of nearly 100 VOCs of different functional types including alcohols, ketones, aldehydes, acids, aromatics, organohalides, and alkenes. We characterize instrument configuration effects on PIDs and find that reactor reduced electric field strength (E/N), ion optic voltage gradients, and quadrupole settings have the strongest impact on measured PIDs. Through an interlaboratory comparison of PIDs measured from calibration cylinders, we characterized the variability of PID production from the same model of PTR-MS across seven participating laboratories. Product ion variability was generally smaller (e.g., < 20 %) for ions with larger contributions to the PIDs (e.g., > 0.30) but less predictable for product ions formed through O2+ and NO+ reactions. We present a publicly available library of H3O+ PTR-MS PIDs that will be updated periodically with user-provided data for the continued investigation into instrument-to-instrument variability of PIDs.

Link, Michael F. (ORCID:0000000218412455)↗
DOE OSTI2021

Proton Traffic Jam: Effect of Nanoconfinement and Acid Concentration on Proton Hopping Mechanism

Abstract The properties of the water network in concentrated HCl acid pools in nanometer‐sized reverse nonionic micelles were probed with TeraHertz absorption, dielectric relaxation spectroscopy, and reactive force field simulations capable of describing proton hopping mechanisms. We identify that only at a critical micelle size of W 0 =9 do solvated proton complexes form in the water pool, accompanied by a change in mechanism from Grotthuss forward shuttling to one that favors local oscillatory hopping. This is due to a preference for H + and Cl − ions to adsorb to the micelle interface, together with an acid concentration effect that causes a “traffic jam” in which the short‐circuiting of the hydrogen‐bonding motif of the hydronium ion decreases the forward hopping rate throughout the water interior even as the micelle size increases. These findings have implications for atmospheric chemistry, biochemical and biophysical environments, and energy materials, as transport of protons vital to these processes can be suppressed due to confinement, aggregation, and/or concentration.

Adams, Ellen M.↗
DOE OSTI2021

Proton Traffic Jam: Effect of Nanoconfinement and Acid Concentration on Proton Hopping Mechanism

Abstract The properties of the water network in concentrated HCl acid pools in nanometer‐sized reverse nonionic micelles were probed with TeraHertz absorption, dielectric relaxation spectroscopy, and reactive force field simulations capable of describing proton hopping mechanisms. We identify that only at a critical micelle size of W 0 =9 do solvated proton complexes form in the water pool, accompanied by a change in mechanism from Grotthuss forward shuttling to one that favors local oscillatory hopping. This is due to a preference for H + and Cl − ions to adsorb to the micelle interface, together with an acid concentration effect that causes a “traffic jam” in which the short‐circuiting of the hydrogen‐bonding motif of the hydronium ion decreases the forward hopping rate throughout the water interior even as the micelle size increases. These findings have implications for atmospheric chemistry, biochemical and biophysical environments, and energy materials, as transport of protons vital to these processes can be suppressed due to confinement, aggregation, and/or concentration.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Effect of electrode rinse solutions on the electrodialysis of concentrated salts

The data presented indicate that modest attention to the chemistry of the electrode rinse solution can yield as much as 56% improvement in process efficiency. When operating electrodialysis (ED) with salt concentrations greater than 10,000 mg/l (as NaCl) the amperage can be relatively high even at low voltages. To maximize the overall rate of ion transport from diluate to concentrate, there is a need to minimize resistances in the electrode cells since these can represent as much as 30% of the total resistances in the entire process and in this particular ED unit, represented resistance roughly equivalent to that within the membrane stack. This work describes the performance of a 10-cell pair, 200 cm 2 (0.02 m 2 ) per membrane, pilot ED unit operated in batch mode at 5 V potential. The feedstock to the stack was varied from 0.5% to 6% NaCl. Results from Volt-amp profiles (2.0–15 V) were used as the rationale for choosing the preferred electrode rinse solution, 90 g/l (kg/m 3 ) disodium sulfate at pH 12.5. The recommended solution of 30 g/l (kg/m 3 ) disodium sulfate at neutral pH was tested against stronger solutions (60, 90, and 120 g/l (kg/m 3 ) disodium sulfate) at neutral pH and with 1 g/l (kg/m 3 ) sodium hydroxide added to yield solutions at pH 12.5. There were stark differences in the performance of the ED unit between the solutions at pH 7 and those at pH 12.5. The slopes of the Volt-amp profiles improved indicating less resistance to ion flow at pH 12.5. Most of the difference can be attributed to the greater conductivity of sodium hydroxide compared to disodium sulfate, where even a modest addition of 1 g/l (kg/m 3 ) sodium hydroxide increased the conductivity of the solution between 8 and 20% depending on the concentration of disodium sulfate. Most notably, the initiation voltage was 2.39 ± 0.08 V with solutions at pH 7 and 1.99 V ± 0.04 V when the rinse solutions were around pH 12.5, a difference of around 0.42 V. Since the full batch runs were performed at 5.0 V, this 0.42 V differential represented a loss of 8% in process efficiency. A series of tests showed a shift in initiation voltage occurred between pH 11.5 and 12.5. Nernst equations for water electrolysis are coupled with a simple flux model that estimates the concentration of hydroxide and hydronium ions at the electrode surfaces. This model indicates that the potential demanded by the electrodes is directly linked to the current. Furthermore, there is a steep drop in the potential demanded by the anode when there is sufficient hydroxide available to generate oxygen from hydroxide as opposed to generation from water. The voltage demand is minimal at pH 12.5 and reflective of the reference standard voltage (just over 1.23 V predicted at 0.1 amps). However, the flux model predicts that the voltage demanded by the electrodes at pH 7 is 1.61 V at 0.1 amps (the lowest amperage measurable with the power pack). In conclusion, comparing this result to the reference standard (E 0 = -1.23 V) yields a satisfactory explanation for the observed difference below reference standard of 0.42 V.

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

Hydrogen Bonding Enhances the Electrochemical Hydrogenation of Benzaldehyde in the Aqueous Phase

Abstract The hydrogenation of benzaldehyde to benzyl alcohol on carbon‐supported metals in water, enabled by an external potential, is markedly promoted by polarization of the functional groups. The presence of polar co‐adsorbates, such as substituted phenols, enhances the hydrogenation rate of the aldehyde by two effects, that is, polarizing the carbonyl group and increasing the probability of forming a transition state for H addition. These two effects enable a hydrogenation route, in which phenol acts as a conduit for proton addition, with a higher rate than the direct proton transfer from hydronium ions. The fast hydrogenation enabled by the presence of phenol and applied potential overcompensates for the decrease in coverage of benzaldehyde caused by competitive adsorption. A higher acid strength of the co‐adsorbate increases the intensity of interactions and the rates of selective carbonyl reduction.

Sanyal, Udishnu↗
DOE OSTI2022

Maximum Impact of Ionic Strength on Acid‐Catalyzed Reaction Rates Induced by a Zeolite Microporous Environment

Abstract The intracrystalline ionic environment in microporous zeolite can remarkably modify the excess chemical potential of adsorbed reactants and transition states, thereby influencing the catalytic turnover rates. However, a limit of the rate enhancement for aqueous‐phase dehydration of alcohols appears to exist for zeolites with high ionic strength. The origin of such limitation has been hypothesized to be caused by the spatial constraints in the pores via, e.g., size exclusion effects. It is demonstrated here that the increase in turnover rate as well as the formation of a maximum and the rate drop are intrinsic consequences of the increasingly dense ionic environment in zeolite. The molecularly sized confines of zeolite create a unique ionic environment that monotonically favors the formation of alcohol‐hydronium ion complexes in the micropores. The zeolite microporous environment determines the kinetics of catalytic steps and tailors the impact of ionic strength on catalytic rates.

Liu, Qiang↗
DOE OSTI2020

Electrochemically tunable proton-coupled electron transfer in Pd-catalyzed benzaldehyde hydrogenation

Acid-functionalization of carbon support allows enhancing the electrocatalytic activity of Pd to hydrogenate benzaldehyde to benzyl alcohol in proportion to the concentration of Brønsted acid sites. The hydrogenation rate is not enhanced when H2 is used. The rate enhancement is attributed to differences in the hydrogenation mechanism between the electrochemical and the H2 induced hydrogenations, in particular to the participation of hydronium ions formed at Brønsted acid sites at the perimeter of metal particles in proton coupled electron transfer.

Koh, Katherine↗
DOE OSTI2022

How Water Attacks MXene

Two-dimensional (2D) transition metal carbides and nitrides (MXenes) have shown outstanding performances in electrochemical energy storage and many other applications. However, the stability of MXene remains a concern, especially its quick degradation in aqueous solutions under ambient conditions. Here, we report on the water/Ti 3 C 2 O 2 -MXene interfacial chemistry from first-principles molecular dynamics simulations at room temperature. Surprisingly, we find that the water molecules can attack the basal plane of Ti 3 C 2 O 2 and pull the surface Ti atoms out, thereby reconstructing the surface. Further, by tracking close encounters of water molecules and surface Ti atoms on the basal plane of Ti 3 C 2 O 2 , we show that the attack is initiated by the chemisorption of a water molecule on a surface Ti atom, followed by the breaking of Ti–C bonds and deprotonation of the water molecule, leading to the formation of Ti–OH on the Ti 3 C 2 O 2 surface and a hydronium ion in the aqueous phase. Our finding highlights the susceptibility of Ti 3 C 2 O 2 MXene to water attack, supporting recent experimental observations. Furthermore, we demonstrate that preventing close encounters of water molecules and the surface Ti atoms is key to the stability of the basal plane and can be realized by negatively charging the surface (thereby reorienting the O atoms of water away from the surface) or converting the surface O to -OH groups (thereby shifting the water layer further away from the surface). Our insights and approach highlight the importance of the reactivity of water when interfacing with 2D materials such as MXenes.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Low-Energy Isomers of the Magic Number H + (H 2 O) 21 Cluster

Electronic structure calculations are used to characterize low-energy isomers of H + (H 2 O) 21 . Eleven different classes of isomers, based on the (H 2 O) 20 pentagonal dodecahedron with the excess proton localized on the surface (as a hydrated hydronium ion) and the “extra” water molecule located in the interior of the cluster, are characterized. In 10 of these classes, the internal water molecule is engaged in six 5-membered rings, but in the remaining class, which is predicted to start at only 0.6 kcal/mol above the global minimum, the internal water is engaged in a 4- membered ring, an additional 6-membered ring, and four 5- membered rings. In addition, isomers with two 4-membered rings and two 6-membered rings on the cluster surface are predicted to start at only ∼1.3 kcal/mol above the lowest-energy dodecahedralbased structure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Size-Dependent Onset of Nitric Acid Dissociation in Cs + ·(HNO 3 )(H 2 O) n =0–11 Clusters at 20 K

We report the water-mediated charge separation of nitric acid upon incorporation into size-selected Cs + ∙(HNO 3 )(H 2 O) n=0-11 clusters at 20 K. Dramatic spectral changes are observed in the range n=7-9 that are traced to the formation of many isomeric structures associated with intermediate transfer of the acidic proton to the water network. This transfer is complete by n=10, which exhibits much simpler vibrational band patterns consistent with those expected for a tri-coordinated hydronium ion (the Eigen motif) along with the NO stretching bands predicted for a hydrated NO 3 – anion that is directly complexed to the Cs + cation. Theoretical analysis of the n=10 spectrum indicates that the dissociated ions adopt a solvent-separated ion-pair configuration such that the Cs + and H 3 O + cations flank the NO 3 – anion in a microhydrated salt bridge. In conclusion, this charge separation motif is evidently assisted by the electrostatic stabilization of the product NO 3 – /H 3 O + ion pair by the proximal metal ion.

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

Rate Enhancement of Acid-Catalyzed Alcohol Dehydration by Supramolecular Organic Capsules

The presence of a (sub)nanometric environment has been demonstrated to enhance the rate of homogeneous acid-catalyzed reactions. Conventionally, such catalysts are constructed by directly embedding a catalytically active acid site into the structure of a porous material, linking the acid properties with the properties of the embedding solid. Here, a holoenzyme mimicking approach was used, in which a self-assembled hexameric resorcinarene capsule (1.4 nm 3 cavity) acts like an apoenzyme that transforms into a catalytically active site by hosting hydrated HCl as a cofactor. This capsule binds the hydronium ion together with cyclohexanol (CyOH) and catalyzes the dehydration to cyclohexene with enhanced rates that are 2 orders of magnitude higher than those in the unconstrained environment. Kinetic analysis shows that cyclohexanol dehydration proceeds via an E2 mechanism on hydrated HCl in the unconstrained environment, while the constrained environment of the active capsule induces the stabilization of an ionic intermediate, allowing an E1 mechanism to dominate. By comparison with the reaction in zeolite environments, we show that the direct chemical environment of the capsule or a zeolite wall exerts only a minor direct influence. The volume constraint increases the reaction rate by inducing a larger activation entropy, indicating the stabilization of a later transition state in the E1 mechanism, as well as a higher reaction space of the carbenium ion constituting the transition state.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Differences in Mechanism and Rate of Zeolite-Catalyzed Cyclohexanol Dehydration in Apolar and Aqueous Phase

The rate of acid-base catalyzed dehydration of alcohols strongly depends on the solvent and the environment of the acid sites. In this work, we find that Brønsted acidic sites in large-pore zeolites, but not in medium-pore zeolites, catalyze cyclohexanol dehydration in decalin at significantly higher rates than hydrated hydronium ions in aqueous phase. Specifically, the difference in turnover rates between the two solvents amounts to two to three orders of magnitude on H-BEA and H-FAU, while being very modest (within a factor of 2) for H-MFI. Combining kinetic, isotopic tracer and 2H NMR measurements, it is established that cyclohexanol dehydration generally follows an E1-elimination pathway in decalin. A notable exception is the monomer dehydration route on H-MFI, which exhibits a much lower activation energy and a substantially negative activation entropy that appear to be associated with an E2-type mechanism. The C-O bond cleavage displays a dominant degree of rate control in decalin, which stands in contrast to deprotonation (C-H cleavage) being rate-limiting in aqueous-phase dehydration.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Solvent molecules form surface redox mediators in situ and cocatalyze O 2 reduction on Pd

Solvent molecules influence the reactions of molecular hydrogen and oxygen on palladium nanoparticles. Organic solvents activate to form reactive surface intermediates that mediate oxygen reduction through pathways distinct from reactions in pure water. Kinetic measurements and ab initio quantum chemical calculations indicate that methanol and water cocatalyze oxygen reduction by facilitating proton-electron transfer reactions. Methanol generates hydroxymethyl intermediates on palladium surfaces that efficiently transfer protons and electrons to oxygen to form hydrogen peroxide and formaldehyde. Formaldehyde subsequently oxidizes hydrogen to regenerate hydroxymethyl. Water, on the other hand, heterolytically oxidizes hydrogen to produce hydronium ions and electrons that reduce oxygen. These findings suggest that reactions of solvent molecules at solid-liquid interfaces can generate redox mediators in situ and provide opportunities to substantially increase rates and selectivities for catalytic reactions.

Adams, Jason S.↗
DOE OSTI2022

Direct and Sensitive Electrochemical Evaluation of Pramipexole Using Graphitic Carbon Nitride (gCN) Sensor

Pramipexole (PMXL) belongs to the benzothiazole class of aromatic compounds and is used in treating Parkinson’s disease; however, overdosage leads to some abnormal effects that could trigger severe side effects. Therefore, it demands a sensitive analytical tool for trace level detection. In this work, we successfully developed an electrochemical sensor for the trace level detection of PMXL, using the voltammetric method. For the analysis, graphitic carbon nitride (gCN) was opted and synthesized by using a high-temperature thermal condensation method. The synthesized nanoparticles were employed for surface characterization, using transmission electron microscopy (TEM), X-ray diffraction (XRD), and atomic force microscopy (AFM) techniques. The electrochemical characterization of the material was evaluated by using the electrochemical impedance spectroscopy (EIS) technique to evaluate the solution–electrode interface property. The cyclic voltammetry (CV) behavior of PMXL displayed an anodic peak in the forward scan, indicating that PMXL underwent electrooxidation, and an enhanced detection peak with lower detection potential was achieved for gCN-modified carbon paste electrode (gCN·CPE). The influence of different parameters on the electrochemical behavior was analyzed, revealing the diffusion governing the electrode process with an equal number of hydronium ions and electron involvement. For the fabricated gCN·CPE, good linearity range was noticed from 0.05 to 500 µM, and a lower detection limit (L D ) of 0.012 µM was achieved for the selected concentration range (0.5 to 30 µM). Selectivity of the electrode in PMXL detection was investigated by conducting an interference study, while the tablet sample analysis demonstrates the sensitive and real-time application of the electrode. The good recovery values for the analysis illustrate the efficiency of the electrode for PMXL analysis.

36 MATERIALS SCIENCE↗