Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “carbonyls”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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

At least 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Understanding the Competition between Alcohol Formation and Dimerization during Electrochemical Reduction of Aromatic Carbonyl Compounds

The electrochemical reductive dimerization of small aromatic carbonyl compounds derived from lignocellulosic biomass is a crucial C−C coupling reaction for upgrading small molecules to longchain hydrocarbons, particularly in the synthesis of drop-in sustainable aviation fuels. Although other electrochemical reduction reactions of these reactants (i.e., hydrogenation and hydrogenolysis) have undergone extensive mechanistic investigation, the understanding of dimerization remains relatively underdeveloped. Most importantly, there is a lack of understanding of the selectivity-determining step between dimerization and monomer reduction and critical factors that can affect this step. In this study, we provide a comprehensive mechanistic model to explain the competition between dimerization and monomer reduction of benzaldehyde under various conditions. Our model proposes that the selectivity between dimerization and monomer reduction depends on the competition between desorption of a ketyl radical from the electrode, necessary for dimerization, and further reduction of the ketyl radical to an alcohol on the electrode by proton-coupled electron transfer (PCET). Computationally comparing the adsorption/desorption energy and PCET activation barrier energy is challenging because conventional DFT calculations substantially underestimate the PCET kinetic barriers. In this study, we employed constrained DFTbased configuration interaction (CDFT-CI) to obtain a reliable comparison of these energies. Our mechanistic model was tested and supported by experimental results obtained with four electrodes (Cu, Pb, Bi, graphite), three pH conditions (acidic, neutral, basic), and three potentials. Our study offers a coherent mechanistic foundation that can explain how each of these conditions impacts the desorption and PCET processes and the selectivities for dimerization and alcohol production.

09 BIOMASS FUELS↗
DOE OSTI2020

Seasonal Evolution of Canopy Stomatal Conductance for a Prairie and Maize Field in the Midwestern United States from Continuous Carbonyl Sulfide Fluxes

Abstract There are inherent challenges in scaling stomatal conductance (g ) from leaf to canopy particularly over seasonal time scales when species distribution and canopy structure evolve. We address this gap using carbonyl sulfide (OCS) and CO fluxes from a predominantly C3 prairie and C4 maize field in the midwestern United States. The g derived from OCS fluxes captured a transition in the stomatal limitation on gross primary productivity (GPP) through the growing season as well as seasonally persistent g dynamics such as temperature optimum and a positive response of nighttime g to vapor pressure deficit. Near the termination of the prairie growing season, we observed a decrease in the relative OCS to CO flux that we hypothesize emerged from a rising contribution of C4 plants to productivity. The results show how plot‐scale OCS and CO fluxes can be used as a trace gas diagnostic for transitions in the limiting factors for community GPP.

Berkelhammer, M.↗
DOE OSTI2020

Anthropogenic Impacts on Atmospheric Carbonyl Sulfide Since the 19th Century Inferred From Polar Firn Air and Ice Core Measurements

Carbonyl sulfide (COS) was measured in firn air collected during seven different field campaigns carried out at four different sites in Greenland and Antarctica between 2001 and 2015. A Bayesian probabilistic statistical model is used to conduct multisite inversions and to reconstruct separate atmospheric histories for Greenland and Antarctica. The firn air inversions cover most of the 20th century over Greenland and extend back to the 19th century over Antarctica. The derived atmospheric histories are consistent with independent surface air time series data from the corresponding sites and the Antarctic ice core COS records during periods of overlap. Atmospheric COS levels began to increase over preindustrial levels starting in the 19th century, and the increase continued for much of the 20th century. Atmospheric COS peaked at higher than present-day levels around 1975 CE over Greenland and around 1987 CE over Antarctica. An atmosphere/surface ocean box model is used to investigate the possible causes of observed variability. The results suggest that changes in the magnitude and location of anthropogenic sources have had a strong influence on the observed atmospheric COS variability.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Quantifying Northern High Latitude Gross Primary Productivity (GPP) Using Carbonyl Sulfide (OCS)

The northern high latitude (NHL, 40°N to 90°N) is where the second peak region of gross primary productivity (GPP) other than the tropics. The summer NHL GPP is about 80% of the tropical peak, but both regions are still highly uncertain. Carbonyl sulfide (OCS) provides an important proxy for photosynthetic carbon uptake. Here we optimize the OCS plant uptake fluxes across the NHL by fitting atmospheric concentration simulation with the GEOS-CHEM global transport model to the aircraft profiles acquired over Alaska during NASA's Carbon in Arctic Reservoirs Vulnerability Experiment (2012–2015). We use the empirical biome-specific linear relationship between OCS plant uptake flux and GPP to derive the six plant uptake OCS fluxes from different GPP data. Such GPP-based fluxes are used to drive the concentration simulations. We evaluate the simulations against the independent observations at two ground sites of Alaska. The optimized OCS fluxes suggest the NHL plant uptake OCS flux of -247 Gg S year -1 , about 25% stronger than the ensemble mean of the six GPP-based OCS fluxes. GPP-based OCS fluxes systematically underestimate the peak growing season across the NHL, while a subset of models predict early start of season in Alaska, consistent with previous studies of net ecosystem exchange. The OCS optimized GPP of 34 PgC yr -1 for NHL is also about 25% more than the ensembles mean from six GPP data. Further work is needed to fully understand the environmental and biotic drivers and quantify their rate of photosynthetic carbon uptake in Arctic ecosystems.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Remotely Sensed Carbonyl Sulfide Constrains Model Estimates of Amazon Primary Productivity

We report understanding the magnitude of tropical gross primary production (GPP) is critical for carbon cycle modeling and climate projections, but this quantity is poorly constrained at regional scales. Biospheric uptake of carbonyl sulfide (OCS) provides a promising approach to estimating regional GPP. Here, we simulate OCS concentrations driven by surface flux scenarios encompassing a wide range of GPP estimates for the Amazon basin. We compare the model output to satellite retrievals and find a regional GPP estimate of 2375 ± 914 g(C) m –2 yr –1 , consistent with previous estimates, including the TRENDY model ensemble range of 1431–3812 g(C) m –2 yr –1 .

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Soil Carbonyl Sulfide (OCS) Fluxes in Terrestrial Ecosystems: An Empirical Model

Measurements of carbonyl sulfide (OCS) enable independent estimates of regional stomatal conductance provided that non-stomatal OCS fluxes are well constrained. OCS is taken up through plant leaves, following the same pathway as CO 2 ; in contrast to CO 2 , OCS is irreversibly destroyed in plant leaves and plants do not typically exhibit OCS emissions. Ecosystem uptake of OCS can indicate changes in stomatal opening. Here we present an empirical model to assess the potential impact of soil OCS exchange, the non-Stomatal OCS exchange Empirical Model (SOCSEM, version 0). We created biome-specific response curves characterizing soil OCS exchange and restricted the model design to require only knowledge of soil moisture and surface temperature because remote sensing observations are available for these two features. Comparing the model to field-based chamber observations reveal deviations that can be attributed to missing complexity of the ground surface (having excluded litter and plants without regulated stomata), shortwave radiation, or the soil environment. For agricultural regions with known net emissions, we use remotely-sensed surface temperature data and demonstrate that data resolution can affect anticipated fluxes. We further investigate the influence of regions with unknown soil OCS responses, for example, Arctic tundra. We compare our model to a process-based and respiration-based soil OCS exchange model that has been implemented in a land surface model. Further field study of tropical and arctic ecosystems in conjunction with studies of non-stomatal surfaces in addition to soil (e.g., bryophytes) will increase confidence in applying OCS as a regional tracer for stomatal conductance.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Carbon and Water Fluxes of the Boreal Evergreen Needleleaf Forest Biome Constrained by Assimilating Ecosystem Carbonyl Sulfide Flux Observations

Gross primary production (GPP) by boreal forests is highly sensitive to environmental changes. However, GPP simulated by land surface models (LSMs) remains highly uncertain due to the lack of direct photosynthesis observations at large scales. Carbonyl sulfide (COS) has emerged as a promising proxy to improve the representation of GPP in LSMs. Because COS is absorbed by vegetation following the same diffusion pathway as CO2 during photosynthesis and not emitted back to the atmosphere, incorporating a mechanistic representation of vegetation COS uptake in LSMs allows using COS observations to refine GPP representation. Here, we perform ecosystem COS flux and GPP data assimilations to constrain the COS- and GPP-related parameters in the ORCHIDEE LSM for boreal evergreen needleleaf forests (BorENF). Assimilating ecosystem COS fluxes at Hyytiälä forest increases the simulated net ecosystem COS uptake by 14%. This increase largely results from changes in the internal conductance to COS, highlighting the need to improve the representation of COS internal diffusion and consumption. Moreover, joint assimilation of ecosystem COS flux and GPP at Hyytiälä improves the simulated latent heat flux, contrary to the GPP-only data assimilation, which fails to do so. Finally, we scaled this assimilation framework up to the boreal region and find that the joint assimilation of COS at Hyytiälä and GPP fluxes at 10 BorENF sites increases the modeled vegetation COS uptake up to 18%, but not GPP. Therefore, this study encourages the use of COS flux observations to inform GPP and latent heat flux representations in LSMs.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

Operando probing dynamic migration of copper carbonyl during electrocatalytic CO2 reduction

Single crystals and shape-controlled nanocrystals are well known to exhibit facet-dependent catalytic properties. However, few studies have investigated how those nanocrystals evolve and (de)activate during reactions, calling for the development of nanoscale time-resolved operando methods. In this context, we have designed Cu nanocubes as a model system to elucidate the underlying driving force of dynamic nanocatalyst reconstruction during the CO2 reduction reaction (CO2RR). Operando electrochemical liquid-cell scanning transmission electron microscopy (EC-STEM) and synchrotron-based X-ray spectroscopy reveal the size- and potential-dependent complete transformation from (100)-oriented Cu@Cu2O nanocubes to polycrystalline metallic Cu nanograins under CO2RR conditions. In addition, machine learning-assisted operando four-dimensional STEM reveals that large Cu nanograins derived from nanocubes form mainly crystalline domains, while their smaller counterparts are more amorphous due to faster evolution kinetics. In situ Raman spectroscopy and density functional theory calculations suggest that CO drives the ejection of single Cu atoms, resulting in few-nanometre Cu clusters and the surface migration of highly mobile copper carbonyl (Cu–CO) species. Combined, these multimodal operando methods and theoretical approaches pave the way for understanding the complex structural evolution of energy-related nanocatalysts under electrochemical conditions.

Yang, Yao↗
DOE OSTI2021

Catalyst carbonylation: a hidden, but essential, step in reaction initiation

The proliferation of increasingly useful reactions for hydrogen transfer in organic synthesis has included the introduction of many new homogeneous catalysts into the organic synthesis lexicon. Unlike the proliferation of palladium-based cross-coupling reactions in which the mechanism is generally conserved, we are learning that these emerging hydrogen transfer catalysts have a rich diversity of mechanisms for catalyst activation, speciation, C–H bond cleavage and formation, and ultimately deactivation. We find that an underappreciated commonality in the catalytic activation for some of these systems is the generation of a (carbonyl)metal group, which dominates the downstream speciation of the catalyst system. In this mini-review we highlight a few well-documented cases of this phenomenon as food for thought for those who are designing new catalytic systems to introduce into this dynamic and impactful area.

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

A nitrogen- and carbonyl-rich conjugated small-molecule organic cathode for high-performance sodium-ion batteries

Organic-based cathode materials have attracted considerable attention for sustainable Na-ion batteries due to their great promise to overcome the issues arising from the insertion of large Na + into the rigid structures of conventional transition-metal-containing inorganic electrodes. The structural flexibility as a result of weak intermolecular interactions and simple electron- and ion-storage mechanisms found in organic compounds ensure facile and reversible transport of Na ions. In order to address the general drawbacks of small-molecule organic electrodes such as material dissolution in commonly used organic electrolytes and poor electronic conductivity, we report the use of a nitrogen- and carbonyl-rich highly extended π-conjugated small molecule, hexaazatrianthranylene (HATA) embedded quinone (HATAQ), as a cathode for sodium-ion batteries. The unique hydrogen bonds between highly functionalized conjugated HATAQ molecules allow supramolecular graphite-like 2D layered arrangements in the solid state which help facilitate the structural stability during long-term cycling and promote charge transfer. The compound delivers a capacity as high as 460 mA h g -1 at 500 mA g -1 and an excellent capacity retention of 99% (~138 mA h g -1 ) after 5000 cycles at an extremely high rate of 60 A g -1 . The reaction kinetics and redox mechanism of the material have been elucidated by several characterization techniques together with density functional theory (DFT) studies. The insights gained in this work could pave the way for ultra-high-performance small-molecule organic cathodes for sustainable energy storage.

25 ENERGY STORAGE↗
DOE OSTI2021

Accelerated Aging of Fast Pyrolysis Bio-Oil Using Carbonyl Titration: Laboratory Analytical Procedure (LAP)

This laboratory analytical procedure covers the accelerated aging of fast pyrolysis bio-oils. Bio-oils undergo reactions that result in physical and chemical changes over time. These changes typically result in an increase in molecular weight, decrease in some functional groups such as carbonyls, and an increase in viscosity; additionally, the aging process often leads to phase separation. Studies have shown that accelerated aging of bio-oils using this method closely mimics room temperature aging for long periods of time (over 3 years). This procedure has been developed for the accelerated aging of fast pyrolysis bio-oils only. Fast pyrolysis bio-oils are more reactive than other bio-oils (e.g., catalytic fast pyrolysis) and undergo aging much more rapidly. Therefore, this procedure should only be used for fast pyrolysis bio-oil samples.

09 BIOMASS FUELS↗
DOE OSTI2024

Iron Carbonyl Complexes of [2.2.2]Hericene as a Rigid Tris(1,3-diene) Ligand

Hericene is an unusual hexaolefin consisting of three 1,3-diene units located on a rigid bicyclo [2.2.2]octane framework that restricts the geometrical relationships of metal atoms bonded to these olefinic units. In order to explore possible effects of this rigidity limiting metal–metal interaction in polynuclear derivatives possibly stabilizing coordinatively unsaturated species, the structures and energetics of the hericene iron carbonyl complexes (hericene)Fem(CO)n (m = 1, n = 3; m = 2, n = 6, 5; m = 3, n = 9, 8) have been investigated by density functional theory. The lowest-energy (hericene)Fem(CO)3m (m = 1, 2, 3) structures have the cavities of the hericene ligand filled with a single Fe(CO)3 moiety bonded to a 1,3-diolefin unit. Such species have been synthesized by the reaction of Fe2(CO)9 with hericene. For the (hericene)Fe2(CO)5 system, the lowest energy structures are singlet structures with an Fe(CO)3 unit bonded to a 1,3-diene unit in one hericene cavity and an Fe(CO)2 unit in another hericene cavity bonded to three C=C double bonds from two 1,3-diene units. Higher energy (hericene)Fe2(CO)5 structures include a structure in which a single hericene cavity contains a Fe2(CO)4(µ-CO) moiety with each iron atom bonded to a 1,3-diene unit. In addition, both singlet and triplet (hericene)Fe2(CO)5 structures are found in which an Fe(CO)3 moiety and an Fe(CO)2 moiety located in separate hericene cavities are each bonded to a 1,3-diene unit. The lowest-energy (hericene)Fe3(CO)8 structures have two hericene cavities containing Fe(CO)3 moieties fully bonded to 1,3-diene units and a third hericene cavity containing an Fe(CO)2 moiety fully bonded to a 1,3-diene unit.

Luo, Jinfeng↗
DOE OSTI2020

Carbonyl Sulfide (OCS): Detections in Comets C/2002 T7 (LINEAR), C/2015 ER61 (PanSTARRS), and 21P/Giacobini–Zinner and Stringent Upper Limits in 46P/Wirtanen

Carbonyl sulfide (OCS) is one of the sulfur-bearing molecules detected in different astronomical environments, including comets. The present-day sulfur chemistry in comets may reveal much about the origin of these ices and their subsequent processing history. Cometary sulfur molecules such as H{sub 2}S, H{sub 2}CS, SO{sub 2}, SO, CS, CS{sub 2}, S{sub 2}, and NS have been detected in many comets. However, OCS, the only sulfur-bearing species with fluorescence emission lines at infrared wavelengths, is under-represented in comet volatile studies, having been reported in only six comets so far. We targeted OCS with the NASA Infrared Telescope Facility in comets 46P/Wirtanen, 21P/Giacobini–Zinner, and C/2015 ER61 (PanSTARRS) in 2017–2018 using the high-resolution iSHELL spectrograph, and in C/2002 T7 (LINEAR) in 2004 using the heritage CSHELL spectrograph. In comet C/2015 ER61, the OCS abundance was similar to those measured in bright comets such as comets C/2012 S1 (ISON) and C/1996 B2 (Hyakutake), whereas in C/2002 T7 it was relatively depleted. Our OCS measurement in 21P/Giacobini–Zinner is the first definitive detection of this molecule in a Jupiter-family comet from a ground-based facility and is close to the average OCS abundance determined in comet 67P/Churyumov–Gerasimenko by the Rosetta mission. Our 3σ upper limit for comet 46P/Wirtanen is the lowest reported OCS abundance in any comet. We present production rates and mixing ratios (with respect to H{sub 2}O) for these comets and place our results in the context of comets measured to date.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2022

An approach to sulfate geoengineering with surface emissions of carbonyl sulfide

Sulfate geoengineering (SG) methods based on lower stratospheric tropical injection of sulfur dioxide (SO 2 ) have been widely discussed in recent years, focusing on the direct and indirect effects they would have on the climate system. Here a potential alternative method is discussed, where sulfur emissions are located at the surface or in the troposphere in the form of carbonyl sulfide (COS) gas. There are two time-dependent chemistry–climate model experiments designed from the years 2021 to 2055, assuming a 40 Tg-Syr -1 artificial global flux of COS, which is geographically distributed following the present-day anthropogenic COS surface emissions (SG-COS-SRF) or a 6 Tg-Syr -1 injection of COS in the tropical upper troposphere (SG-COS-TTL). The budget of COS and sulfur species is discussed, as are the effects of both SG-COS strategies on the stratospheric sulfate aerosol optical depth (~Δτ=0.080 in the years 2046–2055), aerosol effective radius (0.46 µm), surface SO x deposition (+8.9 % for SG-COS-SRF; +3.3 % for SG-COS-TTL), and tropopause radiative forcing (RF; ~-1.5 W m –2 in all-sky conditions in both SG-COS experiments). Indirect effects on ozone, methane and stratospheric water vapour are also considered, along with the COS direct contribution. According to our model results, the resulting net RF is –1.3 W m –2 , for SG-COS-SRF, and –1.5 W m –2 , for SG-COS-TTL, and it is comparable to the corresponding RF of –1.7 W m –2 obtained with a sustained injection of 4 Tg-Syr -1 in the tropical lower stratosphere in the form of SO 2 (SG-SO2, which is able to produce a comparable increase of the sulfate aerosol optical depth). Significant changes in the stratospheric ozone response are found in both SG-COS experiments with respect to SG-SO2 (~5 DU versus +1.4 DU globally). According to the model results, the resulting ultraviolet B (UVB) perturbation at the surface accounts for –4.3 % as a global and annual average (versus –2.4 % in the SG-SO2 case), with a springtime Antarctic decrease of –2.7 % (versus a +5.8 % increase in the SG-SO2 experiment). Overall, we find that an increase in COS emissions may be feasible and produce a more latitudinally uniform forcing without the need for the deployment of stratospheric aircraft. However, our assumption that the rate of COS uptake by soils and plants does not vary with increasing COS concentrations will need to be investigated in future work, and more studies are needed on the prolonged exposure effects to higher COS values in humans and ecosystems.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

Cloud processing of dimethyl sulfide (DMS) oxidation products limits sulfur dioxide (SO 2 ) and carbonyl sulfide (OCS) production in the eastern North Atlantic marine boundary layer

Dimethyl sulfide (DMS) is the major sulfur species emitted from the ocean. The gas-phase oxidation of DMS by hydroxyl radicals proceeds through the stable, soluble intermediate hydroperoxymethyl thioformate (HPMTF), eventually forming carbonyl sulfide (OCS) and sulfur dioxide (SO 2 ). Recent work has shown that HPMTF is efficiently lost to marine boundary layer (MBL) clouds, thus arresting OCS and SO 2 production and their contributions to new-particle formation and growth events. To date, no long-term field studies exist to assess the extent to which frequent cloud processing impacts the fate of HPMTF. Here, we present 6 weeks of measurements of the cloud fraction and the marine sulfur species methanethiol, DMS, and HPMTF made at the Atmospheric Radiation Measurement (ARM) research facility on Graciosa Island, Azores, Portugal. Using an observationally constrained chemical box model, we determine that cloud loss is the dominant sink of HPMTF in this region of the MBL during the study, accounting for 79 %–91 % of HPMTF loss on average. When accounting for HPMTF uptake to clouds, we calculate campaign average reductions in DMS-derived MBL SO 2 and OCS of 52 %–60 % and 80 %–92 % for the study period. Using yearly measurements of the site- and satellite-measured 3D cloud fraction and DMS climatology, we infer that HPMTF cloud loss is the dominant sink of HPMTF in the eastern North Atlantic during all seasons and occurs on timescales faster than what is prescribed in global chemical transport models. Accurately resolving this rapid loss of HPMTF to clouds has important implications for constraining drivers of MBL new-particle formation.

54 ENVIRONMENTAL SCIENCES↗