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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 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Morphology Dependent Reactivity of CsO $x$ Nanostructures on Au(111): Binding and Hydrogenation of CO 2 to HCOOH

Cesium oxide (CsO $x$ ) nanostructures grown on Au(111) behave as active centers for CO 2 binding and hydrogenation reactions. The morphology and reactivity of these CsO $x$ systems were investigated as a function of alkali coverage using scanning tunnelling microscopy (STM), ambient pressure X-ray photoelectron spectroscopy (AP-XPS), and density functional theory (DFT) calculations. STM results show that initially (0.05 - 0.10 ML) cesium oxide clusters (Cs 2 O 2 ) grow at the elbow sites of the herringbone of Au(111), subsequently transforming into two-dimensional islands with increasing cesium coverage (> 0.15 ML). XPS measurements reveal the presence of suboxidic (Cs $y$ O; $y$ ≥ 2) species for the island structures. The higher coverages of cesium oxide nanostructures contain a lower O/Cs ratio resulting in a stronger binding of CO 2 . Moreover, the O atoms in the Cs $y$ O structure undergo a rearrangement upon the adsorption of CO 2 which is a reversible phenomenon. Under CO 2 hydrogenation conditions, the small Cs 2 O 2 clusters are hydroxylated, thereby preventing the adsorption of CO 2 . However, the hydroxylation of the higher coverages of Cs $y$ O did not prevent CO 2 adsorption, and the adsorbed CO 2 transformed to HCOO species that eventually yield HCOOH. DFT calculations further confirm that the dissociated H 2 attacks the C in the adsorbate to produce formate, which is both thermodynamically and kinetically favored during the CO 2 reaction with hydroxylated Cs $y$ O. These results demonstrate that cesium oxide by itself is an excellent catalyst for CO 2 hydrogenation that could produce formate, an important intermediate for the generation of value-added species. The role of the alkali oxide nanostructures as active centers, not merely as promoters, may have broad implications wherein the alkali oxides can be considered in the design of materials tuned for specific applications in heterogeneous catalysis.

03 NATURAL GAS↗
DOE OSTI2021

Understanding the origin of structure sensitivity in hydrodechlorination of trichloroethylene on a palladium catalyst

Periodic density functional theory (DFT) calculations are employed to understand the origin of structure sensitivity in hydrodechlorination (HDC) of trichloroethylene (TCE) over different facets of a palladium catalyst. The HDC reaction is simulated on the terrace (Pd (111) and Pd (100)) and undercoordinated (Pd (211) and Pd (110)) sites of the Pd catalyst. The most stable binding configuration of TCE on the Pd surfaces is observed to be through the di-σ mode of binding, wherein each carbon atom of the TCE molecule is adsorbed atop of the Pd atom. On comparing TCE adsorption over different facets of Pd, a maximum binding energy of –178 kJ mol –1 is calculated over the Pd (110) surface. TCE, upon adsorption on Pd catalyst, undergoes dechlorination followed by hydrogenation of the hydrocarbon intermediates. The activation energies for C–Cl bond dissociation steps are significantly low when compared to the hydrogenation steps. The chlorine released from dechlorination tends to block the active sites, thereby poisoning the surface with high binding energies (B.E > –160 kJ mol –1 ) on all the surfaces. The trend in chlorine binding energies on Pd facets follows: Pd (110) > Pd (211) > Pd (100) > Pd (111). The removal of surface chlorine is facilitated by its reaction with surface hydrogen to form hydrogen chloride. The activation energy for hydrogen chloride formation is calculated to be 90 kJ mol –1 and 88 kJ mol –1 on Pd (111) and Pd (100) terrace sites, respectively and 109 kJ mol –1 and 118 kJ mol –1 on the step Pd (211) and corrugated Pd (110) facets, respectively. This suggests the ease of removal of Cl as HCl from the terrace sites as compared to the step and corrugated sites. The structure sensitivity in the TCE HDC reaction could possibly arise due to the differences in the energetics of Cl removal on different Pd facets. As a result, this mechanistic understanding could provide a rationale for designing suitable catalysts for the HDC of TCE.

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

Mechanistic Insights into Oxygen Reduction Reaction on Metal Cathode Over BaZrO 3 -Based Electrolyte under Moist Atmosphere: Interfacial Interactions and Reaction Pathways

The oxygen reduction reaction (ORR) is a critical process that often governs the overall performance of electrochemical systems such as proton conducting solid oxide fuel cells. Despite its significance, the current understanding about the ORR, especially when it involves H 2 O is still limited. In this study, the proton involved ORR (PI-ORR) on metal cathode (e.g., Pt) over BaZrO 3 (BZO) electrolyte is investigated using density functional theory (DFT) under moist atmosphere. Two scenarios are considered: one at relatively high temperature (900 K) in the presence of oxygen vacancy in BZO substrate and one at relatively low temperature (700 K) without oxygen vacancy. We systematically explored oxygen vacancy effects on adsorption sites and proton transfer pathways, calculated energy profiles and Gibbs free energies for elementary steps along the O 2 dissociated and the O 2 concerted reaction pathways. We also evaluated H 2 O impacts on intermediate oxygen species (*O and *OH) through Ab Initio molecular dynamics. These analyses revealed pathway-dependent reaction mechanisms and hydration effects at triple-phase boundary, advancing fundamental understanding of PI-ORR in metal cathode/Ba-based electrolyte systems for energy applications.

08 - HYDROGEN↗
NASA NTRS1973

Oxygen and sulfur interactions with a clean iron surface and the effect of rubbing contact on these interactions

An investigation was conducted to determine the nature of the chemical interactions of oxygen and sulfur with iron when surfaces are stationary and also during sliding in a vacuum environment. Various gases that contained sulfur, oxygen, or both were adsorbed to iron at 23 C. The gases included oxygen, hydrogen sulfide, methyl mercaptan, and sulfur dioxide. Friction experiments were conducted with a hemispherical rider sliding on a rotating disk. An Auger cylindrical mirror analyzer was used to monitor the iron surface chemistry. The results of this study indicate that oxygen will completely displace sulfide films from iron surfaces. Organic thiols containing sulfur, such as methyl mercaptan, adsorb to an iron surface dissociatively. Only sulfur is detected on the iron surface. Sliding inhibits the formation of sulfide films on iron with the adsorption of hydrogen sulfide and methyl mercaptan. With oxygen and sulfur dioxide, the sliding process does not affect adsorption behavior.

Buckley, D. H.↗
DOE OSTI2025

Irreversible oxygen poisoning: Modeling the initial water dissociation kinetics on δ-Pu(111) and δ-Pu(100) through density functional theory

In this work, the initial kinetics of water dissociation on two facets of δ-plutonium, δ-Pu(111) and δ-Pu(100), are explored through density functional theory in order to understand how water dissociation occurs on these facets. We explored the dissociation of water via the formation of hydroxyls, atomic hydrogen, and atomic oxygen species on each facet. We calculate low energetic barriers for water to split to adsorbed hydrogen and hydroxyl species at 0.19 eV for δ-Pu(111) and 0.07 eV for δ-Pu(100). The hydroxyl has a barrier of 0.64 and 0.37 eV to cleave the hydrogen–oxygen bond on δ-Pu(111) and δ-Pu(100), respectively. Due to the highly exergonic adsorption free energy of atomic oxygen of −2.10 eV, the metallic surfaces are found to be fully covered in oxygen, even with the inclusion of oxygen lateral interactions. When combined with the reaction thermodynamics, this free energy of adsorption forms a molecular oxygen desorption barrier greater than 9.51 eV (918 kJ/mol). These results, combined with simulated temperature programed desorption spectra, indicate that oxygen formed via water dissociation on δ-Pu (111) and (100) facets induces an irreversible poison that prevents further reaction of water directly on metallic plutonium surfaces, most likely due to the strong hybridization of the Pu and O valence states. Therefore, these results imply that another mechanism is responsible for the continuously experimentally measured water dissociation, which is most likely due to the Pu oxide.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Highly-Cyclable Room-Temperature Phosphorene Polymer Electrolyte Composites for Li Metal Batteries

Despite significant interest toward solid-state electrolytes owing to their superior safety in comparison to liquid-based electrolytes, sluggish ion diffusion and high interfacial resistance limit their application in durable and high-power density batteries. Here, a novel quasi-solid Li + ion conductive nanocomposite polymer electrolyte containing black phosphorous (BP) nanosheets is reported. The developed electrolyte is successfully cycled against Li metal (over 550 h cycling) at 1 mA cm -2 at room temperature. The cycling overpotential is dropped by 75% in comparison to BP-free polymer composite electrolyte indicating lower interfacial resistance at the electrode/electrolyte interfaces. Molecular dynamics simulations reveal that the coordination number of Li + ions around (trifluoromethanesulfonyl)imide (TFSI - ) pairs and ethylene-oxide chains decreases at the Li metal/electrolyte interface, which facilitates the Li + transport through the polymer host. Here, density functional theory calculations confirm that the adsorption of the LiTFSI molecules at the BP surface leads to the weakening of N and Li atomic bonding and enhances the dissociation of Li + ions. This work offers a new potential mechanism to tune the bulk and interfacial ionic conductivity of solid-state electrolytes that may lead to a new generation of lithium polymer batteries with high ionic conduction kinetics and stable long-life cycling.

2D materials↗
DOE OSTI2023

Free-standing membrane incorporating single-atom catalysts for ultrafast electroreduction of low-concentration nitrate

The release of wastewaters containing relatively low levels of nitrate (NO 3 ⁻) results in sufficient contamination to induce harmful algal blooms and to elevate drinking water NO 3 ⁻ concentrations to potentially hazardous levels. In particular, the facile triggering of algal blooms by ultra-low concentrations of NO 3 ⁻ necessitates the development of efficient methods for NO 3 ⁻ destruction. However, promising electrochemical methods suffer from weak mass transport under low reactant concentrations, resulting in long treatment times (on the order of hours) for complete NO 3 ⁻ destruction. In this study, we present flow-through electrofiltration via an electrified membrane incorporating nonprecious metal single-atom catalysts for NO 3 ⁻ reduction activity enhancement and selectivity modification, achieving near-complete removal of ultra-low concentration NO 3 ⁻ (10 mg-N L -1 ) with a residence time of only a few seconds (10 s). By anchoring Cu single atoms supported on N-doped carbon in a carbon nanotube interwoven framework, we fabricate a free-standing carbonaceous membrane featuring high conductivity, permeability, and flexibility. The membrane achieves over 97% NO 3 ⁻ removal with high N 2 selectivity of 86% in a single-pass electrofiltration, which is a significant improvement over flow-by operation (30% NO 3 ⁻ removal with 7% N 2 selectivity). This high NO 3 ⁻ reduction performance is attributed to the greater adsorption and transport of nitric oxide under high molecular collision frequency coupled with a balanced supply of atomic hydrogen through H 2 dissociation during electrofiltration. Overall, our findings provide a paradigm of applying a flow-through electrified membrane incorporating single-atom catalysts to improve the rate and selectivity of NO 3 ⁻ reduction for efficient water purification.

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

Molecular-level insights into CO 2 activation on Ni(111) from in situ infrared spectroscopy

The activation of CO 2 on nickel surfaces is the first step of various CO 2 conversion processes. Consequently, understanding the surface intermediates formed during this step and their adsorption sites is crucial for elucidating reaction mechanisms. In this study, we employ in situ infrared spectroscopy to investigate the interaction of 1 mbar CO 2 with a model Ni(111) catalyst between 25°C and 300°C. Under these conditions, CO 2 is activated via a direct dissociation into CO and atomic oxygen, while the oxidation state of the Ni(111) surface is primarily determined by residual H 2 and O 2 . The high surface coverage of CO and oxygen at ambient CO 2 pressure induces a competitive adsorption mechanism on the energetically favored hollow sites. This mechanism leads to a temperature-dependent distribution of CO between top and hollow sites, potentially explaining the effect of reaction conditions on the adsorption site of CO intermediates in CO 2 conversion reactions.

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

Nature of Oxygen Adsorption on Defective Carbonaceous Materials

Here, plane-wave density functional theory has been used to study oxygen adsorption on graphene, graphite, and (12,0) zigzag single-walled carbon nanotubes with and without Stone–Wales (SW) and single-vacancy (SV) defects to understand the role of defects on carbonaceous material reactivity. Atomic oxygen adsorption leads to the formation of an epoxide on defect-free graphene and graphite and an ether on the exterior wall of carbon nanotubes and SW-defected materials. O 2 chemisorption is endothermic on defect-free graphene and graphite and slightly exothermic on defect-free nanotubes. O 2 chemisorption energies are predicted to be –1.1 to –1.4 eV on an SW defect and –6.0 to –8.0 eV on an SV defect. An SW defect lowers the energy barriers by 0.90 and 0.50 eV for O 2 chemisorption on graphene and nanotubes, respectively. The formation of a C–O–O–C group is important for O 2 dissociation on defect-free and SW-defected materials. The energy barrier is less than 0.30 eV on an SV defect. The more reactive SW defect toward O adsorption on graphene is mostly due to the strained defective carbon atoms being able to donate more electrons to an O to form an ether. The larger 2s character in the hybrid orbitals in an ether than in an epoxide makes the ether C–O bond stronger. Stronger C–O binding on an SW-defective carbon nanotube than on a defect-free nanotube is in part due to more flexibility of the defect to release the epoxide ring strain to form an ether.

25 ENERGY STORAGE↗
NASA NTRS2008

Adsorption of Water on Simulated Moon Dust Samples

A lunar regolith simulant dust sample (JSC-1a) supported on a silica wafer (SiO2/Si(111)) has been characterized by scanning electron microscopy (SEM), energy dispersive x-ray spectroscopy (EDX), and Auger electron spectroscopy (AES). The adsorption kinetics of water has been studied primarily by thermal desorption spectroscopy (TDS) and also by collecting isothermal adsorption transients. The support has been characterized by water TDS. JSC-1a consists mostly of aluminosilicate glass and other minerals containing Fe, Na, Ca, and Mg. The particle sizes span the range from a few microns up to 100 microns. At small exposures, H2O TDS is characterized by broad (100 to 450 K) structures; at large exposures distinct TDS peaks emerge that are assigned to amorphous solid water (145 K) and crystalline ice (165 K). Water dissociates on JSC-1a at small exposures but not on the bare silica support. It appears that rather porous condensed ice layers form at large exposures. At thermal impact energies, the initial adsorption probability amounts to 0.92+/-0.05.

Goering, John P.↗
DOE OSTI2022

Counterions under a Surface-Adsorbed Cationic Surfactant Monolayer: Structure and Thermodynamics

The surface adsorption of ionic surfactants is fundamental for many widespread phenomena in life sciences and for a wide range of technological applications. However, direct atomic-resolution structural experimental studies of noncrystalline surface-adsorbed films are scarce. Thus, even the most central physical aspects of these films, such as their charge density, remain uncertain. Consequently, theoretical models based on contradicting assumptions as for the surface films' ionization are widely used for the description and prediction of surface thermodynamics. We employ X-ray reflectivity to obtain the angstrom Ångström-scale surface-normal structure of surface-adsorbed films of the cationic surfactant cetyltrimethylammonium bromide (CTAB) in aqueous solutions at several different temperatures and concentrations. In conjunction with published neutron reflectivity data, we determine the surface-normal charge distribution due to the dissociated surfactants' headgroups. The distribution appears to be inconsistent with the Gouy-Chapman model yet consistent with a compact Stern layer model of condensed counterions. Here, the experimental surfactant adsorption thermodynamics conforms well to classical, Langmuir and Kralchevsky, adsorption models. Furthermore, the Kralchevsky model correctly reproduces the observed condensation of counterions, allowing the values of the adsorption parameters to be resolved, based on the combination of the present data and the published surface tension measurements.

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

PFOA catalytic reaction mechanisms on zerovalent iron (Fe 0 ): A DFT investigation

In this study, density functional theory (DFT) calculations with dispersion corrections are employed to investigate catalytic reactions of perfluorooctanoic acid (PFOA) onto zerovalent iron (Fe 0 ). The main goal of this investigation is to explain the reaction mechanisms, including bond dissociation energies, activation barriers, and rate-determining steps (RDSs), of PFOA degradation. Additionally, we aim to reveal the catalytic effects of Fe 0 by comparing the reaction energy profile for the degradation of PFOA both in solution (i.e., isolated) and after adsorption on Fe 0 . Along with investigating previously reported pathways, this study proposes a new PFOA degradation pathway on Fe0. Overall, the results revealed that Fe 0 plays a key role in the catalytic degradation of PFOA, significantly affecting the RDSs and increasing defluorination rates. For instance, the activation barrier for the decarboxylation step significantly decreased from 3.08 eV to 1.11 eV over the Fe0 surface, while the activation barrier for F dissociation decreased from ∼5 eV to 0.54 eV. Additionally, the proposed pathway in this study (i.e., successive defluorination) was found to be the most favorable pathway for PFOA degradation on Fe 0 . Taken together, the DFT results are consistent with reported experimental findings and provide critical insights that will help advance the design of catalysts for PFAS degradation.

Catalysis↗
DOE OSTI2021

A Model for Atomic Precision p-Type Doping with Diborane on Si(100)-2×1

Diborane (B 2 H 6 ) is a promising molecular precursor for atomic precision p-type doping of silicon that has recently been experimentally demonstrated. In this study, we use density functional theory (DFT) calculations to determine the reaction pathway for diborane dissociating into a species that will incorporate as electrically active substitutional boron after adsorbing onto the Si(100)-2×1 surface. Our calculations indicate that diborane must overcome an energy barrier to adsorb, explaining the experimentally observed low sticking coefficient (<1 × 10 –4 at room temperature) and suggesting that heating can be used to increase the adsorption rate. Upon sticking, diborane has an ≈50% chance of splitting into two BH 3 fragments versus merely losing hydrogen to form a dimer such as B 2 H 4 . As boron dimers are likely electrically inactive, whether this latter reaction occurs is shown to be predictive of the incorporation rate. The dissociation process proceeds with significant energy barriers, necessitating the use of high temperatures for incorporation. Using the barriers calculated from DFT, we parameterize a Kinetic Monte Carlo model that predicts the incorporation statistics of boron as a function of the initial depassivation geometry, dose, and anneal temperature. Our results suggest that the dimer nature of diborane inherently limits its doping density as an acceptor precursor and furthermore that heating the boron dimers to split before exposure to silicon can lead to poor selectivity on hydrogen and halogen resists. This suggests that, while diborane works as an atomic precision acceptor precursor, other non-dimerized acceptor precursors may lead to higher incorporation rates at lower temperatures.

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

Diastereoselectivity Controlled by the Hydrogenation Mechanisms during the Electrochemical Reduction of a Carbonyl Group

Stereocontrol is of critical importance in organic synthesis. In this study, we demonstrate how heterogeneous electrochemical hydrogenation enables diastereocontrol simply by tuning electrochemical hydrogenation mechanisms without altering the adsorption conformation of a reactant on the electrode. We use 4-hydroxy-1-tetralone (4-OH-tetralone) as a model reactant, where diastereomers can be produced during the hydrogenation of the carbonyl group. In traditional thermocatalytic hydrogenation, H 2 first dissociates on the catalyst surface to form surface-adsorbed hydrogen (H*), and therefore, H* is always added to the organic reactant from the catalyst side via hydrogen atom transfer (HAT). Thus, in order to flip the diastereoselectivity, the adsorbed reactant itself must be physically flipped. In contrast, electrochemical hydrogenation can occur either via HAT, where H is added from the electrode surface, or via proton-coupled electron transfer (PCET), where H is added from the solution side of the adsorbed reactant. Thus, without changing the adsorption conformation of the reactant, opposite diastereomers can be obtained by switching the hydrogenation mechanism (HAT vs PCET). In this work, using a combination of experimental and computational studies, we demonstrate two examples of flipping diastereoselectivity by different electrochemical hydrogenation mechanisms. In the first case, we achieve opposite diastereoselectivities using metals that adopt different hydrogenation mechanisms (HAT vs PCET). In the second case, we flip the diastereoselectivity by varying the applied potential, which switches one hydrogenation mechanism to the other on the same metal electrode. In each case, our results offer an atomic-level understanding of the preferred hydrogenation mechanism that enables the corresponding diastereoselectivity.

adsorption↗
DOE OSTI2022

CO 2 Hydrogenation to Methanol over Inverse ZrO 2 /Cu(111) Catalysts: The Fate of Methoxy under Dry and Wet Conditions

Understanding the surface chemistry of CH 3 O species is essential for the production of methanol by CO 2 hydrogenation over Cu-based heterogeneous catalysts, as it facilitates the rational design of more efficient conversion processes. Recent research has identified inverse ZrO 2 /Cu catalysts as highly active and selective systems for the transformation of CO 2 to methanol with a performance that can be better than that of commercial Cu/ZnO catalysts. Here, we employed synchrotron-based ambient pressure X-ray photoelectron spectroscopy (AP-XPS) and calculations based on density functional theory (DFT) to understand the fate of CH 3 O groups under dry and wet environments. AP-XPS spectra revealed that under CO 2 hydrogenation conditions, formate and methoxy are two key intermediates to produce methanol. Furthermore, there are three different types of reactive sites on the surface: One is active for methoxy adsorption, which is stable and responsible for the methanol synthesis; Another one transforms CO 2 into CO; and a third one is active for CO 2 and methoxy dissociation, leading to C and methane formation. The theoretical calculations indicate that CH 3 OH readily dissociates to CH 3 O species following a highly exothermic (ΔE = -20.99 kcal/mol) and barrierless process. The water produced by the reverse water-gas shift reaction (CO 2 + H 2 → H 2 O + CO) can prevent the decomposition of CH 3 O species. We discovered that by introducing a tiny amount of water vapor (2 × 10 -6 Torr) into the reaction chamber, the energy barrier for the reaction CH 3 O(ads) + H(ads) → CH 3 OH(gas) is dramatically reduced. AP-XPS and computational modelling showed that water is quite capable of extracting adsorbed methoxy to form gaseous methanol. With this in mind, one could boost the methanol selectivity by adding appropriate amounts of water or steam, which is an inexpensive and feasible solution for industrial operations.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Zn 2+ -mediated catalysis for fast-charging aqueous Zn-ion batteries

Rechargeable aqueous zinc-ion batteries (AZIBs), renowned for their safety, high energy density and rapid charging, are prime choices for grid-scale energy storage. Historically, ion-shuttling models centring on ion-migration behaviour have dominated explanations for charge/discharge processes in aqueous batteries, like classical ion insertion/extraction and pseudocapacitance mechanisms. However, these models struggle to account for the exceptional performance of AZIBs compared to other aqueous metal-ion batteries. Here, in this study, we present a catalysis model elucidating the Zn 2+ anomaly in aqueous batteries, explaining it through the concept of adsorption in catalysis. Such behaviour can serve the charge/discharge role, predominantly dictated by solvated metal cations and cathode materials. First-principles calculations suggest optimal adsorption/desorption behaviour (water dissociation process) with the Zn 2+ -vanadium nitride (VN) combination. Experimentally, AZIBs implementing VN cathodes demonstrate fast-charging kinetics, showing a capacity of 577.1 mAh g -1 at a current density of 300,000 mA g -1 . The grasp of catalysis steps within AZIBs can drive solutions beyond state-of-the-art fast-charging batteries.

25 ENERGY STORAGE↗
DOE OSTI2026

Tailored polyMOFs for ion transport in lithium-based battery electrolyte

Owing to their low flammability, solid-state and quasi-solid-state electrolytes are safer alternatives to liquid organic electrolytes for energy storage applications. Metal–organic frameworks (MOFs), with facile functional tunability, long-range order, and rich host–guest interactions, have been implemented as electrolyte materials in a wide range of energy storage applications. In this work, we investigate a class of MOFs called polyMOFs as quasi-solid-state electrolyte materials. Unlike MOF–polymer composites, which are physical mixtures of MOF particles and polymers, polyMOFs are composed of polymeric linkers and metal ion nodes that self-assembled into crystalline and porous framework materials. PolyMOFs thus marry the ionic transport properties of liquid electrolyte and polymers with the synthetic versatility and host–guest interactions of MOFs. We demonstrate that the functionality of the polymer backbone of the polyMOF linker can improve room-temperature ion transport in the material. The polyMOF based on poly(ethylene glycol) (PEG) exhibits greater ionic conductivity, lithium transference number, and lower activation energy than its polyethylene (PE) analog. Supported by solid-state 7 Li nuclear magnetic resonance spectroscopy, we propose these improvements are due to stronger coordination of Li + to oxide sites in PEG, allowing for dissociation of Li and its associated anion. DFT studies further reveal that the confined solvent molecule mediates Li + transport in PEG-functionalized UiO-66 via a metastable adsorption and hopping mechanism. This work lies at the interface of inorganic and polymer electrolytes, unveiling fundamental insights into the design of next-generation ion conductive materials for energy technologies.

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

Influence of residual chlorine on Ru/TiO 2 active sites during CO 2 methanation

Titania-supported ruthenium (Ru/TiO 2 ) is an established catalyst for the hydrogenation of carbon dioxide to methane (Sabatier reaction). Chlorine contamination, owed to the RuCl 3 precursor, is demonstrated to have a detrimental impact on methanation activity. After calcination and reduction the catalyst contains residual chlorine, shown by XPS. An aqueous ammonia wash removes Cl without leaching Ru. The washed catalysts exhibit improvements in CH 4 site-time yields. Low Ru loading catalysts encounter the greatest activity enhancements after washing (~4.5-fold). DFT calculations indicate that chlorine and CO 2 directly compete for adsorption on Ru step sites, with Cl impeding the adsorption of CO 2 at under-coordinated sites and at higher Cl coverages. H 2 -chemisorption/TPR show that Cl removal lowers the onset of low temperature H 2 dissociation on Ru. Finally, DRIFTS provide evidence that the removal of Cl facilitates low temperature dissociative binding of CO 2 , indicated by the formation of surface bound linear CO species.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗