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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 613 records · Page 34
All sourcesNASA NTRSDOE OSTI
NASA NTRS1989

Sulfate reduction and oxic respiration in marine sediments: implications for organic carbon preservation in euxinic environments

Compilations have been made of sulfate reduction rates and oxic respiration rates over the entire range of marine sedimentation rates, and sedimentary environments, including several euxinic sites. These data show, consistent with the findings of Jorgensen (1982, Nature, 296, 643-645), that sulfate reduction and oxic respiration oxidize equal amounts of organic carbon in nearshore sediments. As sedimentation rates decrease, oxic respiration, becomes progressively more important, and in deep-sea sediments 100-1000 times more organic carbon is oxidized by oxic respiration than by sulfate reduction. By contrast, nearly as much organic carbon is oxidized by sulfate reduction in euxinic sediments as is oxidized by the sum of sulfate reduction and oxic respiration in normal marine sediments of similar deposition rate. This observation appears at odds with the enhanced preservation of organic carbon observed in euxinic sediments. However, only small reductions in (depth-integrated) organic carbon decomposition rates (compared to normal marine) are required to give both high organic carbon concentrations and enhanced carbon preservation in euxinic sediments. Lower rates of organic carbon decomposition (if only by subtle amounts) are explained by the diminished ability of anaerobic bacteria to oxidize the full suite of sedimentary organic compounds.

NASA Center ARC↗
NASA NTRS1999

Energetics and kinetics of the prebiotic synthesis of simple organic acids and amino acids with the FeS-H2S/FeS2 redox couple as reductant

The thermodynamics of the FeS-H2S/FeS2 redox couple and a select number of reactions critical to the synthesis of simple carboxylic acids and amino acids have been evaluated as a function of temperature. This thermodynamic evaluation shows that the reducing power of the FeS-H2S/FeS2 redox couple decreases drastically with temperature. By contrast the equilibria describing the reduction of CO2 and the formation of simple carboxylic acids and amino acids require an increasingly higher reducing power with temperature. Given these two opposite trends, the thermodynamic driving force for CO2 reduction and amino acid formation with the FeS-H2S/FeS2 redox couple as reductant diminishes with increasing temperature. An evaluation of the mechanism of CO2 reduction by the FeS-H2S/FeS2 couple suggests that the electron transfer from pyrrhotite to CO2 is hindered by a high activation energy, even though the overall reaction is thermodynamically favorable. By comparison the electron transfer from pyrrhotite to either CS2, CO, or HCOOH are far more facile. This theoretical analysis explains the results of experimental work by Keefe et al. (1995), Heinen and Lauwers (1996) and Huber and Wachtershauser (1997). The implication is that a reaction sequence involving the reduction of CO2 with the FeS-H2S/FeS2 couple as reductant is unlikely to initiate a proposed prebiotic carbon fixation cycle (Wachtershauser, 1988b; 1990b, 1990a, 1992, 1993).

Non-NASA Center↗
NASA NTRS2013

Multi-Group Reductions of LTE Air Plasma Radiative Transfer in Cylindrical Geometries

Air plasma radiation in Local Thermodynamic Equilibrium (LTE) within cylindrical geometries is studied with an application towards modeling the radiative transfer inside arc-constrictors, a central component of constricted-arc arc jets. A detailed database of spectral absorption coefficients for LTE air is formulated using the NEQAIR code developed at NASA Ames Research Center. The database stores calculated absorption coefficients for 1,051,755 wavelengths between 0.04 μm and 200 μm over a wide temperature (500K to 15 000K) and pressure (0.1 atm to 10.0 atm) range. The multi-group method for spectral reduction is studied by generating a range of reductions including pure binning and banding reductions from the detailed absorption coefficient database. The accuracy of each reduction is compared to line-by-line calculations for cylindrical temperature profiles resembling typical profiles found in arc-constrictors. It is found that a reduction of only 1000 groups is sufficient to accurately model the LTE air radiation over a large temperature and pressure range. In addition to the reduction comparison, the cylindrical-slab formulation is compared with the finite-volume method for the numerical integration of the radiative flux inside cylinders with varying length. It is determined that cylindrical-slabs can be used to accurately model most arc-constrictors due to their high length to radius ratios.

Reductions↗
DOE OSTI2021

Retrospective analysis of the U.S. corn ethanol industry for 2005–2019: implications for greenhouse gas emission reductions

Since 2000, corn ethanol production in the USA has increased significantly – from 1.6 to 15 billion gallons (6.1 to 57 billion liters) – due to supportive biofuel policies. In this study, we conduct a retrospective analysis of the changes in US corn ethanol greenhouse gas emission intensity, sometimes known as carbon intensity (CI), over the 15 years from 2005 to 2019. Our analysis shows a significant decrease in CI: from 58 to 45 gCO 2 e/MJ of corn ethanol (a 23% reduction). This is due to several factors. Corn grain yield has increased continuously, reaching 168 bushels/acre (10.5 metric tons/ha, a 15% increase) while fertilizer inputs per acre have remained constant, resulting in decreased intensities of fertilizer inputs (e.g., 7% and 18% reduction in nitrogen and potash use per bushel of corn grain harvested, respectively). A 6.5% increase in ethanol yield, from 2.70 to 2.86 gal/bushel corn (0.402 to 0.427 L kg -1 corn), and a 24% reduction in ethanol plant energy use, from 32 000 to 25 000 Btu/gal ethanol (9.0 to 6.9 MJ L -1 ethanol) also helped reduce the CI. The total GHG emission reduction benefits through the reduction in the CI and increased ethanol production volume are estimated at 140 million metric tons (MMT) from 2005 to 2019 in the ethanol industry. Displacement of petroleum gasoline by corn ethanol in the transportation fuel market resulted in a total GHG emission reduction benefit of 544 MMT CO 2 e during the period 2005 to 2019.

09 BIOMASS FUELS↗
DOE OSTI2018

Cr(VI) reduction and physiological toxicity are impacted by resource ratio in Desulfovibrio vulgaris

Desulfovibrio spp. are capable of heavy metal reduction and are well-studied systems for understanding metal fate and transport in anaerobic environments. Desulfovibrio vulgaris Hildenborough was grown under environmentally relevant conditions (i.e., temperature, nutrient limitation) to elucidate the impacts on Cr(VI) reduction on cellular physiology. Growth at 20 °C was slower than 30 °C and the presence of 50 μM Cr(VI) caused extended lag times for all conditions, but once growth resumed the growth rate was similar to that without Cr(VI). Cr(VI) reduction rates were greatly diminished at 20 °C for both 50 and 100 μM Cr(VI), particularly for the electron acceptor limited (EAL) condition in which Cr(VI) reduction was much slower, the growth lag much longer (200 h), and viability decreased compared to balanced (BAL) and electron donor limited (EDL) conditions. When sulfate levels were increased in the presence of Cr(VI), cellular responses improved via a shorter lag time to growth. Similar results were observed between the different resource (donor/acceptor) ratio conditions when the sulfate levels were normalized (10 mM), and these results indicated that resource ratio (donor/acceptor) impacted D. vulgaris response to Cr(VI) and not merely sulfate limitation. The results suggest that temperature and resource ratios greatly impacted the extent of Cr(VI) toxicity, Cr(VI) reduction, and the subsequent cellular health via Cr(VI) influx and overall metabolic rate. The results also emphasized the need to perform experiments at lower temperatures with nutrient limitation to make accurate predictions of heavy metal reduction rates as well as physiological states in the environment.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2018

Mechanism of Low-Temperature Reduction Degradation of Alumina-Containing Hematite Solid Solution Below 550 °C

Low-temperature reduction degradation (LTRD) of sinter has an adverse effect on blast furnace permeability, and it is mainly caused by the stress produced in the reduction process of hematite. This stress is strongly influenced by alumina dissolved in hematite crystal lattice. In this work, the experiments were conducted to investigate the effect of alumina dissolved in hematite solid solution (H{sub ss}) on LTRD by reducing H{sub ss} below 550 °C. Thermogravimetric analysis (TGA), X-ray diffraction (XRD), and optical microscope have been used to characterize the mass change and mineral change of samples, respectively. Jade software has been used to calculate the micro strain in magnetite for quantitatively studying the change of strain in reducing process. The results show that alumina was unfavorable to the reduction of H{sub ss} on thermodynamics, and the starting reduction temperature of H{sub ss} containing 6.0 mol pct alumina was 28 °C higher than that of pure hematite. According to the calculation on kinetics, the generation rate of stress was accelerated by dissolving alumina into hematite crystal lattice. The apparent activation energy of reduction reaction lowered from 47.89 to 28.07 kJ/mol with the increase of alumina content from 0.0 to 6.0 mol pct. The addition of alumina also increased the stress in the reduction products, and this stress was released in the form of LTRD.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Fe(II)- and Sulfide-Facilitated Reduction of 99Tc(VII)O4- in Microbially Reduced Hyporheic Zone Sediments

Redox-reactive, biogeochemical phases generated by reductive microbial activity in hyporheic zone sediments from a dynamic groundwater-river interaction zone were evaluated for their ability to reduce soluble pertechnetate [99Tc(VII)O4-] to less soluble Tc(IV). The sediments were bioreduced by indigenous microorganisms that were stimulated by organic substrate addition in synthetic groundwater with or without sulfate. In most treatments, 20 µmol L-1 initial aqueous Tc(VII) was reduced to near or below detection (3.82×10-9 mol L-1) over periods of days to months in suspensions of variable solids concentrations. Native sediments containing significant lithogenic Fe(II) in various phases were, in contrast, unreactive with Tc(VII). The reduction rates in the bioreduced sediments increased with increases in sediment mass, in proportion to weak acid-extractable Fe(II) and sediment-associated sulfide (AVS). The rate of Tc(VII) reduction was first order with respect to both aqueous Tc(VII) concentration and sediment mass, but correlations between specific reductant concentrations and reaction rate were not found. X-ray microprobe measurements revealed a strong correlation between Tc hot spots and Fe-containing mineral particles in the sediment. However, only a portion of Fe-containing particles were Tc-hosts. The Tc-hot spots displayed a chemical signature (by EDXRF) similar to pyroxene. The application of autoradiography and electron microprobe allowed further isolation of Tc-containing particles that were invariably found to be ca 100 µm aggregates of primary mineral material embedded within a fine-grained phyllosilicate matrix. EXAFS spectroscopy revealed that the Tc(IV) within these were a combination of a Tc(IV)O2-like phase and Tc(IV)-Fe surface clusters, with a significant fraction of a TcSx-like phase in sediments incubated with SO42-. AVS was implicated as a more selective reductant at low solids concentration even though its concentration was below that required for stoichiometric reduction of Tc(VII). These results demonstrate that composite mineral aggregates may be redox reaction centers in coarse-textured hyporheic zone sediments regardless of the dominant anoxic biogeochemical processes.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2014

Reduction And Immobilization Of Hexavalent Chromium By Microbially Reduced Fe-bearing Clay Minerals

Hexavalent chromium (Cr6+) is a major contaminant in the environment. As a redox-sensitive element, the fate and toxicity of chromium is controlled by reduction-oxidation (redox) reactions. Previous research has shown the ability of structural Fe(II) in naturally present and chemically reduced clay minerals to reduce Cr6+ to Cr(III) as a way of immobilization and detoxification. However, it is still poorly known whether or not structural Fe(II) in biologically reduced clay minerals exhibits a similar reactivity and if so, what the kinetics and mechanisms of Cr6+ reduction are. The objective of this study was to determine the kinetics and possible mechanisms of Cr6+ reduction by structural Fe(II) in microbially reduced clay minerals and the nature of reduced Cr(III). Structural Fe(III) in nontronite (NAu-2), montmorillonite (SWy-2), chlorite (CCa-2), and clay-rich sediments from the Ringold Formation of the Hanford site of Washington State, USA was first bioreduced to Fe(II) by an iron-reducing bacterium Geobacter sulfurreducens with acetate as the sole electron donor and anthraquinone-2,6-disulfate (AQDS) as electron shuttle in synthetic groundwater (pH 7). Biogenic Fe(II) was then used to reduce aqueous Cr6+ at three different temperatures, 10°, 20°, and 30°C, in order to determine the temperature dependence of the redox reaction between Cr6+ and clay-Fe(II). The results showed that nontronite and montmorillonite were most effective in reducing aqueous Cr6+ at all three temperatures. In contrast, most Fe(II) in chlorite was not reactive towards Cr6+ reduction at 10°C, though at 30°C there was some reduction. For all the clay minerals, the ratio of total Fe(II) oxidized to Cr6+ reduced was close to the expected stoichiometric value of 3. Characterization of the Cr-clay reaction product with scanning electron microscopy with focused ion beam and transmission electron microscopy with electron energy loss spectroscopy revealed that reduced chromium was possibly in the form of sub-nanometer Cr2O3 in association with residual clay minerals as micro-aggregates. This textural association was expected to minimize the chance of Cr(III) reoxidation upon exposure to oxidants. These results are important for our understanding of how various clay minerals may be used to reductively immobilize the heavy metal contaminant Cr in the environment.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2022

Black carbon emissions and reduction potential in China: 2015–2050

Black carbon is a product of the incomplete combustion of carbonaceous fuels and has significant adverse effects on climate change, air quality, and human health. China has been a major contributor to global anthropogenic black carbon emissions. This study develops a black carbon inventory in China, using 2015 as the base year, and projects annual black carbon emissions in China for the period 2016–2050, under two scenarios: a Reference scenario and an Accelerated Reduction scenario. The study estimates that the total black carbon emissions in China in 2015 were 1100 thousand tons (kt), with residential use being the biggest contributor, accounting for more than half of the total black carbon emissions, followed by coke production, industry, agricultural waste burning, and transportation. This study then projects the total black carbon emissions in China in 2050 to be 278 kt in the Reference scenario and 86 kt in the Accelerated Reduction Scenario. Compared to the Reference scenario, the Accelerated Reduction scenario will achieve much faster and deeper black carbon reductions in all the sectors. The dramatic reductions can be attributed to the fuel switching in the residential sector, faster implementation of high-efficiency emission control measures in the industry, transportation, and coke production sectors, and faster phase-out of agricultural waste open burning. This analysis reveals the high potential of black carbon emission reductions across multiple sectors in China through the next thirty years.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Polysulfide reduction and Li 2 S phase formation in the presence of lithium metal and solid electrolyte interphase layer

Lithium sulfur battery is an attractive next generation technology that can meet many demands of modern society. Unfortunately, the lithium sulfur battery faces unique issues related to the polysulfide shuttle effect, that is due to reduction products dissolving in the electrolyte and their subsequent reduction on the lithium metal electrode. This adds further problems to the already challenging needs of understanding and engineering a solid electrolyte interphase (SEI) layer with desired properties. One of the most important SEI properties is its passivation of lithium metal which is critically important to the overall battery performance. Passivation is difficult to measure experimentally without the influence of many factors. This study reports an investigation of the reduction of the intermediate Li 2 S 8 over lithium already passivated with Li 2 O, Li 2 CO 3 , LiOH, LiF and Li 2 S along with exploration of Li 2 S 8 reduction over pristine lithium nanoclusters using first principles computational models. Significant formation of Li 2 S phase nucleation is found to stabilize the reduction products of the Li 2 S 8 . Here, the formation of Li 2 S is explored in-depth with lithium nanocluster-based models determining a 2 V potential increase for the reduction of polysulfides due to the formation of Li 2 S. This investigation demonstrates passivation effects of important SEI components including Li 2 S.

25 ENERGY STORAGE↗
DOE OSTI2016

Fluoroethylene Carbonate and Vinylene Carbonate Reduction: Understanding Lithium-Ion Battery Electrolyte Additives and Solid Electrolyte Interphase Formation

In this work, we have synthesized the products of fluoroethylene carbonate (FEC) and vinylene carbonate (VC) via lithium naphthalenide reduction. By analyzing the resulting solid precipitates and gas evolution, our results confirm that both FEC and VC decomposition products include HCO 2 Li, Li 2 C 2 O 4 , Li 2 CO 3 , and polymerized VC. For FEC, our experimental data supports a reduction mechanism where FEC reduces to form VC and LiF, followed by subsequent VC reduction. In the FEC reduction product, HCO 2 Li, Li 2 C 2 O 4 , and Li 2 CO 3 were found in smaller quantities than in the VC reduction product, with no additional fluorine environments being detected by solid-state nuclear magnetic resonance or X-ray photoelectron spectroscopy analysis. With these additives being practically used in higher (FEC) and lower (VC) concentrations in the base electrolytes of lithium-ion batteries, our results suggest that the different relative ratios of the inorganic and organic reduction products formed by their decomposition may be relevant to the chemical composition and morphology of the solid electrolyte interphase formed in their presence.

36 MATERIALS SCIENCE↗
DOE OSTI2025

A Rhenium Bis -tetramethylphenanthroline Catalyst for CO 2 Reduction to Formate

Catalytic CO 2 reduction reactions featuring high selectivity toward formate are relatively rare. In some homogeneous molecular CO 2 -reducing electrocatalysis, using triethylamine (TEA) and isopropanol (IPA) as additives improves catalytic performance in producing formate. In this paper, we investigate whether the rhenium(I) bis-diimine dicarbonyl complexes, cis-[Re(N^N) 2 (CO) 2 ] + , where N^N is 2,2’-bipyridine ([1] + ) or 3,4,7,8-tetramethyl-1,10-phenanthroline ([2] + ), are capable of electrocatalytically reducing CO 2 to formate in acetonitrile containing TEA and IPA. Catalyst [1] + was ineffective at CO 2 reduction, yielding formate quantities comparable to those produced in experiments without the catalyst. Catalyst [2] + , however, is a promising electrocatalyst for the CO 2 reduction reaction in the presence of TEA and IPA, with formate being produced in millimolar concentrations (10.5 mM), as detected by 1 H NMR spectroscopy after 6 h electrolysis (formate Faradaic efficiency = 11%, with the major balance going to H 2 ). Upon more detailed examination, [2] + exhibited a turnover frequency (TOF) of 12 s –1 for formate, comparable to other leading molecular catalysts that competently execute this reduction. Combinations of spectroscopy, electrochemistry, and theory were used to better understand the mechanism of CO 2 reduction by [2] + . Fourier transform infrared spectroelectrochemical (FTIR-SEC) data provided no evidence for CO ligand dissociation or substitution upon one- and two-electron reduction of [2] + , suggesting that a mechanism distinct from one that is metal-hydride-based is operative in catalysis. Computational studies guide mechanistic investigations toward the proposed formation of a hydrophenanthroline-based intermediate responsible for hydride transfer to CO 2 and electrocatalytic formate production from [2] + .

Beverages↗
DOE OSTI2015

99Tc(VII) Retardation, Reduction, and Redox Rate Scaling in Naturally Reduced Sediments

Abstract: An experimental and modeling study was conducted to investigate pertechnetate (Tc(VII)) retardation, reduction, and rate scaling in three sediments from Ringold formation at U.S. Department of Energy’s Hanford site, where 99Tc is a major contaminant in groundwater. Tc(VII) was reduced in all the sediments in both batch reactors and diffusion columns, with a faster rate in a sediment containing a higher concentration of HCl-extractable Fe(II). Tc(VII) migration in the diffusion columns was reductively retarded with retardation degrees correlated with Tc(VII) reduction rates. The reduction rates were faster in the diffusion columns than those in the batch reactors, apparently influenced by the spatial distribution of redox-reactive minerals along transport paths that supplied Tc(VII). X-ray computed tomography and autoradiography were performed to identify the spatial locations of Tc(VII) reduction and transport paths in the sediments, and results generally confirmed the newly found behavior of reaction rate changes from batch to column. The results from this study implied that Tc(VII) migration can be reductively retarded at Hanford site with a retardation degree dependent on reactive Fe(II) content and its distribution in sediments. This study also demonstrated that an effective reaction rate may be faster in transport systems than that in well-mixed reactors.

Tc transport↗
DOE OSTI2015

Cool Roofs in Guangzhou, China: Outdoor Air Temperature Reductions during Heat Waves and Typical Summer Conditions

In this work, we simulate temperature reductions during heat-wave events and during typical summer conditions from the installation of highly reflective "cool" roofs in the Chinese megacity of Guangzhou. We simulate temperature reductions during six of the strongest historical heat-wave events over the past decade, finding average urban midday temperature reductions of 1.2 °C. In comparison, we simulate 25 typical summer weeks between 2004 and 2008, finding average urban midday temperature reductions of 0.8 °C, indicating that air temperature sensitivity to urban albedo in Guangzhou varies with meteorological conditions. We find that roughly three-fourths of the variance in air temperature reductions across all episodes can be accounted for by a linear regression, including only three basic properties related to the meteorological conditions: mean daytime temperature, humidity, and ventilation to the greater Guangzhou urban area. While these results highlight the potential for cool roofs to mitigate peak temperatures during heat waves, the temperature reductions reported here are based on the upper bound case, which increases albedos of all roofs (but does not modify road albedo or wall albedo).

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2019

Kinetics and Mechanism of Nickel Oxide Reduction by Methane

Nickel oxide reduction by methane is of particular importance in catalysis, extractive metallurgy, and clean power generation technologies. Despite extensive investigations of the NiO + CH 4 reaction, many questions remain about its kinetics and molecular and structural transformation mechanisms. We discuss the reduction kinetics of bulk polycrystalline NiO by CH 4 using a new calorimetric method. The technique permits rapid, controllable heating of the NiO/Ni wires and continuous data (electrical power, the electrical resistivity of the wire, and temperature) acquisition with a frequency of 10 kHz. The method also allows arresting and preservation of the structure of the sample by programmed termination of electric power in thin specimens. This approach, coupled with ex situ electron microscopy, allows determination of the reaction rate and tracking of the ongoing structural transformations. The mechanism of NiO reduction by methane is suggested based on direct correlations between reaction kinetics and the observed microstructure transformations. The kinetic data treatment revealed that the nucleation-growth model describes the reaction kinetics. Ex situ microscopy observations of reacted specimens showed that the first nuclei rapidly accelerate the process. Pore formation occurs at the nucleation sites, and the porous structure then quickly grows into the bulk NiO. The second type of reduced Ni microstructure, compact layer, can be observed only on the outer surface of the wire. Based on kinetic data and microstructural observations, a mechanism of reduction was suggested according to which porous microstructure forms predominantly by NiO reduction with carbon. The compact layer observed on the outer surface of the wire forms through the diffusion-controlled hydrogen reduction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Mechanism of photocatalytic reduction of CO 2 by Re(bpy)(CO) 3 Cl from differences in carbon isotope discrimination

The rhenium complex Re(bpy)(CO) 3 Cl (1, bpy = 2,2'-bipyridine) catalyzes CO 2 reduction to CO in mixtures containing triethanolamine (TEOA) as a sacrificial reductant. The mechanism of this reaction under photocatalytic conditions remains to be fully characterized. Here, we report the competitive carbon kinetic isotope effects ( 13 C KIEs) on photocatalytic CO 2 reduction by 1 and analyze the results of experimental measurements by comparing with computed KIEs via density functional theory (DFT) calculations as a means of formulating a chemical mechanism and illustrating the utility of this approach. The 13 C KIEs, k( 12 C)/k( 13 C), in acetonitrile (ACN) and dimethylformamide (DMF) were determined to be 1.0718 ± 0.0036 and 1.0685 ± 0.0075, respectively. When [Ru(bpy) 3 ]Cl 2 is added to the reaction mixture in acetonitrile as a photosensitizer, the reduction of CO 2 exhibited a 13 C KIE = 1.0703 ± 0.0043. These values are consistent with the calculated isotope effect of CO 2 binding to the one-electron reduced [ReI(bpy• – )(CO) 3 ] species. The findings reported here provide strong evidence that the reactions in the two different solvents have the same first irreversible step and proceed with similar reactive intermediates upon reduction. Theoretically, we found that the major contribution for the large 13 C isotope effects comes from a dominant zero-point energy (ZPE) term. Lastly, these results lay the groundwork for combined experimental and theoretical approaches for analysis of competitive isotope effects toward understanding CO 2 reduction catalyzed by other complexes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Evaluating the Thermodynamics of Electrocatalytic N 2 Reduction in Acetonitrile

The synthesis of ammonia by proton-coupled electroreduction of dinitrogen (N2) represents a sustainable alternative to currently practiced hydrogenation methods. Developments in this area require knowledge of the standard reduction potentials that describe the thermodynamics of N2 reduction. The first collection of N2 reduction standard potentials in organic solvent are reported here. The potentials for reduction of N2 to ammonia (NH3), hydrazine (N2H4), and diazene (N2H2) in acetonitrile (MeCN) solution are derived using thermochemical cycles. Ammonia is the thermodynamically favored product, with a 0.43 V difference between NH3 and N2H4 and a 1.26 V difference between NH3 and N2H2. The thermodynamics for reduction of N2 to the protonated products ammonium (NH4+) and hydrazinium (N2H5+) under strongly acidic conditions are also presented. Comparison with previously determined values for the H+/H2 potential in MeCN reveals a 63 mV thermodynamic preference for N2 reduction to NH3 over H2 production. Combined with knowledge of the kinetics of electrode-catalyzed H2 evolution, a wide working region is identified to guide future electrocatalytic studies.

Lindley, Brian M.↗
DOE OSTI2024

Catalytic Reduction of Cyanide to Ammonia and Methane at a Mononuclear Fe Site

Nitrogenase enzymes catalyze nitrogen reduction (N 2 R) to ammonia and also the reduction of non-native substrates, including the 7H + /6e – reduction of cyanide to CH 4 and NH 3 . CN – and N 2 are isoelectronic, and it is hence fascinating to compare the mechanisms of synthetic Fe catalysts capable of both CN – and N 2 reduction. Here, we describe the catalytic reduction of CN – to NH 3 and CH 4 by a highly selective (P 3 Si )Fe(CN) catalyst (P 3 Si represents a tris(phosphine)silyl ligand). Catalysis is driven in the presence of excess acid ([Ph 2 NH 2 ]OTf) and reductant ((C 6 H 6 ) 2 Cr), with turnover as high as 73 demonstrated.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗