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At least 721 records · Page 40
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Influence of functional additives, fillers, and pigments on thermal and catalytic pyrolysis of polyethylene for waste plastic upcycling

Pyrolysis offers a relatively green and economical method to convert waste plastics into valuable chemicals and fuels without the need for harmful solvents, toxic chemicals, or costly high-pressure reactors. Despite its popularity among chemical upcycling technologies, industrial adoption suffers from feedstock heterogeneity, low-quality products, and catalyst deactivation. Most plastics in our daily lives are formulated with functional additives, fillers, and colorants. These additives remaining in end-of-life waste streams increase feedstock heterogeneity, creating a challenging issue in recycling plastics. Still, the potential impacts of additives on the chemical upcycling of plastics have been poorly understood. In this study, polyethylene compounded with a range of widely used additives (antioxidants, stabilizers, pigments, fillers, slip agents, and flame retardants) was subjected to both thermal pyrolysis and catalytic pyrolysis in different catalyst-to-feedstock contact modes. It showed that many inorganic additives, such as talc, kaolin, CaCO 3 , TiO 2 , carbon black, and zinc stearate, facilitated polymer decomposition during pyrolysis, increasing light hydrocarbons while also promoting aromatic and carbon residue formation. Conversely, antioxidants and stabilizers inhibited depolymerization, favoring heavier hydrocarbons. During catalytic pyrolysis with HZSM-5 zeolite, additives strongly enhanced aromatic and catalytic coke formation, especially when there was direct contact between plastics and catalysts. Although certain additives seem beneficial in the short term by promoting polymer cracking and improving the selectivity of aromatics, the transport of the additives and their degradation products and increased carbon coking can contaminate products, deactivate or modify catalysts, and foul reactors. These findings address a critical knowledge gap in effectively converting waste plastics via a greener route.

42 ENGINEERING↗
DOE OSTI2019

Stimulated emission of AlGaN layers grown on sapphire substrates using ammonia molecular beam epitaxy

By optimising the growth temperature of the AlGaN layers and using high-temperature AlN buffer layers, high-quality Al{sub x}Ga{sub 1 – x}N layers (x = 0.15, 0.21, 0.26, and 0.3) were obtained, in which stimulated emission in the UV spectral range 330 – 297 nm was implemented with the threshold intensity of excitation I{sub th} ≈ 0.7 – 1.4 MW cm{sup −2}, respectively. It is found that the threshold value of the stimulated emission of AlGaN layers grown by molecular beam epitaxy is largely determined by the intensity of the process of thermal decomposition of GaN, which affects the surface morphology and, consequently, the amount of optical scattering loss. It is shown that no pronounced localisation of nonequilibrium charge carriers occurs in the AlGaN layers, which is manifested in the absence of a large Stokes shift and in the realisation of optical amplification at transitions in an electron-hole plasma, and also indicates a relatively homogeneous material composition. (paper)

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
NASA NTRS1971

Kinetics of the O plus O3 reaction

The gas phase reaction O + O3 yields 2 O2 was studied directly in a flow system under conditions of excess ozone, with O-atoms produced by thermal decomposition of Ar-O3 mixtures on a Nernst Glower, and measurement of the spatial O-atom decay by O + NO chemiluminescence with small, variable NO additions. The rate constant was found to be (9.6 + or - 0.7) x 10 to the minus 15th power cu/cm/molecule/sec at 298 K. Over the temperature range 269 to 409 K a rate expression (1.78 + or - 0.28) x 10 to the 11th power exp((-4.46 + or - 0.10 kcal/mole)/RT) is reported. The effects of interference by O2 (delta sub g) and product excitation are discussed, and the present results are compared with earlier investigations.

Mccrumb, J. L.↗
DOE OSTI2021

Burning velocities of R-32/O 2 /N 2 mixtures: Experimental measurements and development of a validated detailed chemical kinetic model

This work entails characterizing the flammability of the refrigerant R-32 (CH 2 F 2 ) by both experimental measurements and modeling. Burning velocities S u were measured using a constant-volume spherical-flame method for R-32/O2/N 2 mixtures with O 2 /N 2 ratios ranging from 21% (synthetic air) to 40%, pressures of (1 to 3) bar, and equivalence ratios $\phi$ of (0.8 to 1.3). Based on a critical assessment of available data, and extended by our own calculations, a detailed chemical kinetic model was developed and key reactions determined using reaction path and sensitivity analyses. Initiation and combustion were identified as distinct kinetic regimes and burning velocities were found to be controlled by two primary reactions: unimolecular decomposition of CH 2 F 2 → CHF + HF and the subsequent reaction, CHF + O 2 → CHFO + O, the latter reaction initiating the radical chain propagating and branching by producing O atoms. Sensitive rate constants in the kinetic model were critically adjusted within their uncertainties and current knowledge bounds to best fit the experimental burning velocities. We found that rate constants in the model could be adjusted to match a given experimental S u for specific conditions (O 2 loading, P, T, $\phi$). This, however, then fixes predicted burning velocities for other all conditions within (3 to 4)% if physically realistic rate parameters are maintained. Thus, the entire set of experimental data is fit, not just to particular conditions. Relative random uncertainties in the experimental Su measurements were (4 to 6)%, but assumptions made for thermal radiation lost by the burned gas in the spherical-flame experiments add an additional systematic uncertainty. Systematic differences between the limiting cases of adiabatic (no thermal radiation lost) and optically-thin (all thermal radiation lost) varied significantly with conditions and ranged from (4 to 30)% at high to low velocities, respectively, translating into uncertainties of (2 to 15)% considering the average of two limiting cases. Comparison of experimental and kinetically modeled Su values suggests that the burned gas tends towards the optically-thin limit at the lowest pressures and fuel loadings and toward the adiabatic limit at the highest pressures and loadings. We tested and found support for this conclusion with a detailed analysis as a function of all the conditions (T, P, % O 2 , $\phi$). This behavior appears to transition from optically-thin to adiabatic as the density of the initial fuel increases, which results in increased CO 2 in the burned gas and thus increased absorption of the thermal radiation (consistent with the Beer-Lambert Law). The validated detailed model based on evaluated kinetics is shown to accurately predict burning velocities for R-32 O 2 /N 2 mixtures over a wide range of conditions and provides a reliable basis for extrapolation to other conditions.

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

Ab Initio Reaction Kinetics of CH 3 O$\dot{C}$(=O) and $\dot{C}$H 2 OC(=O)H Radicals

The dissociation and isomerization kinetics of the methyl ester combustion intermediates methoxycarbonyl radical (CH3O$\dot{C}$(=O)) and (formyloxy)methyl radical ($\dot{C}$H2OC(=O)H) are investigated theoretically using high-level ab initio methods and Rice–Ramsperger–Kassel–Marcus (RRKM)/master equation (ME) theory. Geometries obtained at the hybrid density functional theory (DFT) and coupled cluster singles and doubles with perturbative triples correction (CCSD(T)) levels of theory are found to be similar. We employ high-level ab initio wave function methods to refine the potential energy surface: CCSD(T), multireference singles and doubles configuration interaction (MRSDCI) with the Davidson–Silver (DS) correction, and multireference averaged coupled-pair functional (MRACPF2) theory. MRSDCI+DS and MRACPF2 capture the multiconfigurational character of transition states (TSs) and predict lower barrier heights than CCSD(T). The temperature- and pressure-dependent rate coefficients are computed using RRKM/ME theory in the temperature range 300–2500 K and a pressure range of 0.01 atm to the high-pressure limit, which are then fitted to modified Arrhenius expressions. Dissociation of CH3O$\dot{C}$(=O) to $\dot{C}$H3 and CO2 is predicted to be much faster than dissociating to CH3$\dot{O}$ and CO, consistent with its greater exothermicity. Isomerization between CH3O$\dot{C}$(=O) and $\dot{C}$H2OC(=O)H is predicted to be the slowest among the studied reactions and rarely happens even at high temperature and high pressure, suggesting the decomposition pathways of the two radicals are not strongly coupled. The predicted rate coefficients and branching fractions at finite pressures differ significantly from the corresponding high-pressure-limit results, especially at relatively high temperatures. Finally, because it is one of the most important CH3$\dot{O}$ removal mechanisms under atmospheric conditions, the reaction kinetics of CH3$\dot{O}$ + CO was also studied along the PES of CH3O$\dot{C}$(=O); the resulting kinetics predictions are in remarkable agreement with experiments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Pyrolysis of Cyclopentadienone: Mechanistic Insights from a Direct Measurement of Product Branching Ratios

The thermal decomposition of cyclopentadienone (C5H4-O) has been studied in a flash pyrolysis continuous flow microreactor. Passing dilute samples of o-phenylene sulfite (C6H4O2SO) in He through the microreactor at elevated temperatures yields a relatively clean source of C5H4-O. The pyrolysis of C5H4-O was investigated over the temperature range 1000-2000 K.

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

Image quality comparison between single energy and dual energy CT protocols for hepatic imaging

Purpose: Multi-detector computed tomography (MDCT) enables volumetric scans in a single breath hold and is clinically useful for hepatic imaging. For simple tasks, conventional single energy (SE) computed tomography (CT) images acquired at the optimal tube potential are known to have better quality than dual energy (DE) blended images. However, liver imaging is complex and often requires imaging of both structures containing iodinated contrast media, where atomic number differences are the primary contrast mechanism, and other structures, where density differences are the primary contrast mechanism. Hence it is conceivable that the broad spectrum used in a dual energy acquisition may be an advantage. In this work we are interested in comparing these two imaging strategies at equal-dose and more complex settings. Methods: We developed numerical anthropomorphic phantoms to mimic realistic clinical CT scans for medium size and large size patients. MDCT images based on the defined phantoms were simulated using various SE and DE protocols at pre- and post-contrast stages. For SE CT, images from 60 kVp through 140 with 10 kVp steps were considered; for DE CT, both 80/140 and 100/140 kVp scans were simulated and linearly blended at the optimal weights. To make a fair comparison, the mAs of each scan was adjusted to match the reference radiation dose (120 kVp, 200 mAs for medium size patients and 140 kVp, 400 mAs for large size patients). Contrast-to-noise ratio (CNR) of liver against other soft tissues was used to evaluate and compare the SE and DE protocols, and multiple pre- and post-contrasted liver-tissue pairs were used to define a composite CNR. To help validate the simulation results, we conducted a small clinical study. Eighty-five 120 kVp images and 81 blended 80/140 kVp images were collected and compared through both quantitative image quality analysis and an observer study. Results: In the simulation study, we found that the CNR of pre-contrast SE image mostly increased with increasing kVp while for post-contrast imaging 90 kVp or lower yielded higher CNR images, depending on the differential iodine concentration of each tissue. Similar trends were seen in DE blended CNR and those from SE protocols. In the presence of differential iodine concentration (i.e., post-contrast), the CNR curves maximize at lower kVps (80–120), with the peak shifted rightward for larger patients. The combined pre- and post-contrast composite CNR study demonstrated that an optimal SE protocol has better performance than blended DE images, and the optimal tube potential for SE scan is around 90 kVp for a medium size patients and between 90 and 120 kVp for large size patients (although low kVp imaging requires high x-ray tube power to avoid photon starvation). Also, a tin filter added to the high kVp beam is not only beneficial for material decomposition but it improves the CNR of the DE blended images as well. The dose adjusted CNR of the clinical images also showed the same trend and radiologists favored the SE scans over blended DE images. Conclusions: Our simulation showed that an optimized SE protocol produces up to 5% higher CNR for a range of clinical tasks. The clinical study also suggested 120 kVp SE scans have better image quality than blended DE images. Hence, blended DE images do not have a fundamental CNR advantage over optimized SE images.

60 APPLIED LIFE SCIENCES↗
NASA NTRS1975

Kinetics of the reaction of nitric oxide with hydrogen

The reaction of nitric oxide with hydrogen has been studied in the temperature range 2400-4500 K using a shock-tube technique. Mixtures of NO and H2 diluted in argon or krypton were heated by incident shock waves, and the infrared emission from the fundamental vibration-rotation band of NO at 5.3 microns was used to monitor the time-varying NO concentration. The decomposition of nitric oxide behind the shock was found to be modeled well by a fifteen-reaction system. A principal result of the study was the determination of the rate constant k1 for the reaction H + NO yields N + OH, which may be the rate-limiting step for NO removal in some combustion systems. Experimental values of k1 were obtained for each test through comparisons of measured and numerically predicted NO profiles. The data are fit closely by the expression k1 = 1.34 times 10 to the fourteenth power exp(-49 200/RT) cu cm/mole-sec. These data appear to be the first available for this rate constant.

Flower, W. L.↗
NASA NTRS2010

Establishing Consensus Turbulence Statistics for Hot Subsonic Jets

Many tasks in fluids engineering require knowledge of the turbulence in jets. There is a strong, although fragmented, literature base for low order statistics, such as jet spread and other meanvelocity field characteristics. Some sources, particularly for low speed cold jets, also provide turbulence intensities that are required for validating Reynolds-averaged Navier-Stokes (RANS) Computational Fluid Dynamics (CFD) codes. There are far fewer sources for jet spectra and for space-time correlations of turbulent velocity required for aeroacoustics applications, although there have been many singular publications with various unique statistics, such as Proper Orthogonal Decomposition, designed to uncover an underlying low-order dynamical description of turbulent jet flow. As the complexity of the statistic increases, the number of flows for which the data has been categorized and assembled decreases, making it difficult to systematically validate prediction codes that require high-level statistics over a broad range of jet flow conditions. For several years, researchers at NASA have worked on developing and validating jet noise prediction codes. One such class of codes, loosely called CFD-based or statistical methods, uses RANS CFD to predict jet mean and turbulent intensities in velocity and temperature. These flow quantities serve as the input to the acoustic source models and flow-sound interaction calculations that yield predictions of far-field jet noise. To develop this capability, a catalog of turbulent jet flows has been created with statistics ranging from mean velocity to space-time correlations of Reynolds stresses. The present document aims to document this catalog and to assess the accuracies of the data, e.g. establish uncertainties for the data. This paper covers the following five tasks: Document acquisition and processing procedures used to create the particle image velocimetry (PIV) datasets. Compare PIV data with hotwire and laser Doppler velocimetry (LDV) data published in the open literature. Compare different datasets acquired at roughly the same flow conditions to establish uncertainties. Create a consensus dataset for a range of hot jet flows, including uncertainty bands. Analyze this consensus dataset for self-consistency and compare jet characteristics to those of the open literature. One final objective fulfilled by this work was the demonstration of a universal scaling for the jet flow fields, at least within the region of interest to aeroacoustics. The potential core length and the spread rate of the half-velocity radius were used to collapse of the mean and turbulent velocity fields over the first 20 jet diameters in a highly satisfying manner.

Bridges, James↗
NASA NTRS2023

Numerical Study on the Aerodynamics of an Iced Airfoil With Scale-Resolving Simulations

Scale-resolving simulations of the NACA 23012 airfoil with horn ice accretion on the leading edge are conducted using the hybrid Reynolds-averaged Navier–Stokes/large-eddy simulation (hybrid RANS/LES) and wall-modeled large-eddy simulation (WMLES) approaches implemented in the Launch, Ascent, and Vehicle Aerodynamics (LAVA) framework. Aerodynamic results at the Reynolds number of 1.8 million show good comparison with the experimental measurements at different angles of attack from pre-stall to post-stall regimes. The pressure plateaus caused by the flow separation and the recovery of pressure inside the separation bubble around the iced leading edge are well predicted with the scale-resolving simulations when sufficient grid resolution is used around the accreted ice. The unsteadiness of the turbulent flows around the iced airfoil is also examined through the turbulent kinetic energy with the Reynolds normal stress anisotropy. Kelvin–Helmholtz instability (KHI) arises at the shear layer triggered by the upper ice horn and leads to rapid laminar-to-turbulent transition over a large range of angle of attack. With the increase of the angle of attack, the region with high turbulence intensity induced by the unstable shear layer spreads quickly over the entire upper surface of the airfoil. The coherent KHI modes from the upper and lower ice horns are extracted using the spectral proper orthogonal decomposition (SPOD) technique. The SPOD modes extracted from the upper shear layer have large-scale variations in the spanwise direction and low-rank behavior where the energy of the leading SPOD mode at each Strouhal number of the KHI largely represents the total energy when the mode number in the spanwise direction is small.

ARMD↗
NASA NTRS2023

Numerical Study on the Aerodynamics of an Iced Airfoil With Scale-Resolving Simulations

Scale-resolving simulations of the NACA 23012 airfoil with horn ice accretion on the leading edge are conducted using the hybrid Reynolds-averaged Navier–Stokes/large-eddy simulation (hybrid RANS/LES) and wall-modeled large-eddy simulation (WMLES) approaches implemented in the Launch, Ascent, and Vehicle Aerodynamics (LAVA) framework. Aerodynamic results at the Reynolds number of 1.8 million show good comparison with the experimental measurements at different angles of attack from pre-stall to post-stall regimes. The pressure plateaus caused by the flow separation and the recovery of pressure inside the separation bubble around the iced leading edge are well predicted with the scale-resolving simulations when sufficient grid resolution is used around the accreted ice. The unsteadiness of the turbulent flows around the iced airfoil is also examined through the turbulent kinetic energy with the Reynolds normal stress anisotropy. Kelvin–Helmholtz instability (KHI) arises at the shear layer triggered by the upper ice horn and leads to rapid laminar-to-turbulent transition over a large range of angle of attack. With the increase of the angle of attack, the region with high turbulence intensity induced by the unstable shear layer spreads quickly over the entire upper surface of the airfoil. The coherent KHI modes from the upper and lower ice horns are extracted using the spectral proper orthogonal decomposition (SPOD) technique. The SPOD modes extracted from the upper shear layer have large-scale variations in the spanwise direction and low-rank behavior where the energy of the leading SPOD mode at each Strouhal number of the KHI largely represents the total energy when the mode number in the spanwise direction is small.

ARMD↗
DOE OSTI2018

A new synergetic mesoporous silica combined to CdSe-graphene nanocomposite for dye degradation and hydrogen evolution in visible light

Highlights: • The SiO{sub 2}/CdSe-graphene material is capable of photocatalytic degradation of different organic dyes under visible light irradiation. • The large surface area of silica was provided a large response surface with a large quantity of reactions centers that needed H{sub 2} generation. • High H{sub 2} generation can be attributed to the effective charge carrier system and a good charge transferability of graphene decorated with SiO{sub 2}, and CdSe semiconductors. • The ternary catalyst holds promise to become a new potential photocatalyst for developing efficient hetero-system for hydrogen production. - Abstract: To promote outstanding qualities of mesoporous silica and enhance photocatalytic activity of CdSe and silica nanoparticles, the combination of SiO{sub 2} nanoparticles from silica precursor with CdSe-graphene nanoparticles was processed under catering of cetyltrimethylammonium bromide (CTAB) and sodium lauryl sulfate (SLS) as the surfactant template. The as-synthesized sample exhibited highly efficient photocatalytic effects for treatment of MB and RBB organic dye solutions at optimum conditions for this study, including pH and catalyst dosage, were at pH 11 for MB dye solution case and pH 3 for RBB dye solution case and initial amount was 0.05 g catalyst for both cases. Besides, hydrogen generation of SiO{sub 2}/CdSe-graphene was markedly higher than that of binary CdSe-graphene nanocomposite under ambient conditions with/without methanol 20% sacrificing reagents at room temperature. The SiO{sub 2}/CdSe-graphene nanocomposite is capable of photocatalytic degradation of different organic dyes under visible light irradiation as well as for developing efficient hetero-system for hydrogen production.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2023

Kinetics and mechanism of light-induced phase separation in a mixed-halide perovskite

Halide ion phase separation is a barrier to the application of mixed-halide perovskites, whereby the presence of large populations of photo-generated or injected carriers causes undesirable changes in the local band gap. Here, we investigate the mechanism of phase separation in CsPbI x Br 3-x perovskite single crystals driven by light. The phase separation process and its dynamics are visualized at the nanometer scale at cryogenic temperatures using in-situ scanning transmission electron microscopy and cathodoluminescence. Combined with phase field modeling that accounts for the coupling between electronic and chemical driving forces, our observations point to a spinodal decomposition mechanism in which both the amplitude of composition fluctuation and the characteristic length scale grow non-linearly with time. Our findings provide microscopic insights that can assist in further engineering mixed-halide perovskites either for stability or for intentional programming of the local halide ion composition, opening pathways to a wide range of applications.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Modeling Aerial Gamma-Ray Backgrounds Using Non-negative Matrix Factorization

Airborne gamma-ray surveys are useful for many applications, ranging from geology and mining to public health and nuclear security. In all these contexts, the ability to decompose a measured spectrum into a linear combination of background source terms can provide useful insights into the data and lead to improvements in the techniques that use spectral energy windows. Multiple methods for the linear decomposition of spectra exist but are subject to various drawbacks, such as allowing negative photon fluxes or requiring detailed Monte Carlo modeling. In this work, we propose using non-negative matrix factorization (NMF) as a data-driven approach to spectral decomposition. Using aerial surveys that include flights over water, we demonstrate that the mathematical approach of NMF finds physically relevant structure in the aerial gamma-ray background, namely, that measured spectra can be expressed as the sum of nearby terrestrial emission, distant terrestrial emission, and radon and cosmic emission. Furthermore, these NMF background components are compared with the background components obtained by noise-adjusted singular value decomposition (NASVD), which contain negative photon fluxes and, thus, do not represent the emission spectra in as straightforward a way. Finally, we comment on the potential areas of research that are enabled by NMF decompositions, such as new approaches to spectral anomaly detection and data fusion.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2014

Evaluation of Thermal Evolution Profiles and Estimation of Kinetic Parameters for Pyrolysis of Coal/Corn Stover Blends Using Thermogravimetric Analysis

The thermal evolution profiles and kinetic parameters for the pyrolysis of two Montana coals (DECS-38 subbituminous coal and DECS-25 lignite coal), one biomass sample (corn stover), and their blends (10%, 20%, and 30% by weight of corn stover) have been investigated at a heating rate of 5°C/min in an inert nitrogen atmosphere, using thermogravimetric analysis. The thermal evolution profiles of subbituminous coal and lignite coal display only one major peak over a wide temperature distribution, ~152–814°C and ~175–818°C, respectively, whereas the thermal decomposition profile for corn stover falls in a much narrower band than that of the coals, ~226–608°C. The nonlinearity in the evolution of volatile matter with increasing percentage of corn stover in the blends verifies the possibility of synergistic behavior in the blends with subbituminous coal where deviations from the predicted yield ranging between 2% and 7% were observed whereas very little deviations (1%–3%) from predicted yield were observed in blends with lignite indicating no significant interactions with corn stover. In addition, a single first-order reaction model using the Coats-Redfern approximation was utilized to predict the kinetic parameters of the pyrolysis reaction. The kinetic analysis indicated that each thermal evolution profile may be represented as a single first-order reaction. Three temperature regimes were identified for each of the coals while corn stover and the blends were analyzed using two and four temperature regimes, respectively.

Bhagavatula, Abhijit↗
NASA NTRS1984

Kinetics of the reaction HO2 + NO2 + M yields HO2NO2 + M

The flash photolysis/ultraviolet absorption technique was used to measure the rate constants for the reaction HO2 + NO2 + M yields HO2NO2 + M over the pressure range 50-700 torr and temperature range 229-362 K using He, O2, and N2 as diluent gases. The data were fit to the expression derived by Troe (1979) and co-workers for describing the pressure and temperature dependence of reactions in the falloff region. By combining these data with recent measurements of the rate constant for HO2NO2 thermal decomposition values of 73.8 + or - 2 eu for the standard entropy and -12.6 + or - kcal/mol for the standard enthalpy of formation of HO2NO2 were obtained. A significant enhancement in the rate constant was observed when water vapor was added to the system.

Sander, S. P.↗
DOE OSTI2020

Electrochemical Oxidation of Organic Molecules at Lower Overpotential: Accessing Broader Functional Group Compatibility with Electron-Proton Transfer Mediators

CONSPECTUS: Electrochemical organic oxidation reactions are highly appealing because protons are often effective terminal electron acceptors, thereby avoiding undesirable stoichiometric oxidants. These reactions are often plagued by high overpotentials, however, that greatly limit their utility. Single-electron transfer (SET) from organic molecules generates high energy radical-cations. Formation of such intermediates often requires electrode potentials far above the thermodynamic potentials of the reaction and frequently causes decomposition and/or side reactions of ancillary functional groups. In this Account, we show how electrocatalytic electron-proton transfer mediators (EPTMs) address this challenge. EPTMs bypass the formation of radical-cation intermediates by supporting mechanisms that operate at electrode potentials much lower (=1 V) than analogous direct electrolysis reactions. The stable aminoxyl radical TEMPO (2,2,6,6-tetramethylpiperidine N-oxyl) is an effective mediator for electrochemical alcohol oxidation, and we have employed such processes for applications ranging from pharmaceutical synthesis to biomass conversion. A complementary electrochemical alcohol oxidation method employs a cooperative Cu/TEMPO mediator system that operates at 0.5 V lower electrode potential than the TEMPO-only mediated process. This difference, which arises from a different catalytic mechanism, rationalizes the broad functional group tolerance of Cu/TEMPO-based aerobic alcohol oxidation catalysts. Aminoxyl mediators address long-standing challenges in the "Shono oxidation", an important method for a-C–H oxidation of tertiary amides and carbamates. Shono oxidations are initiated by a high-potential SET step that limits their utility. Aminoxyl-mediated Shono-type oxidations have been developed that operate at much lower potentials and tolerate diverse functional groups. Analogous reactivity underlies a-C–H cyanation of secondary cyclic amines, a new method that enables efficient diversification of piperidine-based pharmaceutical building blocks and preparation of non-natural amino acids. Electrochemical oxidations of benzylic C–H bonds are commonly initiated by SET to generate radical cations, but such methods are again plagued by large overpotentials. Mediated electrolysis methods that promote hydrogen-atom-transfer (HAT) from benzylic C–H bonds to Fe-oxo species and phthalimide N-oxyl (PINO) support C–H oxygenation, iodination, and oxidative-coupling reactions. A complementary method merges photochemistry with electrochemistry to achieve amidation of C(sp3)–H bonds. This unique process operates at much lower overpotentials compatible with diverse functional groups. These results have broad implications for organic electrochemistry, highlighting the importance of "overpotential" considerations and the prospects for expanding synthetic utility by using mediators to bypass high-energy outer-sphere electron-transfer mechanisms. Principles demonstrated here for oxidation are equally relevant to electrochemical reductions.

Wang, Fei↗
DOE OSTI2016

Quantification and Controls of Wetland Greenhouse Gas Emissions

Wetlands cover only a small fraction of the Earth’s land surface, but have a disproportionately large influence on global climate. Low oxygen conditions in wetland soils slows down decomposition, leading to net carbon dioxide sequestration over long timescales, while also favoring the production of redox sensitive gases such as nitrous oxide and methane. Freshwater marshes in particular sustain large exchanges of greenhouse gases under temperate or tropical climates and favorable nutrient regimes, yet have rarely been studied, leading to poor constraints on the magnitude of marsh gas sources, and the biogeochemical drivers of flux variability. The Sacramento-San Joaquin Delta in California was once a great expanse of tidal and freshwater marshes but underwent drainage for agriculture during the last two centuries. The resulting landscape is unsustainable with extreme rates of land subsidence and oxidation of peat soils lowering the surface elevation of much of the Delta below sea level. Wetland restoration has been proposed as a means to slow further subsidence and rebuild peat however the balance of greenhouse gas exchange in these novel ecosystems is still poorly described. In this dissertation I first explore oxygen availability as a control on the composition and magnitude of greenhouse gas emissions from drained wetland soils. In two separate experiments I quantify both the temporal dynamics of greenhouse gas emission and the kinetic sensitivity of gas production to a wide range of oxygen concentrations. This work demonstrated the very high sensitivity of carbon dioxide, methane, and nitrous oxide production to oxygen availability, in carbon rich wetland soils. I also found the temporal dynamics of gas production to follow a sequence predicted by thermodynamics and observed spatially in other soil or sediment systems. In the latter part of my dissertation I conduct two field studies to quantify greenhouse gas exchange and understand the carbon sources for decomposition in a 1 km2 restored wetland in the Sacramento Delta. By coupling flux measurements at multiple-scales with remote sensing imagery I showed that large methane emissions produce an overall climate warming effect from the wetland for the next several centuries, despite relatively high productivity. I also used radiocarbon analyses of wetland sediment carbon dioxide and methane to show that both bulk peat and recently fixed carbon contribute to decomposition in the wetland, and that their relative importance is regulated by proximity to, and the phenological cycles of, emergent vegetation.

07 ISOTOPE AND RADIATION SOURCES↗