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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 217 records · Page 12
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Understanding the Origin of Highly Selective CO 2 Electroreduction to CO on Ni,N‐doped Carbon Catalysts

Abstract Ni,N‐doped carbon catalysts have shown promising catalytic performance for CO 2 electroreduction (CO 2 R) to CO; this activity has often been attributed to the presence of nitrogen‐coordinated, single Ni atom active sites. However, experimentally confirming Ni−N bonding and correlating CO 2 reduction (CO 2 R) activity to these species has remained a fundamental challenge. We synthesized polyacrylonitrile‐derived Ni,N‐doped carbon electrocatalysts (Ni‐PACN) with a range of pyrolysis temperatures and Ni loadings and correlated their electrochemical activity with extensive physiochemical characterization to rigorously address the origin of activity in these materials. We found that the CO 2 R to CO partial current density increased with increased Ni content before plateauing at 2 wt % which suggests a dispersed Ni active site. These dispersed active sites were investigated by hard and soft X‐ray spectroscopy, which revealed that pyrrolic nitrogen ligands selectively bind Ni atoms in a distorted square‐planar geometry that strongly resembles the active sites of molecular metal–porphyrin catalysts.

Koshy, David M.↗
DOE OSTI2022

Olefin methylation over iron zeolites and the methanol to hydrocarbons reaction

The effect of olefin addition to a stream of dimethyl ether on the methanol homologation reaction is investigated using iron-substituted zeolites Fe-beta and Fe-ZSM-5. The reaction was investigated using plug-flow microreactors in the temperature range of 240–400 °C, at a total pressure of 0.239 MPa and a WHSV of 6.12 (g DME/ gcat -hr). For Fe-beta (Si/Fe= 9.2) catalysts, isobutene co-feeding almost doubles dimethyl ether (DME) consumption rate and shifts selectivity towards larger olefins with carbon numbers from 5 to 7. Addition of isobutene above 6.3%, however, resulted in a reduction of DME consumption rates, an effect assigned to the replacement of surface methoxy groups for adsorbed olefins in the zeolite pores. Below a temperature of 340 °C hydride-transfer rates are negligible; reaction rates are stable for over 5.5 h and the products consist almost exclusively of olefins and a small amount of methane. Above 360 °C the onset of catalytic hydride transfer processes is observed leading to fast catalyst deactivation rates and an increase in the concentration of aromatic species. Iron ZSM-5 (Si/Fe = 21.4) catalysts under similar reaction conditions consumes methanol faster than Fe-beta at approximately three times the TOF (on a per iron basis). The Fe-ZSM-5 catalyst was selective to a distribution of products (C5 to C8) as compared to Fe-beta which was selective to primarily C5 and C7. Co-feeding larger olefins (2-methyl-2-butene, 2,3-dimethyl-2-butene, 2,3,3-trimethyl-1-butene, and 2,4,4-trimethyl-2-pentene) at a 3.9% olefin concentration over Fe-beta changed selectivity towards cracking products (C4 compounds such as isobutene). As the size of the olefin increases, a reduction of DME consumption rate is also observed. Here these results show that co-feeding olefins with DME over Fe-zeolites is a promising route to increase methylation rates at relatively low temperatures producing larger branched olefins and that the product distribution is highly dependent on the zeolite pore size and structure of the olefin.

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

Revisiting Competing Paths in Electrochemical CO 2 Reduction on Copper via Embedded Correlated Wavefunction Theory

We re-evaluate two key steps in the mechanism of CO 2 reduction on copper at a higher level of theory capable of correcting inherent errors in density functional theory (DFT) approximations, namely, embedded correlated wavefunction (ECW) theory. Here, we consider the CO reduction step on Cu(111), which is critical to understanding reaction selectivity. Here, we optimize embedding potentials at the periodic plane-wave DFT level using density functional embedding theory (DFET). All possible adsorption sites (adsites) for each adsorbate then are screened with ECW theory at the catalytically active site to refine the local electronic structure. Unsurprisingly, DFT and ECW theory predict different adsite preferences, largely because of DFT’s inability to properly situate the CO 2π* level. Differing preferred adsites suggest that different reaction pathways could emerge from DFT versus ECW theory. Starting from these preferred ECW theory adsites, we then obtain reaction pathways at the plane-wave DFT level using the climbing-image nudged elastic band method to determine minimum energy paths. Thereafter, we perform ECW calculations at the catalytically active site to correct the energetics at each interpolated structure (image) along the reaction pathways. Via this approach, we confirm that the first step in CO reduction via hydrogen transfer on Cu(111) is to form hydroxymethylidyne (*COH) instead of formyl (*CHO). Although the prediction to preferentially form *COH is consistent with that of DFT, the two theories predict quite different structural and mechanistic behaviors, suggesting that verification is needed for other parts of the mechanism of CO 2 reduction, which is the subject of ongoing work.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2020

Cu 2 O/CuS Nanocomposites Show Excellent Selectivity and Stability for Formate Generation via Electrochemical Reduction of Carbon Dioxide

Formate is an important value-added chemical that can be produced via electrochemical CO 2 reduction reactions (CO 2 RR). Cu 2 O-based catalysts have previously demonstrated decent activity for formate generation; however, they often suffer from poor electrochemical stability under reductive conditions. Here, in this paper, we report a new Cu 2 O/CuS composite catalyst that simultaneously achieves an excellent faradaic efficiency of 67.6% and a large partial current density of 15.3 mA/cm 2 at –0.9 V vs RHE for formate. Importantly, it maintains an average faradaic efficiency of 62.9% for at least 30 h at the same potential. The catalytic selectivity and stability for formate production outperform other Cu, CuS, and Cu 2 O catalysts.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Reversible and Selective CO 2 to HCO 2 − Electrocatalysis near the Thermodynamic Potential

Abstract Reversible catalysis is a hallmark of energy‐efficient chemical transformations, but can only be achieved if the changes in free energy of intermediate steps are minimized and the catalytic cycle is devoid of high transition‐state barriers. Using these criteria, we demonstrate reversible CO 2 /HCO 2 − conversion catalyzed by [Pt(depe) 2 ] 2+ (depe=1,2‐ bis (diethylphosphino)ethane). Direct measurement of the free energies associated with each catalytic step correctly predicts a slight bias towards CO 2 reduction. We demonstrate how the experimentally measured free energy of each step directly contributes to the <50 mV overpotential. We also find that for CO 2 reduction, H 2 evolution is negligible and the Faradaic efficiency for HCO 2 − production is nearly quantitative. A free‐energy analysis reveals H 2 evolution is endergonic, providing a thermodynamic basis for highly selective CO 2 reduction.

Cunningham, Drew W.↗
NASA NTRS2014

CO2 Reduction Assembly Prototype Using Microlith-Based Sabatier Reactor for Ground Demonstration

The utilization of CO2 to produce life support consumables, such as O2 and H2O, via the Sabatier reaction is an important aspect of NASA's cabin Atmosphere Revitalization System (ARS) and In-Situ Resource Utilization (ISRU) architectures for both low-earth orbit and long-term manned space missions. Carbon dioxide can be reacted with H2, obtained from the electrolysis of water, via Sabatier reaction to produce methane and H2O. Methane can be stored and utilized as propellant while H2O can be either stored or electrolyzed to produce oxygen and regain the hydrogen atoms. Depending on the application, O2 can be used to replenish the atmosphere in human-crewed missions or as an oxidant for robotic and return missions. Precision Combustion, Inc. (PCI), with support from NASA, has previously developed an efficient and compact Sabatier reactor based on its Microlith® catalytic technology and demonstrated the capability to achieve high CO2 conversion and CH4 selectivity (i.e., ≥90% of the thermodynamic equilibrium values) at high space velocities and low operating temperatures. This was made possible through the use of high-heat-transfer and high-surface-area Microlith catalytic substrates. Using this Sabatier reactor, PCI designed, developed, and demonstrated a stand-alone CO2 Reduction Assembly (CRA) test system for ground demonstration and performance validation. The Sabatier reactor was integrated with the necessary balance-of-plant components and controls system, allowing an automated, single "push-button" start-up and shutdown. Additionally, the versatility of the test system prototype was demonstrated by operating it under H2-rich (H2/CO2 of >4), stoichiometric (ratio of 4), and CO2-rich conditions (ratio of <4) without affecting its performance and meeting the equilibrium-predicted water recovery rates. In this paper, the development of the CRA test system for ground demonstration will be discussed. Additionally, the performance results from testing the system at various operating conditions and the results from durability testing will be presented.

Junaedi, Christian↗
DOE OSTI2022

Constructing efficient CuO x -CeO 2 catalyst for NO reduction by CO: New insights into the structure–activity relationship

CuO-CeO 2 based materials have been recognized as promising substitutes for precious metal catalysts in emission control field due to their superior redox property and low cost. In this work, by optimizing the deposition process of CeO 2 and CuO onto γ-Al 2 O 3 , highly dispersed CuO clusters on unique CeO 2 -Al 2 O 3 support with small CeO 2 particles (7Cu-Ce/CeAl) were successfully constructed for efficient NO reduction by CO, which exhibited much higher NO removal efficiency and N 2 selectivity than CuO catalysts supported on γ-Al 2 O 3 (7Cu/Al) and conventional CeO 2 -Al 2 O 3 support (7Cu/CeAl). Moreover, H 2 O showed limited inhibition effect on the catalytic performance of 7Cu-Ce/CeAl catalyst. With the help of Raman spectra, X-ray absorption spectroscopy, in situ diffuse reflectance infrared Fourier transform spectroscopy, etc., it was clearly revealed that the abundant Cu + /Ce 3+ paired sites with surface synergetic oxygen vacancies (SSOV) on 7Cu-Ce/CeAl catalyst could effectively facilitate the adsorption and activation of CO and NO, thus significantly enhancing the NO removal efficiency.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Reduced metal nanocatalysts for selective electrochemical hydrogenation of biomass-derived 5-(hydroxymethyl)furfural to 2,5-bis(hydroxymethyl)furan in ambient conditions

Selective electrochemical hydrogenation (ECH) of biomass-derived unsaturated organic molecules has enormous potential for sustainable chemical production. However, an efficient catalyst is essential to perform an ECH reaction consisting of superior product selectivity and a higher conversion rate. Here, we examined the ECH performance of reduced metal nanostructures, i.e., reduced Ag (rAg) and reduced copper (rCu) prepared via electrochemical or thermal oxidation and electrochemical reduction process, respectively. Surface morphological analysis suggests the formation of nanocoral and entangled nanowire structure formation for rAg and rCu catalysts. rCu exhibits a slight enhancement in ECH reaction performance in comparison to the pristine Cu. However, the rAg exhibits more than two times higher ECH performance without compromising the selectivity for 5-(HydroxyMethyl) Furfural (HMF) to 2,5-bis(HydroxyMethyl)-Furan (BHMF) formation in comparison to the Ag film. Moreover, a similar ECH current density was recorded at a reduced working potential of 220 mV for rAg. This high performance of rAg is attributed to the formation of new catalytically active sites during the Ag oxidation and reduction processes. This study demonstrates that rAg can potentially be used for the ECH process with minimum energy consumption and a higher production rate.

2,5- bis(hydroxymethyl)furan (BHMF)↗
DOE OSTI2023

Enhancing the activity of Pd ensembles on graphene by manipulating coordination environment

Atomic dispersion of metal catalysts on a substrate accounts for the increased atomic efficiency of single-atom catalysts (SACs) in various catalytic schemes compared to the nanoparticle counterparts. However, lacking neighboring metal sites has been shown to deteriorate the catalytic performance of SACs in a few industrially important reactions, such as dehalogenation, CO oxidation, and hydrogenation. Metal ensemble catalysts (M n ), an extended concept to SACs, have emerged as a promising alternative to overcome such limitation. Inspired by the fact that the performance of fully isolated SACs can be enhanced by tailoring their coordination environment (CE), we here evaluate whether the CE of M n can also be manipulated in order to enhance their catalytic activity. We synthesized a set of Pd ensembles (Pd n ) on doped graphene supports (Pd n /X-graphene where X = O, S, B, and N). We found that introducing S and N onto oxidized graphene modifies the first shell of Pd n converting Pd–O to Pd–S and Pd–N, respectively. Also, we further found that the B dopant significantly affected the electronic structure of Pd n by serving as an electron donor in the second shell. We examined the performance of Pd n /X-graphene toward selective reductive catalysis, such as bromate reduction, brominated organic hydrogenation, and aqueous-phase CO 2 reduction. We observed that Pd n /N-graphene exhibited superior performance by lowering the activation energy of the rate-limiting step, i.e., H 2 dissociation into atomic hydrogen. The results collectively suggest controlling the CE of SACs in an ensemble configuration is a viable strategy to optimize and enhance their catalytic performance.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Low temperature, ambient pressure electrochemical ammonia synthesis in alkaline media — Mechanistic studies and catalyst design. Final Report

Ammonia synthesis via the Haber-Bosch process is a pillar of modern agriculture, which converts the abundant but inert dinitrogen in the atmosphere to nitrogen-based fertilizers. Despite more than a century of optimization, the Haber-Bosch process remains energy intensive and reliant on fossil fuels and produces large amounts of CO 2 . Distributed and modular ammonia synthesis via the electrochemical nitrogen reduction reaction (ENRR) at or close to ambient conditions, powered by renewable electricity is an attractive alternative because it allows as needed production of ammonia, and in turn fertilizers. However, selective ENRR catalysts remain lacking. In this project, we systematically investigated two categories of catalytic materials, i.e., precious metals and transition metal nitrides, in the ENRR. Precious metals exhibit low activity and selectivity in the ENRR, which is in agreement with recent computational studies. Transition metal nitrides, especially VN, has been demonstrated as active and selective ENRR catalysts. We developed the first quantitative method to determine the amount of ammonia produced in the ENRR on N-containing containing catalysts in the membrane electrode assembly configuration. An initial ammonia production rate of 6.6 × 10 -10 mol s -1 mg -1 and a Faradaic efficiency of 6.0% at -0.1 V were reached on VN. After the initial deactivation, VN was shown to be stable in the ENRR for 116 hours with a steady state ammonia production rate of 1.1 × 10 -10 mol s -1 cm -2 . A vanadium oxynitride species was identified as the active phase in the ENRR via a combination of operando and ex situ characterization techniques. In addition, we established that the ENRR proceeded on transition metal nitrides via the Mars van Krevelen mechanism and determined the initial and steady state active site densities by developing a quantitative isotopic exchange method.

42 ENGINEERING↗
DOE OSTI2023

Surfactants Used in Colloidal Synthesis Modulate Ni Nanoparticle Surface Evolution for Selective CO 2 Hydrogenation

Colloidal chemistry holds promise to prepare uniform and size-controllable pre-catalysts; however, it remains a challenge to unveil the atomic-level transition from pre-catalysts to active catalytic surfaces under the reaction conditions to enable the mechanistic design of catalysts. In this work, we report an ambient-pressure X-ray photoelectron spectroscopy study, coupled with in situ environmental transmission electron microscopy, infrared spectroscopy, and theoretical calculations, to elucidate the surface catalytic sites of colloidal Ni nanoparticles for CO 2 hydrogenation. We show that Ni nanoparticles with phosphine ligands exhibit a distinct surface evolution compared with amine-capped ones, owing to the diffusion of P under oxidative (air) or reductive (CO 2 + H 2 ) gaseous environments at elevated temperatures. The resulting NiP x surface leads to a substantially improved selectivity for CO production, in contrast to the metallic Ni, which favors CH 4 . The further elimination of surface metallic Ni sites by designing multi-step P incorporation achieves unit selectivity of CO in high-rate CO 2 hydrogenation.

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

Solar–Driven CO 2 Conversion via Optimized Photothermal Catalysis in a Lotus Pod Structure

Photothermal CO 2 reduction is one of the most promising routes to efficiently utilize solar energy for fuel production at high rates. However, this reaction is currently limited by underdeveloped catalysts with low photothermal conversion efficiency, insufficient exposure of active sites, low active material loading, and high material cost. Herein, we report a potassium-modified carbon-supported cobalt (K + –Co–C) catalyst mimicking the structure of a lotus pod that addresses these challenges. As a result of the designed lotus-pod structure which features an efficient photothermal C substrate with hierarchical pores, an intimate Co/C interface with covalent bonding, and exposed Co catalytic sites with optimized CO binding strength, the K + –Co–C catalyst shows a record-high photothermal CO 2 hydrogenation rate of 758 mmol gcat –1 h –1 (2871 mmol gCo –1 h –1 ) with a 99.8 % selectivity for CO, three orders of magnitude higher than typical photochemical CO 2 reduction reactions. Here, we further demonstrate with this catalyst effective CO 2 conversion under natural sunlight one hour before sunset during the winter season, putting forward an important step towards practical solar fuel production.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Fluorine-Tuned Carbon-Based Nickel Single-Atom Catalysts for Scalable and Highly Efficient CO 2 Electrocatalytic Reduction

Electrocatalytic CO 2 reduction is garnering significant interest due to its potential applications in mitigating CO 2 and producing fuel. However, the scaling up of related catalysis is still hindered by several challenges, including the cost of the catalytic materials, low selectivity, small current densities to maintain desirable selectivity. In this study, Fluorine (F) atoms were introduced into an N-doped carbon-supported single nickel (Ni) atom catalyst via facile polymer-assisted pyrolysis. This method not only maintains the high atom utilization efficiency of Ni in a cost-effective and sustainable manner but also effectively manipulates the electronic structure of the active Ni-N 4 site through F doping. The catalyst has also been further optimized by controlling the F states, including convalent and semi-ionic states, by adjusting the fluorine sources involved. Consequently, this catalyst with unique structure exhibited comparable electrocatalytic performance for CO 2 -to-CO conversion, achieving a Faradaic efficiency (FE) of over 99% across a wide potential range and an exceptional CO evolution rate of 9.5 x 10 4 h -1 at -1.16 V vs reversible hydrogen electrode (RHE). It also delivered a practical current of 400 mA cm -2 while maintaining more than 95% CO FE. Experimental analysis combined with density functional theory (DFT) calculations have also shown that F-doping modifies the electron configuration at the central Ni-N 4 sites. In conclusion, this modification lowers the energy barrier for CO 2 activation, thereby facilitating the production of the crucial *COOH intermediate.

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

Tuning Proton Transfer Thermodynamics in SARS-CoV-2 Main Protease: Implications for Catalysis and Inhibitor Design

The catalytic reaction in SARS-CoV-2 main protease is activated by a proton transfer (PT) from Cys145 to His41. The same PT is likely also required for the covalent binding of some inhibitors. Here we use a multiscale computational approach to investigate the PT thermodynamics in the apo enzyme and in complex with two potent inhibitors, N3 and the α-ketoamide 13b. We show that with the inhibitors the free energy cost to reach the charge-separated state of the active-site dyad is lower, with N3 inducing the most significant reduction. We also show that a few key sites (including specific water molecules) significantly enhance or reduce the thermodynamic feasibility of the PT reaction, with selective desolvation of the active site playing a crucial role. The approach presented is a cost-effective procedure to identify the enzyme regions that control the activation of the catalytic reaction and is thus also useful to guide the design of inhibitors.

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

Solar‐Driven CO 2 Conversion via Optimized Photothermal Catalysis in a Lotus Pod Structure

Abstract Photothermal CO 2 reduction is one of the most promising routes to efficiently utilize solar energy for fuel production at high rates. However, this reaction is currently limited by underdeveloped catalysts with low photothermal conversion efficiency, insufficient exposure of active sites, low active material loading, and high material cost. Herein, we report a potassium‐modified carbon‐supported cobalt (K + −Co−C) catalyst mimicking the structure of a lotus pod that addresses these challenges. As a result of the designed lotus‐pod structure which features an efficient photothermal C substrate with hierarchical pores, an intimate Co/C interface with covalent bonding, and exposed Co catalytic sites with optimized CO binding strength, the K + −Co−C catalyst shows a record‐high photothermal CO 2 hydrogenation rate of 758 mmol g cat −1 h −1 (2871 mmol g Co −1 h −1 ) with a 99.8 % selectivity for CO, three orders of magnitude higher than typical photochemical CO 2 reduction reactions. We further demonstrate with this catalyst effective CO 2 conversion under natural sunlight one hour before sunset during the winter season, putting forward an important step towards practical solar fuel production.

Wang, Hongmin↗
DOE OSTI2022

Strategies for breaking molecular scaling relationships for the electrochemical CO 2 reduction reaction

The electrocatalytic CO 2 reduction reaction (CO 2 RR) is a promising strategy for converting CO 2 to fuels and value-added chemicals using renewable energy sources. Molecular electrocatalysts show promise for the selective conversion of CO 2 to single products with catalytic activity that can be tuned through synthetic structure modifications. However, for the CO 2 RR by traditional molecular catalysts, beneficial decreases in overpotentials are usually correlated with detrimental decreases in catalytic activity. This correlation is sometimes referred to as a “molecular scaling relationship”. Overcoming this inverse correlation between activity and effective overpotential remains a challenge when designing new, efficient molecular catalyst systems. Here, in this perspective, we discuss some of the concepts that give rise to the molecular scaling relationships in the CO 2 RR by molecular catalysts. We then provide an overview of some reported strategies from the last decade for breaking these scaling relationships. We end by discussing strategies and progress in our own research designing efficient molecular catalysts with redox-active ligands that show high activity at low effective overpotentials for the CO 2 RR.

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

Separations Consortium: Lignin Rich Stream Fractionation and Purification

In support of the Bioenergy Technologies Office in converting lignin to fuels and chemicals, this project develops scalable separations based on membranes and Electordeionization (EDI) to recover low molecular weight (LMW) compounds from lignin rich streams. The project addresses three technology barriers in developing the bioeconomy; (1) Cost of production (2) Selective separation of organic acid species, and (3) Advanced bioprocess development. Specifically, membrane cascades using Tangential Flow Filtration (TFF) are investigated for the recovery of LMW lignin compounds from lignin rich streams such as Alkaline Pretreatment Liquor (APL), Reductive Catalytic Fractionation (RCF) oil, and Catalytic Oxidation oil. Process concepts, including dynamic filtration, are investigated to meet specific performance targets indicated by the consortium's Industrial Advisory Board for the membrane filtration including maintaining permeance > 1 LMH/bar and an overall cost target of < $1/kg of LMW lignin. EDI is investigated as an integral part of the membrane cascade to recover LMW aromatic acids and as an alternative to nanofiltration. Economic analysis of the processes is presented with a focus on minimizing energy consumption and capital expenditure. Furthermore, a sensitivity analysis is presented to identify key cost drivers and optimize holistic process operating conditions.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗