Developing Cheap but Useful Machine Learning-Based Models for Investigating High-Entropy Alloy Catalysts
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36 MATERIALS SCIENCE↗
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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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The Influence of Fe substitution into LaCoO 3 -Electrocatalysts on Oxygen-Reduction Activity
The development of commercially friendly and stable catalysts for oxygen reduction reaction (ORR) is critical for many energy conversion systems such as fuel cells and metal-air batteries. Many Co-based perovskite oxides such as LaCoO 3 have been discovered as the stable and active ORR catalysts, which can be good candidates to replace platinum (Pt). Although researchers have tried substituting various transition metals into the Co-based perovskite catalysts to improve the ORR performance, the influence of substitution on the ORR. mechanism is rarely studied. In this paper, we explore the evolution of ORR mechanism after substituting Fe into LaCoO 3 , using the combination of X-ray photoelectron spectroscopy, high-resolution X-ray microscopy, X-ray diffraction, surface-sensitive soft X-ray absorption spectroscopy characterization, and electrochemical tests. We observed enhanced catalytic activities and increased electron transfer numbers during the ORR in Co-rich perovskite, which are attributed to the optimized e(g) filling numbers and the stronger hybridization of transition metal 3d and oxygen 2p bands. The discoveries in this paper provide deep insights into the ORR catalysis mechanism on metal oxides and new guidelines for the design of Pt-free ORR catalysts.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Structure and Oxygen Evolution Activity of β-NiOOH: Where Are the Protons?
Ni oxides and oxyhydroxides (NiO x ) have been studied for a long time as cathode materials for alkaline batteries and electrocatalysts for the oxygen evolution reaction (OER). Yet, understanding of the connection between their atomic and electronic structures and electrochemical performance or stability is still incomplete. In this work, we use first-principles density functional theory (DFT) calculations to revisit the structure, electronic properties, and OER activity of β-NiOOH, the catalytically active phase of NiO x . Following extensive DFTbased screening, we identify a hitherto overlooked structure characterized by a uniform distribution of H atoms on the NiO 2 layers. All the Ni 3+ cations in this structure exhibit an identical t g 6 e g 1 electronic configuration with an occupied 3d z2 orbital. Comparison of the calculated bond lengths with extended X-ray absorption fine structure (EXAFS) data unequivocally supports this structure relative to all other low-energy configurations. Based on this structure, we uncover and detail defect-dominated OER mechanisms on the basal β-NiOOH (001) surface, with overpotentials as low as 0.39 V. The present results should provide a valuable contribution to ongoing efforts for understanding and developing enhanced transition-metal hydroxide catalysts for the OER.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Potential-Dynamic Surface Chemistry Controls the Electrocatalytic Processes of Ethanol Oxidation on Gold Surfaces
Electro-catalysis has various important applications especially fuel cells. As a key element in electro-catalysis, the surface chemistry of electro-catalysts may strongly influence the catalytic activity and reaction mechanism, the fundamental understanding of which would provide guidance for designing high-efficiency catalysts. Herein, we utilized our recently developed in situ liquid SIMS approach to investigate the electro-catalytic oxidation of ethanol on gold surfaces in alkaline environments involved in direct alcohol fuel cells. Formation of adsorbed hydroxide intermediates on the gold surfaces upon electro-oxidation was molecularly witnessed under operando conditions, the evolution of which was revealed to govern the electro-catalytic processes. Moreover, the hydroxide intermediates as active sites participated in the reaction through transferring nucleophilic hydroxyl groups into the adjacent ethanol molecules. This work brings new light into electro-catalytic research and will facilitate the improvement of catalytic systems on the basis of surface chemistry-catalytic performance relationship.
Zhang, Yanyan↗
A High-Entropy Oxide as High-Activity Electrocatalyst for Water Oxidation
High-entropy materials are an emerging pathway in the development of high-activity (electro)catalysts because of the inherent tunability and coexistence of multiple potential active sites, which may lead to earth-abundant catalyst materials for energy-efficient electrochemical energy storage. In this report, we identify how the multication composition in high-entropy perovskite oxides (HEO) contributes to high catalytic activity for the oxygen evolution reaction (OER), i.e., the key kinetically limiting half-reaction in several electrochemical energy conversion technologies, including green hydrogen generation. We compare the activity of the (001) facet of LaCr 0.2 Mn 0.2 Fe 0.2 Co 0.2 Ni 0.2 O 3-δ with the parent compounds (single B-site in the ABO 3 perovskite). While the single B-site perovskites roughly follow the expected volcano-type activity trends, the HEO clearly outperforms all of its parent compounds with 17 to 680 times higher currents at a fixed overpotential. As all samples were grown as an epitaxial layer, our results indicate an intrinsic composition–function relationship, avoiding the effects of complex geometries or unknown surface composition. In-depth X-ray photoemission studies reveal a synergistic effect of simultaneous oxidation and reduction of different transition metal cations during the adsorption of reaction intermediates. The surprisingly high OER activity demonstrates that HEOs are a highly attractive, earth-abundant material class for high-activity OER electrocatalysts, possibly allowing the activity to be fine-tuned beyond the scaling limits of mono- or bimetallic oxides.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Defective Carbon-Based Materials for the Electrochemical Synthesis of Hydrogen Peroxide
Hydrogen peroxide (H 2 O 2 ), an important industrial chemical, is currently produced through an energy-intensive anthraquinone process that is limited to large-scale facilities. Small-scale decentralized electrochemical production of H 2 O 2 via a two-electron oxygen reduction reaction (ORR) offers unique opportunities for sanitization applications and the purification of drinking water. The development of inexpensive, efficient, and selective catalysts for this reaction remains a challenge. Here in this paper, we examine two different porous carbon-based electrocatalysts and show that they exhibit high selectivity for H 2 O 2 under alkaline conditions. By rationally varying synthetic methods, we explore the effect of pore size on electrocatalytic performance. Furthermore, by means of density functional calculations, we point out the critical role of carbon defects. Our theory results show that the majority of defects in graphene are naturally selective for the two-electron reduction of O 2 to H 2 O 2 , and we identify the types of defects with high activity.
36 MATERIALS SCIENCE↗
Lignin Deoxygenation for the Production of Sustainable Aviation Fuel Blendstocks
Lignin is an abundant source of renewable aromatics that has long been targeted for valorization. Traditionally, the inherent heterogeneity and reactivity of lignin has relegated it to direct combustion, but its higher energy density compared with polysaccharides makes it an ideal candidate for biofuel production. This Review critically assesses lignin's potential as a substrate for sustainable aviation fuel blendstocks. Lignin can generate the necessary cyclic compounds for a fully renewable, sustainable aviation fuel when integrated with current paraffinic blends and can meet the current demand 2.5 times over. Using an energy-centric analysis, we show that lignin conversion technologies have the near-term potential to match the enthalpic yields of existing commercial sustainable aviation fuel production processes. Key factors influencing the viability of technologies for converting lignin to sustainable aviation fuel include lignin structure, delignification extent, depolymerization performance, and the development of stable and tunable deoxygenation catalysts.
09 BIOMASS FUELS↗
Accelerated optimization of pure metal and ligand compositions for light-driven hydrogen production
Photocatalytic hydrogen production is a promising alternative to traditional hydrogen production. To implement photocatalytic hydrogen production the development of efficient, sustainable, and stable catalysts is necessary, and overcoming the current challenges surrounding high dimensional search spaces requires both computational and experimental efforts. Utilizing photo driven processes, stable colloidal metal catalysts can be formed in situ for efficient hydrogen production from water. When considering colloidal catalysts, stability is typically a concern solved through the addition of supports or ligands. In this work, poly(ethylene glycol) methyl ether thiol acts as a stabilizing ligand eliminating the need for catalyst supports while providing stable and active nanoparticle catalysts for more than 45 hours of reaction time and illumination. These systems utilize molecular photosensitizers, water reduction catalysts, stabilizing ligands, water, a sacrificial reductant, and organic solvents, posing new challenges pertaining to the optimization of multi-variable systems. Design of experiments (DOE) is applied to accelerate the understanding of variable interactions and is used as a tool to rapidly optimize the compositions of Au, Cu, Ni, and Fe containing systems. Through a collaboration leveraging computation and experimentation (both high throughput and characterizations), optimized performance peaks were obtained for each of these metals alongside distinct mapping of expected activity associated with photosensitizer, metal, and ligand concentration variations. With the highly digitized workflow, this study allowed for comparative generalizations to be made regarding photo driven hydrogen production for all four metals.
08 HYDROGEN↗
Reversibility limitations of metal exsolution reactions in niobium and nickel co-doped strontium titanate
Reversible metal exsolution and re-dissolution of metal cations in perovskite host lattices hold the potential for the development of regenerable metal-oxide catalysts. However, the reversibility of metal exsolution reactions is often limited.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Faceted NiO(111) nanosheets: morphological and catalytic evolution for the oxygen evolution reaction
The renaissance of the energy system through the use of green hydrogen by water electrolysis lies behind the development of abundant, active, and scalable catalysts for the oxygen evolution reaction (OER). A fundumental understanding of the surface properties for these materials is of vital importance in producing viable heterogenous catalysts. In this feature article, we summarize several years of collaborative work on a uniquely faceted NiO(111) nanosheet possessing hexagonal holes with a focus on understanding how the evolution of the catalyst surface and bulk composition effects OER performance. The importance of surface faceting, morphological evolution, and metal combination by different doping strategies are all analyzed and summarized to further improve the material's performance. Furthermore, microwave and supercritical synthesis processes are utilized to understand how varying wet-chemical techniques effect the formation of the NiO(111) nanosheet and activity of the material. We discuss our chosen strategies and the difficulties encountered with optimizing a catalyst surface for the OER.
08 HYDROGEN↗
Low pH Titanium Electrochemistry in the Presence of Sulfuric Acid and its Implications for Redox Flow Battery Applications
Titanium (Ti) is a promising elemental redox active species for redox flow batteries (RFBs) due to its 100x availability in the Earth crust, and 10x lower cost (compared to elemental vanadium). Furthermore, Ti salts are highly soluble in water and concentrations >5 M can be easily obtained. Seeking to harness the higher solubility (and hence energy density) of the Ti electrolyte for flow battery applications, the Ti 4+ /Ti 3+ redox couple was investigated at high concentrations (up to 5 M) relevant to RFB applications. The behavior of Ti ions in H 2 SO 4 supported electrolytes was investigated by varying the ratio of Ti redox active species to counterion. The electrochemical characteristics, transport properties, and redox kinetics of the Ti 4+ /Ti 3+ redox couple were measured and the impact of the Ti x+ to solvating ligand ratio was examined. The coordination structures around solvated Ti x+ ions were spectroscopically determined and the effect of solvation structure on the Ti 3+ /Ti 4+ redox rate constants were examined and correlated to the calculated solvation energy (hence distinguishing between inner- and outer-sphere processes) and the role of catalysts was addressed. The Ti electrolyte development guidelines presented herein will advance the development of Ti-based RFBs as a promising pathway towards cost effective, grid-scale energy storage.
Electrochemistry↗
Catalytic Upgrading of Key Biorefining Building Blocks to Renewable Chemicals, Polymeric Materials, and Liquid Fuels
The central objective of this project is to develop efficient, selective, and cost-effective catalytic systems for upgrading of key biorefining building blocks derived from catalytic conversion of plant biomass into value-added chemicals, polymeric materials, and liquid fuels. More specifically, the proposed work for the current grant period seeks to accomplish the following three specific objectives: (a) developing cost-effective and recyclable catalysts for selective upgrading (direct coupling) of the C 6 biorefining building block 5-hydroxymethylfurfural (HMF) into C 12 intermediates and for integrating biomass conversion and upgrading processes; (b) transforming the upgraded C 12 intermediates into polyols, polyurethanes, polyesters, and diesel fuels; and (c) reforming the upgraded intermediates into premium C 12 centered liquid hydrocarbon transportation fuels via selective hydrodeoxygenation catalysis.
09 BIOMASS FUELS↗
Abstract for CRADA between National Energy Technology Laboratory and American Institute of Chemical Engineers dba RAPID Manufacturing Institute
NETL and RAPID Manufacturing will develop advanced electromagnetic (EM) reactors and catalysts to produce light olefins from alternative feedstocks using CO2 soft oxidation. Light olefins are the building blocks for many plastic products, in addition to synthetic fibers, rubbers, and polymers. This project has the potential to produce high-value light olefins from alternative feedstocks with reduced energy consumption (50-70%), carbon intensity (50-70%), and production cost (15-25%) compared to the traditional olefin production processes.
32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
Hydrogen-oxygen electrolytic regenerative fuel cells
Hydrogen-oxygen electrolytic regenerative fuel cell development and cycling tests of cathode catalyst loading and asbestos mat type, and electrolyte/asbestos weight ratio variations
ASBESTOS↗
Performance of solar shields
The loss of the micrometeoroid shield from the Orbital Workshop section of Skylab 1 about 63 seconds after lift-off, was the catalyst for a prodigious effort to develop a substitute for the passive portion of the thermal control system. An intensive effort is described in which numerous potential thermal shield materials were assessed, and during which period ten specific shield designs were developed and carried through various stages of development and test. Thermal shield materials data are discussed, including optical, strength, fatigue, outgassing, tackiness, ultraviolet radiation, and material memory properties. Specifically addressed are thermal shield materials selection criteria and the design, development, and test requirements associated with the successful development of Skylab thermal shields, and specifically the two thermal shields subsequently deployed over the exposed gold foil skin of the Orbital Workshop. Also considered are the general performance and thermal improvements provided by both the parasol design deployed by the Skylab 1 crew, and the sail design deployed by the Skylab 2 crew.
Schwinghamer, R. J.↗
Solid polymer electrolyte (SPE) fuel cell technology program, phase 2/2A
Test evaluations were performed on a fabricated single solid polymer electrolyte cell unit. The cell operated at increased current density and at higher performance levels. This improved performance was obtained through a combination of increased temperature, increased reactant pressures, improved activation techniques and improved thermal control over the baseline cell configuration. The cell demonstrated a higher acid content membrane which resulted in increased performance. Reduced catalyst loading and low cost membrane development showed encouraging results.
Source record↗
Gasification of carbon fiber composites for the alleviation of electrical hazards
A mixture of calcium acetate and lithium acetate applied to the surface of carbon fibers caused the fibers to gasify in a simulated airplane-crash fire. Tests conducted with a JPL-developed electrical detector showed the catalyst-modified composites to release few fibers during burning, while state-of-the-art composites released several hundred. Mechanical property tests demonstrated nearly identical behavior of catalyst-modified and state-of-the-art composites. Aging tests also showed little difference in the composite strength except for a severe reduction when soaked in water. Several promising new concepts resulted from the project, including catalytic elimination of carbon particulates from diesel exhaust, catalytic improvement of coal combustion, and electrical destruction of carbon particulates in combustion systems.
Hull, G.↗
Making A Noble-Metal-On-Metal-Oxide Catalyst
Catalyst exhibits superior performance in oxidation of CO in CO2 lasers. Two-step process developed for preparing platinum- or palladium-on-tin-oxide catalyst for recombination of CO and O2, decomposition products that occur in high-voltage discharge region of closed-cycle CO2 laser. Process also applicable to other noble-metal/metal-oxide combinations.
Miller, Irvin M.↗