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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 865 records · Page 48
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Cobalt-Modulated Molybdenum–Dinitrogen Interaction in MoS 2 for Catalyzing Ammonia Synthesis

Dinitrogen conversion to ammonia via electrochemical reduction with over 10% Faradaic efficiency is demonstrated in this work. Co-doped MoS 2-x polycrystalline nanosheets with S vacancies as the catalysts are loaded onto carbon cloth by hydrothermal growth from Mo, Co, and S precursors. A sulfur vacancy on the MoS 2-x basal plane mimicking the natural Mo-nitrogenase active site is modified by Co doping and exhibits superior dinitrogen-to-ammonia conversion activity. Density-functional simulation reveals that the free energy barrier, which can be compensated by applied overpotential, is reduced from 1.62 to 0.59 eV after Co doping. Meanwhile, dinitrogen tends to be chemically adsorbed to defective MoS 2-x , which effectively activates the dinitrogen molecule for the dissociation of the N≡N triple bond. Here, this process is further accelerated by Co doping, resulting from the modulation of Mo–N bonding configuration.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2019

Graphite Conjugation Eliminates Redox Intermediates in Molecular Electrocatalysis

The efficient interconversion of electrical and chemical energy requires the intimate coupling of electrons and small-molecule substrates at catalyst active sites. In molecular electrocatalysis, the molecule acts as a redox mediator which typically undergoes oxidation or reduction in a separate step from substrate activation. These mediated pathways introduce a high-energy intermediate, cap the driving force for substrate activation at the reduction potential of the molecule, and impede access to high rates at low overpotentials. Here we show that electronically coupling a molecular hydrogen evolution catalyst to a graphitic electrode eliminates stepwise pathways and forces concerted electron transfer and proton binding. Electrochemical and X-ray absorption spectroscopy data establish that hydrogen evolution catalysis at the graphite-conjugated Rh molecule proceeds without first reducing the metal center. These results have broad implications for the molecular-level design of energy conversion catalysts.

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

Three-Dimensional Phthalocyanine Metal-Catecholates for High Electrochemical Carbon Dioxide Reduction

The synthesis of a new anionic 3D metal-catecholate framework, termed MOF-1992, is achieved by linking tetratopic cobalt phthalocyanin-2,3,9,10,16,17,23,24-octaol linkers with Fe 3 (-C 2 O 2 -) 6 (OH 2 ) 2 trimers into an extended framework of roc topology. MOF-1992 exhibits sterically accessible Co active sites together with charge transfer properties. Cathodes based on MOF-1992 and carbon black (CB) display a high coverage of electroactive sites (270 nmol cm -2 ) and a high current density (-16.5 mA cm -2 ; overpotential, -0.52 V) for the CO 2 to CO reduction reaction in water (faradaic efficiency, 80%). Finally, over the 6 h experiment, MOF-1992/CB cathodes reach turnover numbers of 5800 with turnover frequencies of 0.20 s -1 per active site.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2011

Electrochemical Kinetics and X-ray Absorption Spectroscopic Investigations of Oxygen Reduction on Chalcogen-Modified Ruthenium Catalysts in Alkaline Media

The oxygen reduction reaction (ORR) in alkaline media has been investigated on chalcogen-modified ruthenium nanoparticles (Ru/C, Se/Ru/C, Se/RuMo/C, S/Ru/C, S/RuMo/C) synthesized in-house via aqueous routes. In acidic medium, it is well known that modification by a chalcogen prevents the oxidation of the underlying transition-metal (Ru) surface, thereby promoting direct molecular O{sub 2} adsorption on the Ru metal. On an unmodified Ru catalyst in alkaline media, the surface oxides on Ru mediate the 2e{sup -} reduction of molecular O{sub 2} to a stable peroxide anion (HO{sub 2}{sup -}) intermediate via an outer-sphere electron-transfer mechanism. This increases the activity of HO{sub 2}{sup -} near the electrode surface and decreases the overpotential for ORR by effectively carrying out the reduction of HO{sub 2}{sup -} to OH{sup -} at the oxide-free ruthenium metal site. An increase in ORR activity of Ru is observed by modification with a chalcogen; however, the increase is not as significant as observed in acidic media. Ternary additives, such as Mo, were found to significantly improve the stability of the chalcogen-modified catalysts. Detailed investigations of the ORR activity of this class of catalyst have been carried out in alkaline media along with comparisons to acidic media wherever necessary. A combination of electrochemical and X-ray absorption spectroscopic (EXAFS, XANES, {Delta}{mu}) studies has been performed in order to understand the structure/property relationships of these catalysts within the context of ORR in alkaline electrolytes.

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

Morphological Evolution of Nanocluster Aggregates and Single Crystals in Alkaline Zinc Electrodeposition

The morphology of Zn electrodeposits is studied on carbon-coated transmission electron microscopy grids. At low over-potentials (eta = -50 mV), the morphology develops by aggregation at two distinct length scales: similar to 5 nm diameter monocrystalline nanoclusters form similar to 50 nm diameter polycrystalline aggregates, and the aggregates form a branched network. Epitaxial (00 (0) over bar2) growth above an overpotential of vertical bar eta(c)vertical bar > 125 mV leads to the formation of hexagonal single crystals up to 2 mu m in diameter. Potentiostatic current transients were used to calculate the nucleation rate from Scharifker et al.'s model. The exp(eta) dependence of the nucleation rates indicates that atomistic nucleation theory explains the nucleation process better than Volmer-Weber theory. A kinetic model is provided using the rate equations of vapor solidification to simulate the evolution of the different morphologies. On solving these equations, we show that aggregation is attributed to cluster impingement and cluster diffusion while single-crystal formation is attributed to direct attachment.

Desai, D↗
DOE OSTI2015

Role of strain and conductivity in oxygen electrocatalysis on LaCoO3 thin films

The slow kinetics of the oxygen reduction and evolution reactions (ORR, OER) hinder energy conversion and storage in alkaline fuel cells and electrolyzers employing abundant transition metal oxide catalysts. Systematic studies linking material properties to catalytic activity are lacking, in part due to the heterogeneous nature of powder-based electrodes. We demonstrate, for the first time, that epitaxial strain can tune the activity of oxygen electrocatalysis in alkaline solutions, focusing on the model chemistry of LaCoO 3 , where moderate tensile strain can further induce changes in the electronic structure via spin state to increase activity. The resultant decrease in charge transfer resistance to the electrolyte reduces the overpotential in the ORR more notably than the OER and suggests a different dependence of the respective rate-limiting steps on electron transfer. This provides new insight into the reaction mechanism applicable to a range of perovskite chemistries, key to the rational design of highly active catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

Nanoscale Strontium Titanate Photocatalysts for Overall Water Splitting

SrTiO3 (STO) is a large band gap (3.2 eV) semiconductor that catalyzes the overall water splitting reaction under UV light irradiation in the presence of a NiO cocatalyst. As we show here, the reactivity persists in nanoscale particles of the material, although the process is less effective at the nanoscale. To reach these conclusions, Bulk STO, 30 ± 5 nm STO, and 6.5 ± 1 nm STO were synthesized by three different methods, their crystal structures verified with XRD and their morphology observed with HRTEM before and after NiO deposition. In connection with NiO, all samples split water into stoichiometric mixtures of H2 and O2, but the activity is decreasing from 28 μmol H2 g–1 h–1 (bulk STO), to 19.4 μmol H2 g–1 h–1 (30 nm STO), and 3.0 μmol H2 g–1 h–1 (6.5 nm STO). The reasons for this decrease are an increase of the water oxidation overpotential for the smaller particles and reduced light absorption due to a quantum size effect. Overall, these findings establish the first nanoscale titanate photocatalyst for overall water splitting.

complete water splitting↗
DOE OSTI2025

Facile One-Pot Block Copolymer-Mediated Solvothermal Approach for Synthesis of High-Entropy Alloy with Enhanced OER Activity

Herein, we introduce a straightforward synthesis approach for highly active dendritic multimetallic high-entropy alloy (DMHEA@PtIrPdAgRu) nanoparticles with sufficient entropic mixing, featuring uniform distribution of five noble group metals (Pt, Ir, Pd, Ag, and Ru) via a block copolymer-mediated one-pot solvothermal reduction method for oxygen evolution reaction (OER). In this synthesis, N,N -dimethylformamide (DMF) is used as a reductant as well as solvent and core–shell-corona-type (poly(styrene)- block -poly(vinylpyridine)- block -poly(ethylene oxide)) (PS-PVP-PEO) block copolymer as a structure directing agent. The cooperative effect between the copolymer architecture and the reducing environment of DMF promoted a confined nucleation mechanism for forming a single-phase dendritic structure HEA with high compositional uniformity, thereby mitigating phase segregation, a common challenge in the synthesis of multimetallic nanoparticles. This prepared DMHEA@PtIrPdAgRu catalyst exhibits a low overpotential of 490 mV to attain a high current density of 100 mA cm –2 with a Tafel slope of 442 mV dec –1 for oxygen evolution. The superior OER performance is attributed to the synergistic cooperation among its active and coordinated metal centers as well as the incorporation of corrosion-resistant metal like platinum.

block copolymer↗
DOE OSTI2017

Theory-driven design of high-valence metal sites for water oxidation confirmed using in situ soft X-ray absorption

The efficiency with which renewable fuels and feedstocks are synthesized from electrical sources is limited at present by the sluggish oxygen evolution reaction (OER) in pH-neutral media. Here, we took the view that generating transition metal sites with high valence at low applied bias should improve the activity of neutral OER catalysts. Using density functional theory, we find that the formation energy of desired Ni 4+ sites is systematically modulated by incorporating judicious combinations of Co, Fe and non-metal phosphorus. Here we synthesized NiCoFeP oxyhydroxides and probed their oxidation kinetics by employing in situ soft X-ray absorption (sXAS). In situ sXAS studies of neutral-pH OER catalysts indicate ready promotion of Ni 4+ under low overpotential conditions. NiCoFeP catalyst outperforms IrO 2 and retains its performance following 100 hours of operation. We showcase NiCoFeP in a membrane-free CO 2 electroreduction system that achieves a 1.99 V cell voltage at 10 mA cm -2 , reducing CO 2 into CO and oxidizing H 2 O to O 2 with a 64% electricity-to-chemical-fuel efficiency.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2016

Highly selective plasma-activated copper catalysts for carbon dioxide reduction to ethylene

There is an urgent need to develop technologies that use renewable energy to convert waste products such as carbon dioxide into hydrocarbon fuels. Carbon dioxide can be electrochemically reduced to hydrocarbons over copper catalysts, although higher efficiency is required. We have developed oxidized copper catalysts displaying lower overpotentials for carbon dioxide electroreduction and record selectivity towards ethylene (60%) through facile and tunable plasma treatments. Herein we provide insight into the improved performance of these catalysts by combining electrochemical measurements with microscopic and spectroscopic characterization techniques. Operando X-ray absorption spectroscopy and cross-sectional scanning transmission electron microscopy show that copper oxides are surprisingly resistant to reduction and copper + species remain on the surface during the reaction. Furthermore, our results demonstrate that the roughness of oxide-derived copper catalysts plays only a partial role in determining the catalytic performance, while the presence of copper + is key for lowering the onset potential and enhancing ethylene selectivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Heme biomolecule as redox mediator and oxygen shuttle for efficient charging of lithium-oxygen batteries

One of the greatest challenges with lithium-oxygen batteries involves identifying catalysts that facilitate the growth and evolution of cathode species on an oxygen electrode. Heterogeneous solid catalysts cannot adequately address the problematic overpotentials when the surfaces become passivated. But, there exists a class of biomolecules which have been designed by nature to guide complex solution-based oxygen chemistries. We show that the heme molecule, a common porphyrin cofactor in blood, can function as a soluble redox catalyst and oxygen shuttle for efficient oxygen evolution in non-aqueous Li-O 2 batteries. The heme’s oxygen binding capability facilitates battery recharge by accepting and releasing dissociated oxygen species while benefiting charge transfer with the cathode. We reveal the chemical change of heme redox molecules where synergy exists with the electrolyte species. Our study brings focus to the rational design of solution-based catalysts and suggests a sustainable cross-link between biomolecules and advanced energy storage.

25 ENERGY STORAGE↗
DOE OSTI2017

Proton enhanced dynamic battery chemistry for aprotic lithium–oxygen batteries

Water is generally considered to be deteriorating to the performance of aprotic Li-air batteries, while it is challenged by the disparate effects observed recently. This has provoked a range of discussion on the role of water and its impact on the battery operation. In this work, a distinct battery chemistry that prevails in water-contaminated aprotic Li-O 2 batteries was discovered. Both lithium ions and protons were found to be involved in the oxygen reduction (ORR) and evolution reactions (OER), and LiOOH and LiOH were identified as predominant materials in the discharge product. As a new lithium compound, the crystallographic and spectroscopic characteristics of LiOOH∙H 2 O were scrutinized both experimentally and theoretically. The structure of LiOOH∙H 2 O was found to be closely related to that of LiOH∙H 2 O implying a fast conversion kinetics between the two phases. Intriguingly, LiOOH∙H 2 O exhibits superior dynamic property towards the reaction with I 3 - , which renders considerably lower overpotential during the charging process. We anticipate that the new battery chemistry unveiled in this mechanistic study would provide important insights to the understanding of nominally aprotic Li-O 2 batteries and help to tackle the critical issues confronted.

25 ENERGY STORAGE↗
DOE OSTI2015

A porous proton-relaying metal-organic framework material that accelerates electrochemical hydrogen evolution

The availability of efficient hydrogen evolution reaction (HER) catalysts is of high importance for solar fuel technologies aimed at reducing future carbon emissions. Even though Pt electrodes are excellent HER electrocatalysts, commercialization of large-scale hydrogen production technology requires finding an equally efficient, low-cost, earth-abundant alternative. Here, high porosity, metal-organic framework (MOF) films have been used as scaffolds for the deposition of a Ni-S electrocatalyst. Compared with an MOF-free Ni-S, the resulting hybrid materials exhibit significantly enhanced performance for HER from aqueous acid, decreasing the kinetic overpotential by more than 200 mV at a benchmark current density of 10 mA cm -2 . In conclusion, although the initial aim was to improve electrocatalytic activity by greatly boosting the active area of the Ni-S catalyst, the performance enhancements instead were found to arise primarily from the ability of the proton-conductive MOF to favourably modify the immediate chemical environment of the sulfide-based catalyst.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Anion-redox nanolithia cathodes for Li-ion batteries

The development of lithium-air batteries is plagued by a high potential gap (>1.2 V) between charge and discharge, and poor cyclability due to the drastic phase change of O-2 (gas) and Ox- (condensed phase) at the cathode during battery operations. Here we report a cathode consisting of nanoscale amorphous lithia (nanolithia) confined in a cobalt oxide, enabling charge/discharge between solid Li2O/Li2O2/LiO2 without any gas evolution. The cathode has a theoretical capacity of 1,341 Ah kg(-1), a mass density exceeding 2.2 g cm(-3), and a practical discharge capacity of 587 Ah kg(-1) at 2.55V versus Li/Li+. It also displays stable cycling performance (only 1.8% loss after 130 cycles in lithium-matched full-cell tests against Li4Ti5O12 anode), as well as a round-trip overpotential of only 0.24V. Interestingly, the cathode is automatically protected from O-2 gas release and overcharging through the shuttling of self-generated radical species soluble in the carbonate electrolyte.

Zhu, Zhi↗
DOE OSTI2017

Electrolyte additive enabled fast charging and stable cycling lithium metal batteries

Batteries using lithium (Li) metal as anodes are considered promising energy storage systems because of their high energy densities. However, safety concerns associated with dendrite growth along with limited cycle life, especially at high charge current densities, hinder their practical uses. Here we report that an optimal amount (0.05 M) of LiPF6 as an additive in LiTFSI-LiBOB dual-salt/carbonate-solvent-based electrolytes significantly enhances the charging capability and cycling stability of Li metal batteries. In a Li metal battery using a 4-V Li-ion cathode at a moderately high loading of 1.75mAh cm(-2), a cyclability of 97.1% capacity retention after 500 cycles along with very limited increase in electrode overpotential is accomplished at a charge/discharge current density up to 1.75 mA cm(-2). The fast charging and stable cycling performances are ascribed to the generation of a robust and conductive solid electrolyte interphase at the Li metal surface and stabilization of the Al cathode current collector.

25 ENERGY STORAGE↗
DOE OSTI2017

Self-optimizing, highly surface-active layered metal dichalcogenide catalysts for hydrogen evolution [Surface-active metal dichalcogenide electrocatalysts with self-improving performance for hydrogen evolution]

Low-cost, layered transition-metal dichalcogenides (MX 2 ) based on molybdenum and tungsten have attracted substantial interest as alternative catalysts for the hydrogen evolution reaction (HER). These materials have high intrinsic per-site HER activity; however, a significant challenge is the limited density of active sites, which are concentrated at the layer edges. Here we unravel electronic factors underlying catalytic activity on MX 2 surfaces, and leverage the understanding to report group-5 MX 2 (H-TaS 2 and H-NbS 2 ) electrocatalysts whose performance instead mainly derives from highly active basal-plane sites, as suggested by our first-principles calculations and performance comparisons with edge-active counterparts. Beyond high catalytic activity, they are found to exhibit an unusual ability to optimize their morphology for enhanced charge transfer and accessibility of active sites as the HER proceeds, offering a practical advantage for scalable processing. In conclusion, the catalysts reach 10 mA cm –2 current density at an overpotential of ~50–60 mV with a loading of 10–55 μg cm –2 , surpassing other reported MX 2 candidates without any performance-enhancing additives.

30 DIRECT ENERGY CONVERSION↗