Search NASA⌕ Search

SEARCH · Search NASA

Results for “catalyst development.”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 1,189 records · Page 66
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

First-row transition metal polypyridine complexes that catalyze proton to hydrogen reduction

Proton reduction is a critical reaction for the efficient utilization of solar fuels and the development of a hydrogen economy. Molecular proton reduction catalysts help us to understand how hydrogenases function in nature, on one hand, and inspire us to design new practical materials on the other. This manuscript introduces the concept of electrocatalytic and photocatalytic proton (hydrogen evolution) in a homogeneous system, and then reviews recent studies on molecular proton reduction catalysts that contain 3d transition metal centers (Mn, Fe, Co, and Ni) surrounded by polypyridine ligands. The discussion focuses on the design, structure, and catalytic behavior of these metal polypyridine catalysts. Catalytic pathways, and how they are affected by complex structure, are addressed in order to offer rational suggestions for the future preparation of promising hydrogen evolution catalysts.

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

Comparing Tandem Cell Designs for Electrochemical CO 2 Reduction to Ethylene

Electrochemical carbon dioxide reduction (CO 2 R) is a promising approach for the decentralized production of fuels such as ethylene (C 2 H 4 ). However, the use of Cu, the most efficient metal CO 2 R catalyst for the generation of C 2 H 4 known to date, generally yields a product stream with poor selectivity. In an effort to increase selectivity, the reaction from CO 2 to C 2 H 4 can be broken down into two steps using tandem CO 2 R electrolyzers: formation of CO from CO 2 and subsequent reduction of CO to C 2 H 4 . Here, in this study, we present two novel tandem electrolyzer architectures that closely integrate two cathodes, one for CO generation and one for conversion to C 2 H 4 , while still enabling independent electrical control of the cathodic surfaces. Cathode segmentation in each of these designs also permits the controlled sequencing of mass flow of chemical intermediates in the order of Au to Cu cathode catalysts, in contrast to earlier work relying on uncontrolled, passive diffusion to facilitate the flow of chemical intermediates between catalysts. When comparing the performance of the newly developed electrolyzer cell designs with a dual electrolyzer system, we found that the dual electrolyzer system yields the highest C 2 H 4 faradaic efficiencies (FEs) of 31% and C 2 H 4 concentrations (∼8 mol %). However, a single Cu-containing electrolyzer outperformed all three tandem systems in terms of C 2 H 4 FE (34%). Our findings, enabled by independent control of the two tandem cathode surfaces, indicate that tandem CO 2 R systems need to be evaluated carefully by testing them at various relevant current densities.

C2H4↗
DOE OSTI2024

Challenging thermodynamics: combining immiscible elements in a single-phase nano-ceramic

Abstract The Hume-Rothery rules governing solid-state miscibility limit the compositional space for new inorganic material discovery. Here, we report a non-equilibrium, one-step, and scalable flame synthesis method to overcome thermodynamic limits and incorporate immiscible elements into single phase ceramic nanoshells. Starting from prototype examples including (NiMg)O, (NiAl)O x , and (NiZr)O x , we then extend this method to a broad range of Ni-containing ceramic solid solutions, and finally to general binary combinations of elements. Furthermore, we report an “encapsulated exsolution” phenomenon observed upon reducing the metastable porous (Ni 0.07 Al 0.93 )O x to create ultra-stable Ni nanoparticles embedded within the walls of porous Al 2 O 3 nanoshells. This nanoconfined structure demonstrated high sintering resistance during 640 h of catalysis of CO 2 reforming of methane, maintaining constant 96% CH 4 and CO 2 conversion at 800 °C and dramatically outperforming conventional catalysts. Our findings could greatly expand opportunities to develop novel inorganic energy, structural, and functional materials.

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

Interconnected nanoconfining pore networks enhance catalyst CO 2 interaction in electrified reactive capture

Systems that sequentially capture and upgrade CO 2 from air to fuels/fuel-intermediates, such as syngas and ethylene, rely on an energy-intensive CO 2 release process. Electrified reactive capture systems transform CO 2 obtained directly from carbonate capture liquid into products. Previous reactive capture systems show a decline in Faradaic efficiencies (FE) at current densities above 200 mA/cm 2 . Here we show the chemical origins of this problem, finding that prior electrocatalyst designs failed to arrest, activate, and reduce in situ-generated CO 2 (i-CO 2 ) before it traversed the catalyst layer and entered the tailgas stream. We develop a templated synthesis to define pore structures and the sites of Ni single atoms, and find that carbon-nitrogen-based nanopores are effective in accumulating i-CO 2 via short-range, non-electrostatic interactions between CO 2 molecules and the nanochannel walls. These interactions confine and enrich i-CO 2 within the pores, enhancing its binding and activation. We report as a result carbonate electrolysis at 300 mA/cm 2 with FE to CO of 50% ± 3%, and with <1% CO 2 in the tailgas outlet stream. This corresponds to a projected energy efficiency (EE) to 2:1 syngas of 46% at 300 mA/cm 2 when H 2 is added using a water electrolyzer.

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

On the use of NMR distance measurements for assessing surface site homogeneity

The past few decades have seen tremendous growth in the area of single-site heterogeneous catalysis, which aims to combine the best aspects of homogeneous and heterogeneous catalysis, namely molecular-level site control and ease of separation/recycling. Despite this, we still do not have a means of assessing site homogeneity and whether the produced catalyst is indeed a “single-site”. Recent developments have enabled the use of NMR-based distance measurements to determine the conformations and configurations of surface sites, leading to the question whether such measurements can be used to distinguish materials containing either single or multiple surface sites with otherwise indistinguishable NMR properties. Here, we describe a Monte Carlo-based multi-structure search algorithm and its application to the determination of multi-site structures from supported metal complexes. The sensitivity of REDOR data to the existence of multiple sites is assessed using synthetic data and prior literature examples are revisited to determine whether the single-site approximation was indeed appropriate. We lastly apply this new methodology to differentiate the configurations of zirconocene complexes grafted onto alumina supports that were thermally treated at different temperatures.

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

Cutting-edge methods for amplifying the oxygen evolution reaction during seawater electrolysis: a brief synopsis

Electrochemical water splitting has been considered a clean and continual way for hydrogen (H 2 ) production. Direct seawater electrolysis is a potentially attractive technology due to the ample access to seawater and scarce freshwater resources in some regions. However, the presence of impurities (e.g., Cl - , Mg 2+ ) and the resulting corrosion and side reactions, such as the chloride oxidation reaction (ClOR), makes seawater electrocatalysis more challenging than that of fresh or alkaline water due to competition with the oxygen evolution reaction (OER) at the anode. Consequently, much effort has been devoted to developing approaches to enhance OER performance and suppress the ClOR. In this minireview, we summarize three general strategies for enhancing OER activity and selectivity in seawater electrolysis based on three different concepts: (1) the sole development of robust and high-performance OER catalysts in pure seawater electrolytes, (2) the introduction of additives to seawater electrolytes (e.g., alkalis and/or salts without chloride) to enhance the potential equilibrium gap between the ClOR and OER in combination with regular highly active OER catalysts, and (3) a combination of approaches (1) and (2). Finally, the current challenges and potential opportunities for green H 2 production from seawater electrolysis are briefly presented.

08 HYDROGEN↗
DOE OSTI2023

Discovery of structure–property relations for molecules via hypothesis-driven active learning over the chemical space

The discovery of the molecular candidates for application in drug targets, biomolecular systems, catalysts, photovoltaics, organic electronics, and batteries necessitates the development of machine learning algorithms capable of rapid exploration of chemical spaces targeting the desired functionalities. Here, we introduce a novel approach for active learning over the chemical spaces based on hypothesis learning. We construct the hypotheses on the possible relationships between structures and functionalities of interest based on a small subset of data followed by introducing them as (probabilistic) mean functions for the Gaussian process. This approach combines the elements from the symbolic regression methods, such as SISSO and active learning, into a single framework. The primary focus of constructing this framework is to approximate physical laws in an active learning regime toward a more robust predictive performance, as traditional evaluation on hold-out sets in machine learning does not account for out-of-distribution effects which may lead to a complete failure on unseen chemical space. Here, we demonstrate it for the QM9 dataset, but it can be applied more broadly to datasets from both domains of molecular and solid-state materials sciences.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Abstract - Cooperative Research and Development Agreement between Princeton University and National Energy Technology Laboratory

This research effort will develop a novel nanodischarge reactor loaded with nanotemplated catalysts to achieve high-efficiency plasma-enhanced conversion of CO2 and methane for the production of chemicals or fuels. The primary objective of this study is to demonstrate low temperature operation of a novel nanoplasma catalysis reactor that is characterized by a uniform discharge. Another objective is to address the most significant challenge in the plasma-catalysis hybrid system, which is to achieve the strongest synergistic interaction between the plasma and catalyst and to increase the selectivity for producing methanol and alkanes/alkenes. This enhanced synergy will be enabled by using bimetallic nanoparticles synthesized on nanorods present on surfaces of a nanotemplated oxide support.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2020

Cooperative Research and Development Agreement between National Energy Technology Laboratory and The Trustees of Princeton University (Final Report)

This research effort will develop a novel nanodischarge reactor loaded with nanotemplated catalysts to achieve high-efficiency plasma-enhanced conversion of CO2 and methane for the production of chemicals or fuels. The primary objective of this study is to demonstrate low temperature operation of a novel nanoplasma catalysis reactor that is characterized by a uniform discharge. Another objective is to address the most significant challenge in the plasma-catalysis hybrid system, which is to achieve the strongest synergistic interaction between the plasma and catalyst and to increase the selectivity for producing methanol and alkanes/alkenes. This enhanced synergy will be enabled by using bimetallic nanoparticles synthesized on nanorods present on surfaces of a nanotemplated oxide support.

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

Integrated Carbon Capture and Propane Oxidative Dehydrogenation for Olefins Production under Isothermal Conditions over Cr₂O₃-ZSM-5/CaO-CaZrO₃ Reactive Capture Materials

Converting captured CO₂ into fuels and marketable chemicals using bifunctional materials (BFMs) represents a promising sustainable solution. In this study, a BFM composed of a Cr₂O₃/ZSM-5 catalyst and a CaO-CaZrO₃ sorbent was developed and tested for the integrated CO₂-oxidative dehydrogenation of propane (CO₂-ODHP) in a fixed bed reactor. The CaO-CaZrO₃ sorbent, prepared using the citrate sol-gel method, demonstrated high CO₂ adsorption capacity and improved cyclic stability compared to pure CaO. The BFM achieved 23.5% propane conversion, 52.5% propylene selectivity, and 68.7% olefin selectivity at isothermal adsorption-reaction conditions (630-630 °C). Overall, this study provides insights into enhancing CO2 adsorption and developing materials for integrated CO2 capture and conversion.

Baamran, Khaled↗
DOE OSTI2026

Catalytic Reaction Intermediates Revealed with Femtosecond M-edge XANES (Final Technical Report)

The major goals of this work were to measure the electronic structure of earth-abundant catalysts at key steps in their catalytic cycles using ultrafast UV/Visible, Extreme Ultraviolet, and X-ray spectroscopy. Our central idea was that by using these sophisticated probes, we could uncover hidden reaction mechanisms and provide guidance for catalyst design. A second major goal was the development of Extreme Ultraviolet (XUV) spectroscopy as an accessible, tabletop probe of transition metal electronic structure. Spectra in this 30-100 eV energy range probe 3d→3p transitions in 3d metals and 5p/4f→5d transitions in 5d metals, and share the oxidation state, spin state, and ligand field specificity of hard X-ray spectroscopy. The Vura-Weis group previously established the basic utility of this technique for measuring the excited-state cascades of transition metal chromophores, and in this grant we intended to extend its scope to catalytic intermediates.

36 MATERIALS SCIENCE↗
NASA NTRS1972

The development of a non-cryogenic nitrogen/oxygen supply system

Development of the hydrazine/water electrolysis process in a manned spacecraft to provide metabolic oxygen and both oxygen and nitrogen for cabin leakage makeup was studied. Electrode development efforts were directed to stability, achieved with catalyst additives and improved processing techniques, and a higher hydrazine conversion efficiency, achieved by reducing catalyst loading on the cathodes. Extensive testing of the one-man breadboard N2/02 system provided complete characterization of cabin atmosphere control aspects. A detailed design of a prototype modular N2/02 unit was conducted. The contact heat exchanger which is an integral component of this design was fabricated and sucessfully design-verification tested.

Greenough, B. M.↗
NASA NTRS1985

Optimization of the catalytic oxidation of CO for closed-cycle CO2 laser applications

This report develops a basis for the design of a catalyst bed for the recombination of CO and O2 in a closed-cycle CO2 laser system. The catalyst is 1% Pt on SnO2 having a BET surface area of 6.7 sq m/g and a specific void volume of 0.374 cu cm/g. The design conditions are: a catalyst bed temperature of 100 C and a circulating flow rate of 10 lambda/min. Under these conditions, the required quantity of catalyst for prolonged laser operation of 668g. The rat law for the reaction of a stoichiometric mixture of 1% CO + 1/2% O2 in helium was determined to be overall first order; however, additional experiments with non-stoichiometric gas mixtures of CO and O2 are needed to determine the order of the CO concentration and the order of the O2 concentration in the rate law.

Miller, I. M.↗
NASA NTRS2011

Sustainability of the Catalytic Activity of a Silica-Titania Composite (STC) for Long-Term Indoor Air Quality Control

TiO2-assisted photocatalytic oxidation (PCO) is an emerging technology for indoor air quality control and is also being evaluated as an alternative trace contaminant control technology for crew habitats in space exploration. Though there exists a vast range of literature on the development of photocatalysts and associated reactor systems, including catalyst performance and performance-influencing factors, the critical question of whether photocatalysts can sustain their initial catalytic activity over an extended period of operation has not been adequately addressed. For a catalyst to effectively serve as an air quality control product, it must be rugged enough to withstand exposure to a multitude of low concentration volatile organic compounds (VOCs) over long periods of time with minimal loss of activity. The objective of this study was to determine the functional lifetime of a promising photocatalyst - the silica-titania composite (STC) from Sol Gel Solutions, LLC in a real-world scenario. A bench-scale STC-packed annular reactor under continuous irradiation by a UV-A fluorescent black-light blue lamp ((lambda)max = 365 nm) was exposed to laboratory air continuously at an apparent contact time of 0.27 sand challenged with a known concentration of ethanol periodically to assess any changes in catalytic activity. Laboratory air was also episodically spiked with halocarbons (e.g., octafluoropropane), organosulfur compounds (e.g., sulfur hexafluoride), and organosilicons (e.g., siloxanes) to simulate accidental releases or leaks of such VOCs. Total organic carbon (TOC) loading and contaminant profiles of the laboratory air were also monitored. Changes in STC photocatalytic performance were evaluated using the ethanol mineralization rate, mineralization efficiency, and oxidation intermediate (acetaldehyde) formation. Results provide insights to any potential catalyst poisoning by trace halocarbons and organosulfur compounds.

Coutts, Janelle L.↗
DOE OSTI2019

Atomically Dispersed Metal Catalysts for Oxygen Reduction

The unprecedented oxygen reduction reaction (ORR) activity of atomically dispersed and nitrogen-coordinated metal site (e.g., Fe, Co, or Mn) catalysts makes them promising low-cost candidates to replace platinum group metal (PGM) catalysts in proton exchange membrane fuel cells (PEMFCs). This Perspective focuses on emerging developments in mechanistic understanding, innovative synthetic concept, and performance improvement of these high-risk, high-reward PGM-free catalysts. Starting from theoretical and computational analysis of active sites and ORR pathways, here we provide a concise overview of recent progress in catalyst synthesis, characterization, and catalytic performance with an aim to elucidate structure–property correlations. We also examine remaining challenges and future directions to realize atomically dispersed metal catalysts with sufficient activity and stability for viable PEMFC applications.

08 HYDROGEN↗
DOE OSTI2019

Seven Coordinated Molecular Ruthenium–Water Oxidation Catalysts: A Coordination Chemistry Journey: Focus Review

Molecular water oxidation catalysis is a field that has experienced an impressive development over the past decade mainly fueled by the promise of generation of a sustainable carbon neutral fuel society, based on water splitting. Most of these advancements have been possible thanks to the detailed understanding of the reactions and intermediates involved in the catalytic cycles. Today’s best molecular water oxidation catalysts reach turnover frequencies that are orders of magnitude higher than that of the natural oxygen evolving center in photosystem II. These catalysts are based on Ru complexes where at some stage, the first coordination sphere of the metal center becomes seven coordinated. The key for this achievement is largely based on the use of adaptative ligands that adjust their coordination mode depending on the structural and electronic demands of the metal center at different oxidation states accessed within the catalytic cycle. Here, this Review covers the latest and most significant developments on Ru complexes that behave as powerful water oxidation catalysts and where at some stage the Ru metal attains coordination number 7. Further it provides a comprehensive and rational understanding of the different structural and electronic factors that govern the behavior of these catalysts.

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

Hierarchically Porous Multimetal‐Based Carbon Nanorod Hybrid as an Efficient Oxygen Catalyst for Rechargeable Zinc–Air Batteries

Abstract The lack of efficient strategies to address the intrinsic activity, site accessibility, and structural stability issues of metal‐carbon hybrid catalysts is restricting their real‐world implementation on the basis of rechargeable zinc–air batteries. Herein, a dual metal–organic frameworks (MOFs) pyrolysis strategy is developed to regulate the intrinsic activity and porous structure of the derived catalysts, where a Fe 2 Ni_MIL‐88@ZnCo_zeolitic imidazolate framework (ZIF), with a hierarchically porous structure, multifunctional components, and an integrated architecture, acts as an ideal precursor to obtain multimetal based porous nanorod (FeNiCo@NC‐P). Benefitting from the synergetic effect of the multimetal components, facilitated reactant accessibility, and the well‐retained integrated structure, the resultant FeNiCo@NC‐P catalyst exhibits an oxygen reduction reaction half‐wave potential of 0.84 V as well as an oxygen evolution reaction potential of 1.54 V at 10 mA cm –2 . Furthermore, the practical application of FeNiCo@NC‐P in the zinc–air battery displays a low voltage gap and long‐term durability (over 130 h at a current density of 10 mA cm –2 ), which outperforms the commercial noble metal benchmarks. This work not only affords a competitive bifunctional oxygen electrocatalyst for zinc–air batteries but also paves a new way to design and fabricate MOF‐derived materials with tunable catalytic properties.

Ren, Dezhang↗