Design Strategies for Coupling CO 2 Reduction Molecular Electrocatalysts to Silicon Photocathodes
Not Available
14 SOLAR ENERGY↗
SEARCH · Engineering Papers
Results for “carbon reduction”
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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Dissolution and reduction of magnetite by bacteria
Magnetite (Fe3O4) is an iron oxide of mixed oxidation state [Fe(II), Fe(III)] that contributes largely to geomagnetism and plays a significant role in diagenesis in marine and freshwater sediments. Magnetic data are the primary evidence for ocean floor spreading and accurate interpretation of the sedimentary magnetic record depends on an understanding of the conditions under which magnetite is stable. Though chemical reduction of magnetite by dissolved sulfide is well known, biological reduction has not been considered likely based upon thermodynamic considerations. This study shows that marine and freshwater strains of the bacterium Shewanella putrefaciens are capable of the rapid dissolution and reduction of magnetite, converting millimolar amounts to soluble Fe(II)in a few days at room temperature. Conditions under which magnetite reduction is optimal (pH 5-6, 22-37 degrees C) are consistent with an enzymatic process and not with simple chemical reduction. Magnetite reduction requires viable cells and cell contact, and it appears to be coupled to electron transport and growth. In a minimal medium with formate or lactate as the electron donor, more than 10 times the amount of magnetite was reduced over no carbon controls. These data suggest that magnetite reduction is coupled to carbon metabolism in S. putrefaciens. Bacterial reduction rates of magnetite are of the same order of magnitude as those estimated for reduction by sulfide. If such remobilization of magnetite occurs in nature, it could have a major impact on sediment magnetism and diagenesis.
Non-NASA Center↗
Net-Zero Carbon Microgrids
The microgrid concept has been effective in creating aggregations of distributed energy resources—generation, storage and loads—for resiliency, in the form of energy security. The success of microgrids in bringing energy security to a wide range of customers—from individual residences to commercial and industrial installations to military bases—has been exemplified during power disruptions and extended outages due to extreme weather events, cybersecurity attacks, and equipment failures. Now microgrids have an opportunity to meet the challenges of climate change and contribute to a carbon-free power delivery system. The transition to net-zero starts within microgrids themselves. In fact, today’s microgrids are largely dominated by generators using fossil fuels, natural gas and diesel, with high greenhouse gas emissions. In short, the transition to net-zero means replacing fossil fueled generators with renewable generation in microgrids. This transition is extended by including new dispatchable generation technologies that are 100% carbon-free and that offer additional advantage of a more-dependable and sustainable source of energy and power. Basically, the decarbonization of microgrids requires three elements: 1) maximizing generation from renewable energy resources, 2) management of storage and flexible loads to balance the variability and intermittency of renewable energy resources, and 3) introducing new clean power sources, including hydrogen-based generation and small modular reactors. This report affirms a need for specific focus by governmental agencies at national, regional, and local levels to establish technology, policy, and investment in this area. The intention of the Net-Zero Microgrid (NZM) Program is to inform these constituencies with cross-cutting research and tools for the reduction of GHG in microgrids – to net-zero in the near term eventually to zero in the longer term. The NZM Program is committed to achieving decarbonization for resiliency and for providing clean energy at the local or distribution level, from remote communities to underserved communities, and large industrial and military facilities. The NZM Planning and Design Platform is a core tool to be developed as an early deliverable of the NZM Program because only a fully integrated microgrid-design approach will ensure maximum carbon reduction in energy production.
13 HYDRO ENERGY↗
Reduction of aircraft gas turbine engine pollutant emissions
To accomplish simultaneous reduction of unburned hydrocarbons, carbon monoxide, and oxides of nitrogen, required major modifications to the combustor. The modification most commonly used was a staged combustion technique. While these designs are more complicated than production combustors, no insurmountable operational difficulties were encountered in either high pressure rig or engine tests which could not be resolved with additional normal development. The emission reduction results indicate that reductions in unburned hydrocarbons were sufficient to satisfy both near and far-termed EPA requirements. Although substantial reductions were observed, the success in achieving the CO and NOx standards was mixed and depended heavily on the engine/engine cycle on which it was employed. Technology for near term CO reduction was satisfactory or marginally satisfactory. Considerable doubt exists if this technology will satisfy all far-term requirements.
Diehl, L. A.↗
An improved semi-global intrinsic kinetics model for high temperature carbon oxidation
Measurements of the oxidation rates of various forms of carbon (soot, graphite, coal char) have often shown an unexplained attenuation with increasing temperatures in the vicinity of 2000 K, even when accounting for diffusional transport limitations and gas-phase chemical effects (e.g. CO 2 dissociation). With the development of oxy-fuel combustion approaches for pulverized coal utilization with carbon capture, high particle temperatures are readily achieved in sufficiently oxygen-enriched environments. Here, in this work, a new semi-global intrinsic kinetics model for high temperature carbon oxidation is created by starting with a previously developed 5-step mechanism that was shown to reproduce all major known trends in carbon oxidation, except for its high temperature kinetic falloff, and incorporating a recently discovered surface oxide decomposition step. The predictions of this new model are benchmarked by deploying the kinetic model in a steady-state reacting particle code (SKIPPY) and comparing the simulated results against a carefully measured set of pulverized coal char combustion temperature measurements over a wide range of oxygen concentrations in N 2 and CO 2 environments. The results show that the inclusion of the spontaneous surface oxide decomposition reaction step significantly improves predictions at high particle temperatures. Furthermore, the simulations reveal that O atoms released from the oxide decomposition step enhance the radical pool in the near-surface region and within the particle interior itself. Incorporation of literature rates for O and OH reactions with the carbon surface results in a reduction in the predicted radical pool concentrations and a very minor enhancement of the overall carbon oxidation rate.
33 ADVANCED PROPULSION SYSTEMS↗
The Impact of Back-Sputtered Carbon on the Accelerator Grid Wear Rates of the NEXT and NSTAR Ion Thrusters
A study was conducted to quantify the impact of back-sputtered carbon on the downstream accelerator grid erosion rates of the NEXT (NASA's Evolutionary Xenon Thruster) Long Duration Test (LDT1). A similar analysis that was conducted for the NSTAR (NASA's Solar Electric Propulsion Technology Applications Readiness Program) Life Demonstration Test (LDT2) was used as a foundation for the analysis developed herein. A new carbon surface coverage model was developed that accounted for multiple carbon adlayers before complete surface coverage is achieved. The resulting model requires knowledge of more model inputs, so they were conservatively estimated using the results of past thin film sputtering studies and particle reflection predictions. In addition, accelerator current densities across the grid were rigorously determined using an ion optics code to determine accelerator current distributions and an algorithm to determine beam current densities along a grid using downstream measurements. The improved analysis was applied to the NSTAR test results for evaluation. The improved analysis demonstrated that the impact of back-sputtered carbon on pit and groove wear rate for the NSTAR LDT2 was negligible throughout most of eroded grid radius. The improved analysis also predicted the accelerator current density for transition from net erosion to net deposition considerably more accurately than the original analysis. The improved analysis was used to estimate the impact of back-sputtered carbon on the accelerator grid pit and groove wear rate of the NEXT Long Duration Test (LDT1). Unlike the NSTAR analysis, the NEXT analysis was more challenging because the thruster was operated for extended durations at various operating conditions and was unavailable for measurements because the test is ongoing. As a result, the NEXT LDT1 estimates presented herein are considered preliminary until the results of future posttest analyses are incorporated. The worst-case impact of carbon back-sputtering was determined to be the full power operating condition, but the maximum impact of back-sputtered carbon was only a four percent reduction in wear rate. As a result, back-sputtered carbon is estimated to have an insignificant impact on the first failure mode of the NEXT LDT at all operating conditions.
Soulas, George C.↗
The Impact of Back-Sputtered Carbon on the Accelerator Grid Wear Rates of the NEXT and NSTAR Ion Thrusters
A study was conducted to quantify the impact of back-sputtered carbon on the downstream accelerator grid erosion rates of the NASA's Evolutionary Xenon Thruster (NEXT) Long Duration Test (LDT1). A similar analysis that was conducted for the NASA's Solar Electric Propulsion Technology Applications Readiness Program (NSTAR) Life Demonstration Test (LDT2) was used as a foundation for the analysis developed herein. A new carbon surface coverage model was developed that accounted for multiple carbon adlayers before complete surface coverage is achieved. The resulting model requires knowledge of more model inputs, so they were conservatively estimated using the results of past thin film sputtering studies and particle reflection predictions. In addition, accelerator current densities across the grid were rigorously determined using an ion optics code to determine accelerator current distributions and an algorithm to determine beam current densities along a grid using downstream measurements. The improved analysis was applied to the NSTAR test results for evaluation. The improved analysis demonstrated that the impact of back-sputtered carbon on pit and groove wear rate for the NSTAR LDT2 was negligible throughout most of eroded grid radius. The improved analysis also predicted the accelerator current density for transition from net erosion to net deposition considerably more accurately than the original analysis. The improved analysis was used to estimate the impact of back-sputtered carbon on the accelerator grid pit and groove wear rate of the NEXT Long Duration Test (LDT1). Unlike the NSTAR analysis, the NEXT analysis was more challenging because the thruster was operated for extended durations at various operating conditions and was unavailable for measurements because the test is ongoing. As a result, the NEXT LDT1 estimates presented herein are considered preliminary until the results of future post-test analyses are incorporated. The worst-case impact of carbon back-sputtering was determined to be the full power operating condition, but the maximum impact of back-sputtered carbon was only a 4 percent reduction in wear rate. As a result, back-sputtered carbon is estimated to have an insignificant impact on the first failure mode of the NEXT LDT1 at all operating conditions.
Soulas, George C.↗
Circumventing Radical Generation on Fe–V Atomic Pair Catalyst for Robust Oxygen Reduction and Zinc–Air Batteries
Iron–nitrogen–carbon (Fe–N–C) catalysts are considered the most active platinum-free alternative for oxygen reduction reaction (ORR), yet the generated reactive oxygen species (ROS) from general mechanistic pathway rapidly impair the ORR activity and stability of Fe–N–C. Herein, we establish and report an ORR pathway-switching strategy to circumvent ROS generation and fundamentally improve the activity and stability of Fe–N–C via DFT guided catalyst design. The constructed Fe–V atomic pair catalyst (Fe 1 V 1 -NC) with N 2 Fe-N 2 -VN 2 configuration enables side-on adsorption of O 2 and subsequent direct-breaking of the O═O bond to form O*, thereby avoiding the formation of ROS radicals. Importantly, there is intersite electron interaction between FeN 4 and VN 4 , which further boosts the ORR activity. Consequently, Fe 1 V 1 -NC exhibits outstanding ORR activity with onset and half-wave (E 1/2 ) potentials at 1.02 and 0.89 V versus RHE, respectively, in 0.1 M KOH. Record-high stability is achieved on Fe 1 V 1 -NC with a minimal decay in E 1/2 by 16 mV over 50000 cycles, surpassing Fe–N–C counterpart and most of the catalysts reported to date. The Fe 1 V 1 -NC-based zinc-air battery reported here demonstrates exceptional durability up to 400 h at 10 mA·cm −2 . This work identifies the intrinsic correlation between ORR pathway, activity, and stability, advancing development of stable catalytic systems.
Fe-N-C↗
Reduction of iron-bearing lunar minerals for the production of oxygen
The kinetics and mechanism of the reduction of simulants of the iron-bearing lunar minerals olivine ((Fe,Mg)2SiO4), pyroxene ((Fe,Mg,Ca)SiO3), and ilmenite (FeTiO3) are investigated, extending previous work with ilmenite. Fayalite is reduced by H2 at 1070 K to 1480 K. A layer of mixed silica glass and iron forms around an unreacted core. Reaction kinetics are influenced by permeation of hydrogen through this layer and a reaction step involving dissociated hydrogen. Reaction mechanisms are independent of Mg content. Augite, hypersthene, and hedenbergite are reduced in H2 at the same temperatures. The products are iron metal and lower iron silicates mixed throughout the mineral. Activation energy rises with calcium content. Ilmenite and fayalite are reduced with carbon deposited on partially reduced minerals via the CO disproportionation reaction. Reduction with carbon is rapid, showing the carbothermal reduction of lunar minerals is possible.
Massieon, Charles↗
A Dicationic fac -Re(bpy)(CO) 3 Cl for CO 2 Electroreduction at a Reduced Overpotential
Here, a dicationic Re bipyridine-type complex, fac-Re(6,6'-(2-((trimethylammonio)-methyl)phenyl)-2,2'-bipyridine)(CO) 3 Cl hexafluorophosphate (1 2+ ), has been synthesized and its electrochemical behavior under Ar and CO 2 has been investigated. The presence of pendent tetra-alkylammonium cations induces an anodic shift in the electrocatalytic potential for CO 2 reduction relative to structurally similar model complexes. The electrochemical mechanisms in anhydrous CH 3 CN and in the presence of weak acids (water or trifluoroethanol) have been analyzed using cyclic voltammetry assisted by infrared spectroelectrochemistry and theoretical calculations. The dication enables catalysis at a diminished potential through coulombic stabilization of the doubly reduced pentacoordinate species, its CO 2 adduct, the hydroxide anion, and the conjugate base formed during acid-assisted C-OH bond cleavage of the metallocarboxylic acid to the metallocarbonyl and H 2 O. The major reduction product is CO, but in the presence of trifluoroethanol, formate is also produced with 14% Faradaic efficiency.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Export of Organic Carbon from Reduced Fine-Grained Zones Governs Biogeochemical Reactivity in a Simulated Aquifer
Not Available
54 ENVIRONMENTAL SCIENCES↗
Covalent Functionalization of Silicon with Plasma-Grown “Fuzzy” Graphene: Robust Aqueous Photoelectrodes for CO 2 Reduction by Molecular Catalysts
Carbon electrodes are ideal for electrochemistry with molecular catalysts, exhibiting facile charge transfer and good stability. Yet for solar-driven catalysis with semiconductor light absorbers, stable semiconductor/carbon interfaces can be difficult to achieve, and carbon’s high optical extinction means it can only be used in ultrathin layers. Here, we demonstrate a plasma-enhanced chemical vapor deposition process that achieves well-controlled deposition of out-of-plane “fuzzy” graphene (FG) on thermally oxidized Si substrates. The resulting Si|FG interfaces possess a silicon oxycarbide (SiOC) interfacial layer, implying covalent bonding between Si and the FG film that is consistent with the mechanical robustness observed from the films. The FG layer is uniform and tunable in thickness and optical transparency by deposition time. Using p-type Si|FG substrates, noncovalent immobilization of cobalt phthalocyanine (CoPc) molecular catalysts was employed for the photoelectrochemical reduction of CO 2 in aqueous solution. The Si|FG|CoPc photocathodes exhibited good catalytic activity, yielding a current density of ∼1 mA/cm 2 , Faradaic efficiency for CO of ∼70% (balance H 2 ), and stable photocurrent for at least 30 h at −1.5 V vs Ag/AgCl under 1-sun illumination. Furthermore, the results suggest that plasma-deposited FG is a robust carbon electrode for molecular catalysts and suitable for further development of aqueous-stable Si photocathodes for CO 2 reduction.
CO2 reduction↗
2023 Project Peer Review Report
The Bioenergy Technologies Office (BETO) within the U.S. Department of Energy’s Office of Energy Efficiency and Renewable Energy supports the research, development, and demonstration (RD&D) of technologies aimed at mobilizing domestic renewable carbon resources for the reduction of greenhouse gas emissions across the U.S. economy. BETO systematically prioritizes RD&D into technology opportunities across a range of emerging scientific breakthroughs and technology readiness levels in the subprogram areas illustrated in Figure 1. This approach supports a diverse portfolio while developing the most promising and widely applicable technologies, testing technologies as integrated processes, and demonstrating integrated processes to support scale-up. These technologies will use a broad variety of renewable carbon resources to produce increasing volumes of biofuels and bioproducts. More information on BETO’s mission, goals, and strategic approaches can be found in the Bioenergy Technologies Office Multi-Year Program Plan. The biennial Peer Review process enables external stakeholders to provide feedback on the responsible use of taxpayer funding and develop recommendations for the most efficient and effective ways to accelerate the development of a bioenergy industry. This report includes the results of the Project Peer Review meeting held on April 3–7, 2023, in Denver, Colorado.
09 BIOMASS FUELS↗
Hierarchically structured MoO 2 /dopamine-derived carbon spheres as intercalation electrodes for lithium-ion batteries
A hydrogen peroxide initiated sol-gel process involving molybdenum transformation in the presence of dopamine (Dopa) hydrochloride excess produced the metastable precipitate composed of polydopamine (PDopa) spheres coated with Dopa preintercalated molybdenum oxide, (Dopa) x MoO y @PDopa. The hydrothermal treatment (HT) of the (Dopa) x MoO y @PDopa precursor resulted in the simultaneous carbonization of Dopa and molybdenum reduction generating MoO 2 nanoplatelets distributed and confined on the surface of the Dopa-derived carbon matrix (HT-MoO 2 /C). The consecutive annealing (An) of the HT-MoO 2 /C sample at 600 °C under Ar atmosphere led to the formation of MoO 2 with increased Mo oxidation state and improved structural stability (AnHT-MoO 2 /C). Annealing had also further facilitated interaction between the molybdenum-derived and Dopa-derived components resulting in the modification of the carbon matrix confirmed by Raman spectroscopy. Morphology of both materials is best described as Dopa-derived carbon spheres decorated with MoO 2 nanoplatelets. These integrated metal oxide and carbon structures were tested as electrodes for lithium-ion batteries in the potential window that corresponds to the intercalation mechanism of charge storage. The AnHT-MoO 2 /C electrode showed enhanced electrochemical activity, with an initial specific discharge capacity of 260 mAh/g and capacity retention of 67% after 50 cycles, compared to the HT-MoO 2 /C electrode which exhibited an initial specific discharge capacity of 235 mAh g –1 and capacity retention of 47% after 50 cycles. The rate capability experiments revealed that the capacity of 93 mAh/g and 120 mAh/g was delivered by the HT-MoO 2 /C and AnHT-MoO 2 /C electrodes, respectively, when the current density was increased to 100 mA/g. Here, the improved specific capacity, electrochemical stability, and rate capability achieved after annealing were attributed to higher crystallinity of MoO 2 , increased oxidation state of Mo, and formation of the tighter MoO 2 /carbon contact accompanied by the annealing assisted interaction between MoO 2 and Dopa-derived carbon.
25 ENERGY STORAGE↗
Integrating CO2 Electrolysis with Gas Fermentation to Produce Valuable Fuels and Chemicals
Many industrial activities squander CO2, decreasing process yield. We envision a future where this waste carbon is instead captured, upgraded, and valorized directly at the point of emission. Within the CO2 Reduction and Upgrading Consortium (a collaboration of seven US national laboratories and industrial partners), we are pursuing this goal by developing and de-risking new technologies for low temperature CO2 electrolysis, coupled with biological upgrading of intermediates into more valuable compounds. One such process involves electrocatalytic reduction of CO2 to generate carbon monoxide (CO). As both a carbon and energy source, CO represents an attractive feedstock for microbial upgrading by certain syngas-fermenting species, such as the autotrophic bacterium Clostridium autoethanogenum. Our team has developed new genetic tools and optimized cultivation techniques to enhance C. autoethanogenum as a platform host for the biological conversion of syngas into value-added products. For example, we have created novel CRISPR-based genetic engineering techniques to build new, genome-reduced, platform strains of C. autoethanogenum with improved growth rates. Further, we ve introduced heterologous biochemical pathways into C. autoethanogenum to enable the production of high-value compounds from syngas, such as the isoprenoid precursor mevalonic acid. With the tools of electrochemistry and synthetic biology, there is virtually no limit to the spectrum of products that could be sustainably manufactured from CO2.
09 BIOMASS FUELS↗
Warming decreases desert ecosystem functioning by altering biocrusts in drylands
Warming and precipitation fluctuations are changing desert ecosystems in global drylands. However, the effects of climate change on keystone species such as cryptogamic biocrust in drylands remain relatively under-investigated, even though biocrusts play a vital role in desert ecosystems. Here we conducted a long-term experiment (14 years) to simulate the responses of two main types of biocrusts to warming coupled with reduction in precipitation that was achieved by open-top chambers (OTCs) to simulate the predicted warming and precipitation decreasing under climate change scenario. We also conduct a structural analysis to evaluate the resulting changes in desert ecosystem functioning (carbon and nitrogen cycling). Neither warming and corresponding rainfall reduction treatments had a negative effect on lichen species richness, but both treatments reduced lichen cover and biomass. The negative effects of warming on moss-dominated crusts were much greater than those on lichen-dominated crusts. Although mosses and lichens had varying degree responses to warming, the loss of mosses and decreased lichen cover and biomass, as well as the shortening of the wet time, resulted in a reduction in carbon and nitrogen fixation, soil enzyme activity and water-holding capacity of biocrusts and topsoil. These impacts collectively change the water balance of drylands and weaken the hydrological and biogeochemical function of biocrusts. Synthesis and applications: Results from this long-term experiment suggest that the ecosystem C and N cycling and water balance of global drylands may be highly impacted by climate change, in part because of the response of biocrusts, which contribute an important implication for both dryland restoration and earth system dynamics.
54 ENVIRONMENTAL SCIENCES↗
Acetyl-CoA Synthesis Through a Bicyclic Carbon-Fixing Pathway in Gas-Fermenting Bacteria
Gas-fermenting acetogens can upgrade one-carbon (C1) compounds (such as CO2 and CO) to the two-carbon (C2) metabolite acetyl coenzyme A (CoA) and convert sugar feedstocks to acetyl-CoA with minimal CO2 emissions. Fulfilling the biosynthetic potential of these microbes requires overcoming challenges in pathway engineering. Here we design a synthetic acetyl-CoA bi-cycle-in addition to the natural carbon-fixing pathways-for C2 metabolite synthesis. This pathway produces an acetyl-CoA by fixation of two CO2 equivalents via three functional modules acting in sequence: carbon fixation, gluconeogenesis and non-oxidative glycolysis. The pathway was examined by in silico thermodynamic and kinetic analyses. The prototypic pathway was implemented in a syngas-fermenting organism, Clostridium ljungdahlii DSM 13528, by expressing a heterologous phosphoketolase that can work with other native enzymes in the host acetogen. The carbon conversion pathway is possible under various growth conditions and is independent of the Wood-Ljungdahl pathway for the valorization of H2 and CO2. This study reports the improvement of carbon conversion using a reductive acetyl-CoA bi-cycle and the potential impact of redox homoeostasis in the acetogenic host for industrial applications of gas fermentation.
Acetyl-CoA↗
Research on processes for utilization of lunar resources Final report, 22 Apr. 1963 - 15 Jul. 1965
Laboratory apparatus designed, fabricated, and operated for studying catalytic reduction of igneous rock with carbon, hydrogen, and methane, and of carbon monoxide with hydrogen
REDUCTION↗