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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 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Oxidation Chemistry of Bicarbonate and Peroxybicarbonate: Implications for Carbonate Management in Energy Storage

Carbonate formation presents a major challenge to energy storage applications based on low-temperature CO 2 electrolysis and recyclable metal–air batteries. While direct electrochemical oxidation of (bi)carbonate represents a straightforward route for carbonate management, knowledge of the feasibility and mechanisms of direct oxidation is presently lacking. Herein, we report the isolation and characterization of the bis(triphenylphosphine)iminium salts of bicarbonate and peroxybicarbonate, thus enabling the examination of their oxidation chemistry. Infrared spectroelectrochemistry combined with time-resolved infrared spectroscopy reveals that the photoinduced oxidation of HCO 3 – by an Ir(III) photoreagent results in the generation of the short-lived bicarbonate radical in less than 50 ns. The highly acidic bicarbonate radical undergoes proton transfer with HCO 3 – to furnish the carbonate radical anion and H 2 CO 3 , leading to the eventual release of CO 2 and H 2 O, thus accounting for the appearance of H 2 O and CO 2 in both electrochemical and photochemical oxidation experiments. Here, the back reaction of the carbonate radical subsequently oxidizes the Ir(II) photoreagent, leading to carbonate. In the absence of this back reaction, dimerization of the carbonate radical provides entry into peroxybicarbonate, which we show undergoes facile oxidation to O 2 and CO 2 . Together, the results reported identify tangible pathways for the design of catalysts for the management of carbonate in energy storage applications.

25 ENERGY STORAGE↗
DOE OSTI2021

A comparative techno-economic analysis of renewable methanol synthesis from biomass and CO 2 : Opportunities and barriers to commercialization

Global demand for methanol as both a chemical precursor and a fuel additive is rising. At the same time, numerous renewable methanol production pathways are under development, which, if commercialized, could provide significant environmental benefits over traditional methanol synthesis pathways. However, it is difficult to compare technologies at different maturity levels, with differing feedstocks, and with significant differences in overall process design. Thus, there is a need to harmonize the analyses of renewable pathways using a consistent techno-economic approach to evaluate the potential for commercialization of various pathways. This analysis uses a novel cross-comparison method to assess near-term and long-term viability of both low- and high-maturity level technologies. Furthermore, the techno-economic assessment considers cost factors critical to market acceptance combined with carbon- and energy-efficiency assessments of three renewable pathways compared with a commercial baseline. We find that biomass gasification to methanol represents a near-term viable pathway with a high technology readiness level and commercially competitive market price. If cost-reducing technological improvements can be realized and scaled up in the CO 2 electrolysis pathways, the potential for higher carbon efficiencies may help drive market adoption of these more modular, direct conversion pathways in future markets as they present an opportunity to better support global decarbonization efforts through efficient waste carbon utilization.

09 BIOMASS FUELS↗
DOE OSTI2023

Controlling Mass Transport in Direct Carbon Dioxide Zero-Gap Electrolyzers via Cell Compression

The development of high-performance CO 2 electrolyzers is crucial for accelerating the sustainable production of fuels and chemicals integrated with renewable energy sources. Here, we introduce a methodology to actively control mass transport inside a realistic zero-gap membrane electrode assembly of a CO 2 electrolyzer by varying the gasket thickness, which consequently changes the cell compression. This allows control over the thickness and porosity of the gas diffusion electrodes, influencing the overall electrolyzer performance, as demonstrated using Ag-deposited electrodes. At low operating voltages (<2.9 V), both high- and low-compression electrolyzers exhibit similar faradaic efficiencies and partial current densities for CO formation. However, at high voltages, the low-compression electrolyzer with high electrode porosity demonstrates superior CO selectivity and activity with suppressed H 2 formation. These experimental results are validated by the computational membrane electrode assembly (MEA) model developed by using the measured in situ electrode thicknesses and electrode porosities. Additionally, liquid electrolyte saturation at the catalyst layer is found to play a dominant role in determining the mass transport, resulting in a decreased electrolyzer performance with low electrode porosity. Finally, the systematic investigation in this study improves the understanding of the transport dynamics in MEA-based devices and provides insights into optimizing device design parameters for industry-relevant CO 2 electrolysis.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2024

Production of Bioproducts from Electrochemically-Generated C1 Intermediates

The overarching objective of the project was to develop an integrated process that converts carbon dioxide (CO 2 ) into the platform chemical isopropanol (IPA) using a combination of two key technologies: CO 2 electrolysis and gas fermentation. The final goal was to demonstrate the full process at bench scale with a minimum carbon conversion efficiency of 37% and to evaluate the economics and environmental impact of scaling up the electrochemical-biochemical process.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2021

Water and Solute Activities Regulate CO 2 Reduction in Gas-Diffusion Electrodes

Electrolysis of CO 2 at gas-diffusion electrodes (GDEs) has typically been limited by the supply of gas to the electrocatalyst, overshadowing the importance of the supply of water. However, at high current densities that approach 1 A cm –2 , where the electrolyte becomes highly concentrated in the catalyst layer of a GDE, the activity of water and solutes deviate from their bulk dilute solution values, potentially slowing reaction rates and changing reaction equilibrium potentials. In addition, as flow plates for the gas stream are introduced to enable larger electrodes and high single pass conversion of CO 2 to product, variations in the gas composition will become important. By drawing upon literature for the oxygen reduction reaction (ORR), here we explain how to account for these effects in future modeling and experimental work, with particular attention to accurate use of the Nernst equation for electrode potentials and the Arrhenius equation for reaction rates. Specifically, using measurements of KOH solvent and solute activity reported in literature, and assuming the second protonation of CO 2 by water as the rate-determining step, we show the Nernst equation dilute-solution approximation of the CO 2 to CO equilibrium potential to be accurate below 5 M KOH, but it has a 74 mV error when increasing the concentration up to 10 M KOH. Finally, a simple one-dimensional model of a serpentine flow-field on a GDE demonstrated that a reactor with constant pressure of 1 bar and 1 A cm –2 at the inlet had only ~0.3 A cm –2 at the outlet for a conversion in CO 2 partial pressure from 0.90 to 0.48 bar, showing the significant practical implications of this work.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Alkaline cation enrichment and water electrolysis to provide CO 2 mineralization and global-scale carbon management

Provided herein are methods of removing carbon dioxide from an aqueous stream or gaseous stream by: contacting the gaseous stream comprising carbon dioxide, when present, with an aqueous solution comprising ions capable of forming an insoluble carbonate salt; contacting the aqueous solution comprising carbon dioxide with an electroactive mesh that induces its alkalinization thereby forcing the precipitation of a carbonate solid from the solution and thereby the removal of dissolved inorganic carbon by electrolysis; and removing the precipitated carbonate solids from the solution, or the surface of the mesh where they may deposit. Also provided herein are flow-through electrolytic reactors comprising an intake device in fluid connection with a rotating cylinder comprising an electroactive mesh, and a scraping device and/or liquid-spray based device for separating a solid from the mesh surface.

Sant, Gaurav↗
DOE OSTI2022

Promoting CO 2 Release from CO 3 2- -Containing Solvents during Water Electrolysis for Direct Air Capture

The pH swings from water electrolysis are leveraged to condition OH – -based facile CO 2 capture solvents using an electrochemical flow cell for direct air capture (DAC). Besides demonstrating the DAC using a membrane contactor, promoting CO 2 release from a CO 3 2– solution at the anode is specifically studied by adjusting the volumetric flow rate, anode chamber volume, residence time, and K 2 CO 3 concentration. Through case-by-case comparisons coupled with modeled results, increasing current, reducing volumetric flow rate, and/or reducing CO 3 2– concentration are the effective methods to promote CO 2 release from a CO 3 2– -containing solvent, whereas enlarging the anode chamber volume poses a minor effect. Moreover, the discrepancies between the experimental and modeled results may be caused by H + crossover rather than K + transport through the Nafion membrane during water electrolysis based upon the total alkalinity measurements for the K 2 CO 3 solutions gleaned from the anode. Here, it is believed that such results will provide guidance to design and operate an electrochemical flow cell for electrochemistry-assisted DAC and point source CO 2 capture.

20 FOSSIL-FUELED POWER PLANTS↗
DOE OSTI2025

Assessing the Long-Term Stability of Anion Exchange Membranes for Electrochemical CO 2 Reduction

Materials and cell components used in CO 2 electrolysis have largely been adapted from technologies initially developed for water electrolysis and fuel cells. However, electrochemical CO 2 reduction introduces distinct material challenges due to the unique chemical environment in this process. Here, in this study, we conducted ex-situ 1000 h stability tests on commonly used anion exchange membranes, exposing them exclusively to electrolytes and organic molecules used or produced during CO 2 electrolysis, at concentrations relevant to and compatible with postseparation processes. Notably, 15% w/w n-propanol and 5 M acetic acid caused complete dissolution or partial disintegration of the membranes unless cross-linking was present and remained stable throughout the test. When the membranes stayed physically intact, most of them exhibited excellent chemical stability in alkaline medium containing alcohols or formic acid, which was confirmed by vibrational spectroscopy and ion exchange capacity measurements. However, exposure to alcohol-and acid-containing solutions led to a substantial increase in swelling and water uptake, with potential implications for mechanical stability, ion/product crossover, and compression management of adjacent components. The potential effects of CO 2 electroreduction products on membrane stability, their subsequent impact on electrolyzer performance, and mitigation strategies are discussed.

CO2RR↗
DOE OSTI2026

Pulsed Electrolysis Promotes Catalyst Activity in Dilute CO 2 Streams

Industrial CO 2 streams vary widely in composition, from pure to as low as 3%, posing challenges for purification or direct conversion. Electrochemical reduction offers a route for converting dilute CO 2 streams but faces severe mass transport limitations. This study demonstrates that pulsed electrolysis effectively overcomes these limitations, enhancing CO 2 electroreduction across variable feed compositions and current densities, particularly at low CO 2 concentrations and high current densities. At 25% CO 2 and 400 mA cm −2 , pulsing improved selectivity from 25.6 to 78.6%, production rate from 13.7 to 21.0 mol m −2 h −1 , and energy productivity from 0.77 to 2.59 mol kWh −1 . A dynamic, multiphysics continuum model confirms a 64% increase in CO 2 concentration within the catalyst layer during pulsing, resolving the transient chemical microenvironment. These findings establish pulsed electrolysis as a viable strategy for converting dilute industrial CO 2 streams into valuable feedstocks, bypassing costly pre-separation.

Orfali, Dania Muhieddine [New York University (NYU↗
DOE OSTI2023

Prolonged Stability of Pb-Catalyzed CO 2 Electroreduction to Methyl Formate in Acidic Methanol

Electrochemical CO 2 reduction from renewable energy is a promising route to mitigate greenhouse gas emissions from waste sources while generating value-added products. CO 2 electroreduction in methanol is particularly interesting due to the increased CO 2 solubility compared to water and the propensity to form methyl formate, a product absent in aqueous electrolysis. Here, four factors have been identified as critical to achieving prolonged high selectivity for methyl formate production on a Pb cathode in methanol: high pH near the electrode, low bulk pH, low water content, and regeneration of Pb 2+ sites. Increasing concentration of the formic acid product was observed to induce a selectivity shift towards hydrogen, which was mitigated by the in-situ conversion of the formic acid to methyl formate via an esterification reaction. Furthermore, co-electrolysis of CO 2 with dilute molecular oxygen (4% O 2 ) led to Pb catalyst repair through in-situ surface oxidation. Using CO 2 and dilute O 2 along with single-pass catholyte flow to maintain a low formic acid concentration, sustained high selectivity for methyl formate was attained at ~60% faradaic efficiency at -20 mA cm -2 for over 72 hours.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

CO 2 to Fuels Through Novel Electrochemical Catalysis (Final Report)

Electrochemical upgrading of CO 2 into hydrocarbon fuels via CO 2 –H 2 O co-electrolysis using solid oxide electrolysis cells (SOECs) presents an encouraging approach to cost-effective storage of renewable power. In this study, we harness the unique property of protonic ceramic electrolysis cells (PCEC) and demonstrate direct electro-catalytic production of CH 4 from CO 2 –H 2 O in a unit-cell stack configuration. The unit-cell stack was developed to evaluate the scalability and the applicability of PCECs from a broader system-level viewpoint. Tradeoffs between operating conditions and performance metrics were explored and thoroughly characterized. An exceptional CH 4 -yield ratio of 34.6% from only CO 2 –H 2 O reactants was achieved under an electrolysis current of 1 A cm –2 at 450 °C. With exhaust-H 2 recycle, this value was boosted to greater than 70%. In addition, the electrochemical co-conversion of CO 2 –H 2 O offers a higher CH 4 -yield ratio compared to traditional thermo-catalytic conversion of CO 2 –H 2 under certain operating conditions, indicating possible electrochemical promotion of catalytic CO 2 methanation. The demonstrated good performance is a promising result for further scale-up and for the practical utilization of electrochemical CO 2 upgrade using PCECs. Techno-economic analyses reveal operating conditions that yield cost-competitive levelized cost of fuel production.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2024

CO 2 fixation into carbon nanofibres using electrochemical–thermochemical tandem catalysis

Carbon dioxide (CO 2 ) fixation into value-added solid carbon such as carbon nanofibres (CNF) for longer-term storage represents a promising avenue for achieving net-negative carbon emissions. However, directly converting CO 2 to CNF via thermocatalytic approaches faces thermodynamic constraints, while electrocatalytic methods typically lead to amorphous carbon with limited yields or require energy-intensive conditions (>720 °C). Here, we present an electrocatalytic-thermocatalytic tandem strategy for CNF production, which circumvents the aforementioned thermodynamic limitations by integrating the co-electrolysis of CO 2 and water into syngas (CO and H 2 ) with a subsequent thermochemical process at relatively mild conditions (370-450 °C, 1 atm), yielding CNF at a high production rate (average 2.5 g carbon g metals -1 h -1 ). Further, the optimal coordinated actions of FeCo alloy and extra metallic Co were ascertained to enhance the dissociative activation of syngas and favour the carbon-carbon bond formation to produce CNF. This tandem strategy opens a door to leverage renewable energy for decarbonizing CO 2 into valuable solid carbon products while producing renewable H 2 .

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

Electrocatalytic Effects of Au Nanoclusters in its Electrochemiluminescence Enhanced by Coreactant Tertiary Amines

Abstract Atomically precise metal nanoclusters are increasingly exploited in electrocatalysis such as water electrolysis and CO 2 reduction. The catalytic effects are generally evaluated by conventional electrochemical methods or end‐product analysis. Herein, near infrared electrochemiluminescence (ECL) of the nanoclusters is introduced as a new signaling mechanism to complement classical voltammetric analysis for elucidating essential electrocatalytic parameters. Coreactant ECL from an aqueous soluble Au 22 nanocluster (NCs) enhanced by a common pH buffer materials 4‐(2‐hydroxyethyl)‐1‐piperazineethanesulfonic acid (HEPES) and by a piperazine drug hydroxyzine (HDZ) is studied under oxidative reduction pathways. Foot of the wave analysis on voltametric features and the kinetics profiles in potential‐step experiments are studied in different nanocluster and coreactant concentrations. Benchmark parameters such as rate constants are determined under EC (Electron‐transfer‐Chemical‐reaction) mechanism as feasibility validations. Because the luminescence properties of AuNCs are sensitive to the surface ligands or adsorbents, ECL is proposed as a new signal readout for operando studies providing insights for governing reaction mechanism and kinetics during catalytic reactions. Retrospectively, mechanistic understanding of the complex multi‐step reactions during ECL generation can provide guidance for the evaluation and optimization of ECL property for better quantitative applications.

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

Aqueous electrocatalytic CO 2 reduction using metal complexes dispersed in polymer ion gels

We use fac-[Re(bpy)(CO) 3 Cl] ([Re–Cl]) dispersed in polymer ion gel (PIG) ([Re]–PIG) to carry out electrocatalytic CO 2 reduction in water. Electrolysis at -0.68 V vs. RHE in a CO 2 -saturated KOH and K 2 CO 3 solution produces CO with over 90% Faradaic efficiency. The PIG electrode is readily combined with water oxidation catalysts to generate a full electrochemical cell. Additionally, we provide evidence that the PIG electrode can be implemented with other molecular catalysts.

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

Enhancing carbon dioxide gas-diffusion electrolysis by creating a hydrophobic catalyst microenvironment

Electroreduction of carbon dioxide (CO 2 ) over copper-based catalysts provides an attractive approach for sustainable fuel production. While efforts are focused on developing catalytic materials, it is also critical to understand and control the microenvironment around catalytic sites, which can mediate the transport of reaction species and influence reaction pathways. Here, we show that a hydrophobic microenvironment can significantly enhance CO 2 gas-diffusion electrolysis. For proof-of-concept, we use commercial copper nanoparticles and disperse hydrophobic polytetrafluoroethylene (PTFE) nanoparticles inside the catalyst layer. Consequently, the PTFE-added electrode achieves a greatly improved activity and Faradaic efficiency for CO 2 reduction, with a partial current density >250 mA cm -2 and a single-pass conversion of 14% at moderate potentials, which are around twice that of a regular electrode without added PTFE. The improvement is attributed to a balanced gas/liquid microenvironment that reduces the diffusion layer thickness, accelerates CO 2 mass transport, and increases CO 2 local concentration for the electrolysis.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Challenges in Product Selectivity for Electrocatalytic Reduction of Amine-Captured CO 2 : Implications for Reactive Carbon Capture

CO 2 is a potential feedstock for carbon-based fuels or materials, but is only available in dilute streams. Integrated processes for CO 2 capture and conversion directly valorize the CO 2 captured by sorbent materials, skipping the energetically expensive sorbent regeneration step. Amines are the most heavily studied liquid-phase sorbent materials for CO 2 capture from dilute streams. Amines react with CO 2 in a 2:1 ratio to form the corresponding ammonium carbamate. Ammonium carbamate [NH 4 ][H 2 NCO 2 ] was tested as the substrate using the highly selective and robust CO 2 -to-formate reduction electrocatalyst [( tBu POCOP)Ir(H)(NCCH 3 ) 2 ], where ( tBu POCOP) is the tridentate pincer ligand 2,6-bis(di tert -butyl-phosphonito). When ammonium carbamate was used as the substrate instead of CO 2 , only hydrogen was produced. An equivalent electrolysis with ammonium hexafluorophosphate with CO 2 also resulted in primarily hydrogen. Methyl carbamate and urea were also tested as substrates as proxies for carbamate that do not contain an equivalent of ammonium, and there was also negligible reduction to carbon-based products. These results indicate that the loss of selectivity observed for aminecaptured CO 2 , or ammonium carbamate, is likely due to the generation of the acidic ammonium equivalent as well as the greater challenge of reducing carbamate compared to CO 2 . This study illustrates that catalysts with high selectivity for concentrated CO 2 can favor hydrogen evolution and loss of carbon-based products when amine-captured CO 2 is used instead.

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

Intensified Co-electrolysis Process for Syngas Production from Captured CO 2

CO 2 reduction to syngas provides a way of ameliorating carbon footprint and storing energy in high-energy-density and versatile feedstock. This current work explores the isothermal integration of CO2 capture with an intensified unit operation for the reduction of CO2 and capture media regeneration. Intensified captured CO2 co-electrolysis (ICC) to syngas (H2:CO ratio of 2) with low CO2 content (<10%) was demonstrated with over 70% CO2 conversion at a current density up to 0.20 A/cm2 for 14 hours of operation. Integration of the co-electrolysis unit with CO2 capture was performed feeding pure and diluted CO2, for which CO2 conversions >65% were observed. Performance of the capture unit becomes critical to maintain syngas ratios (SR). Technology feasibility was assessed through comparative techno-economic and life cycle analysis showing that process intensification enables competitive performance, even at the higher energy consumption featured at the current state of the technology. This because several unit operations can be avoided. LCA also showed that based on the current US electricity mix the reduction of life cycle CO2 emissions is possible at scenarios observed with 0.15 A/cm2 to accomplish a carbon-negative technology.

08 HYDROGEN↗
DOE OSTI2024

Seawater electrolysis enables Mg(OH) 2 production and CO 2 mineralization

A method for producing one or more hydroxide solids includes providing a catholyte comprising an electrolyte solution; contacting the catholyte with an electroactive mesh cathode to electrolytically generate hydroxide ions, thereby precipitating the one or more hydroxide solid(s); and removing the one or more hydroxide solids from the surface of the mesh where they may deposit.

Chen, Xin↗