Zinc Titanium Nitride Semiconductor toward Durable Photoelectrochemical Applications
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30 DIRECT ENERGY CONVERSION↗
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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The sensitive surface chemistry of Co-free, Ni-rich layered oxides: identifying experimental conditions that influence characterization results
Recent studies have suggested that Co-free, Ni-rich layered cathodes (e.g., doped LiNiO2) can provide promising battery performance for practical applications. However, these layered cathodes suffer from significant surface instability during various stages of the sample history, which generates inherent challenges for achieving stable battery performance and obtaining statistically representative characterization results. To reliably report the surface chemistry of these materials, delicate controls of stepwise sample preparation are required. In this study, we aim to reveal how the surface chemistry of LiNiO2 based materials changes with various environments, including human exhalation, sample storage, sample preparation, electrochemistry cycling, and surface doping. Our results demonstrate that the surface of these materials is highly reactive and prone to alter at various stages of sample handling and characterization. The sensitive surface could impact the interpretation of the surface chemical and structural information, including surface carbonate formation, transition metal reduction and dissolution, and surface reconstruction. Importantly, the heterogeneity of the surface degradation calls for a consolidation of nanoscale, high-resolution characterization, and ensemble-averaged methods in order to improve statistical representation. Furthermore, the doping chemistry can effectively mitigate the surface degradation and improve overall battery performance due to the enhanced surface oxygen retention. Our study highlights the necessity of strict measurements through complementary characterizations at multiple length scales to eliminate unintentional biased conclusions.
surface chemistry, Co-free Ni-rich cathodes, Istab↗
Ultrathin electron and proton-conducting membranes for nanoscale integrated artificial photosystems
Reducing the thickness of separation membranes without compromising their selectivity and robustness is the most effective way of maximizing the areal conductivity. This is especially important for the integration of visible light-driven water oxidation and carbon dioxide (or proton) reduction into a complete artificial photosystem on the shortest possible length scale – the nanoscale – because of the efficiency advantages over macroscale photosystems. In addition to their excellent separation property, ultrathin membranes of 10 nm thickness or less need to exhibit sufficient electrical and proton conductivity in order for the photocatalytic rates to keep up with the photon flux at maximum solar intensity. Furher, two materials, graphene and amorphous silica with embedded molecular wires, have emerged as promising ultrathin membranes for the development of nanoscale integrated solar-fuel systems. Moreover, electrically conducting metal–organic or covalent–organic frameworks can be used to fabricate high surface area-supports that enable the use of molecular catalysts and/or light absorbers at an adequate areal density for nanoscale integration with graphene membranes. Following an overview of the electron and proton conductivity of these ultrathin materials and recent examples of photoelectrocatalytic applications that take advantage of some but not all the properties that constitute a complete functional membrane, the status and future opportunities for complete nanoscale integrated photosystems featuring an ultrathin membrane are discussed.
59 BASIC BIOLOGICAL SCIENCES↗
Effects of surface diffusion in electrocatalytic CO 2 reduction on Cu revealed by kinetic Monte Carlo simulations
We report Kinetic Monte Carlo (KMC) methods are frequently used for mechanistic studies of thermally driven heterogeneous catalysis systems but are underused for electrocatalysis. Here, we develop a lattice KMC approach for electrocatalytic CO 2 reduction. The work is motivated by a prior experimental report that performed electroreduction of a mixed feed of 12 CO 2 and 13 CO on Cu; differences in the 13 C content of C2 products ethylene and ethanol (Δ 13 C) were interpreted as evidence of site selectivity. The lattice KMC model considers the effect of surface diffusion on this system. In the limit of infinitely fast diffusion (mean-field approximation), the key intermediates 12 CO* and 13 CO* would be well mixed on the surface and no evidence of site selectivity could have been observed. Using a simple two-site model and adapting a previously reported microkinetic model, we assess the effects of diffusion on the relative isotope fractions in the products using the estimated surface diffusion rate of CO* from literature reports. We find that the size of the active sites and the total surface adsorbate coverage can have a large influence on the values of Δ 13 C that can be observed. Δ 13 C is less sensitive to the CO* diffusion rate as long as it is within the estimated range. We further offer possible methods to estimate surface distribution of intermediates and to predict intrinsic selectivity of active sites based on experimental observations. This work illustrates the importance of considering surface diffusion in the study of electrochemical CO 2 reduction to multi-carbon products. Our approach is entirely based on a freely available open-source code, so will be readily adaptable to other electrocatalytic systems.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Assessing the design of integrated methane sensing networks
Abstract While methane is the second largest contributor to global warming after carbon dioxide, it has a larger warming effect over a much shorter lifetime. Despite accelerated technological efforts to radically reduce global carbon dioxide emissions, rapid reductions in methane emissions are needed to limit near-term warming. Being primarily emitted as a byproduct from agricultural activities and energy extraction, methane is currently monitored via bottom–up (i.e. activity level) or top–down (via airborne or satellite retrievals) approaches. However, significant methane leaks remain undetected and emission rates are challenging to characterize with current monitoring frameworks. In this paper, we study the design of a layered monitoring approach that combines bottom–up and top–down approaches as an integrated sensing network. By recognizing that varying meteorological conditions and emission rates impact the efficacy of bottom–up monitoring, we develop a probabilistic approach to optimal sensor placement in its bottom–up network. Subsequently, we derive an inverse Bayesian framework to quantify the improvement that a design-optimized integrated framework has on emission-rate quantifications and their uncertainties. We find that under realistic meteorological conditions, the overall error in estimating the true emission rates is approximately 1.3 times higher, with their uncertainties being approximately 2.4 times higher, when using a randomized network over an optimized network, highlighting the importance of optimizing the design of integrated methane sensing networks. Further, we find that optimized networks can improve scenario coverage fractions by more than a factor of 2 over experimentally-studied networks, and identify a budget threshold beyond which the rate of optimized-network coverage improvement exhibits diminishing returns, suggesting that strategic sensor placement is also crucial for maximizing network efficiency.
54 ENVIRONMENTAL SCIENCES↗
Limitation of C4 photosynthesis by low carbonic anhydrase activity increases with temperature but does not influence mesophyll CO2 conductance
The CO2-concentrating mechanism (CCM) in C4 plants is initiated by the uptake of bicarbonate (HCO3…) via phosphoenolpyruvate carboxylase (PEPC). Generation of HCO3– for PEPC is determined by the interaction between mesophyll CO2 conductance and the hydration of CO2 to HCO3– by carbonic anhydrase (CA). Genetic reduction of CA was previously shown not to limit C4 photosynthesis under ambient atmospheric partial pressures of CO2 (pCO2). However, CA activity varies widely across C4 species and it is unknown if there are specific environmental conditions (e.g. high temperature) where CA may limit HCO3– production for C4 photosynthesis. Additionally, CA activity has been suggested to influence mesophyll conductance, but this has not been experimentally tested. We hypothesize that CA activity can limit PEPC at high temperatures, particularly at low pCO2, but does not directly influence gm. Here we tested the influence of genetically reduced CA activity on photosynthesis and gm in the C4 plant Zea mays under a range of pCO2 and temperatures. Reduced CA activity limited HCO3– production for C4 photosynthesis at low pCO2 as temperatures increased, but did not influence mesophyll conductance. Therefore, high leaf CA activity may enhance C4 photosynthesis under high temperature when stomatal conductance restricts the availability of atmospheric CO2.
Plant Sciences↗
Selected advances in small-angle scattering and applications they serve in manufacturing, energy and climate change
Innovations in small-angle X-ray and neutron scattering (SAXS and SANS) at major X-ray and neutron facilities offer new characterization tools for researching materials phenomena relevant to advanced applications. For SAXS, the new generation of diffraction-limited storage rings, incorporating multi-bend achromat concepts, dramatically decrease electron beam emittance and significantly increase X-ray brilliance over previous third-generation sources. This results in intense X-ray incident beams that are more compact in the horizontal plane, allowing significantly improved spatial resolution, better time resolution, and a new era for coherent-beam SAXS methods such as X-ray photon correlation spectroscopy. Elsewhere, X-ray free-electron laser sources provide extremely bright, fully coherent, X-ray pulses of <100 fs and can support SAXS studies of material processes where entire SAXS data sets are collected in a single pulse train. Meanwhile, SANS at both steady-state reactor and pulsed spallation neutron sources has significantly evolved. Developments in neutron optics and multiple detector carriages now enable data collection in a few minutes for materials characterization over nanometre-to-micrometre scale ranges, opening up real-time studies of multi-scale materials phenomena. SANS at pulsed neutron sources is becoming more integrated with neutron diffraction methods for simultaneous structure characterization of complex materials. In this paper, selected developments are highlighted and some recent state-of-the-art studies discussed, relevant to hard matter applications in advanced manufacturing, energy and climate change.
36 MATERIALS SCIENCE↗
The Electrochemical Behavior of Tellurium Tetrachloride in LiCl-KCl Eutectic Molten Salt at 450 ºC
Cyclic voltammetry CV), square wave voltammetry (SWV), and electrochemical impedance spectroscopy measurements were carried out in 1 and 5 wt% TeCl 4 containing LiCl-KCl eutectic molten salt at 450 °C using tungsten and glassy carbon as working electrodes. Reduction of Te(IV) to Te(0) occurred in three steps at potentials more negative than -0.4 V Ag/AgCl . The Te(0) was further reduced to Te 2- at more negative potentials. Formation of Te 2- was observed at potentials more negative than -2.2 V Ag/AgCl . Diffusivities of Te 4+ , Te 2+ , and Te 2- and their formal potentials were estimated from the CV data. The diffusion coefficients of Te 4+ , Te 2+ and Te 2- were 0.9 × 10 -5 , 3.8 × 10 -5 , and 1.5 × 10 -5 cm 2 s -1 , respectively in the 1 wt% TeCl 4 containing LiCl-KCl molten salt. The diffusivity of Te species generally decreased with increase in the concentration of TeCl 4 .
Electrochemistry↗
Electrolytes Containing Triethyl Phosphate Solubilized Lithium Nitrate for Improved Silicon Anode Performance
An electrolyte consisting of lithium nitrate (LiNO3) and lithium difluoro(oxalato)borate (LiDFOB) in ethylene carbonate (EC), ethylmethyl carbonate (EMC), and triethyl phosphate (TEP) is used to improve the long-term cycling stability of silicon anodes. TEP was selected for its ability to dissolve LiNO 3 in carbonates to a concentration of ~0.2 M. The large amount of LiNO 3 combined with the LiDFOB salt leads to a capacity retention of 87.1% after one hundred cycles due to the formation of a relatively stable solid electrolyte interphase (SEI). Ex-situ surface analysis reveals that the SEI consists of oxalates, lithium alkyl carbonates, borates, and nitrate reduction products. By selecting two components which are preferentially reduced (LiNO 3 and LiDFOB), the SEI is able to inhibit continuous solvent decomposition and allows for improved electrochemical cycling for pure silicon anodes.
25 ENERGY STORAGE↗
Final Science Report of the Joint Center for Artificial Photosynthesis (JCAP)
The Joint Center for Artificial Photosynthesis (JCAP) was designated as the U.S. Department of Energy (DOE) Fuels from Sunlight Energy Innovation Hub on July 22, 2010, and began operations according to a cooperative agreement between the DOE and the California Institute of Technology on September 30, 2010. The cooperative agreement was renewed on September 30, 2015. This final science report outlines JCAP research activities from September 30, 2010 to September 30, 2021.
08 HYDROGEN↗
Cooling Egypt: Cost and benefits of room air conditioner efficiency improvement in Egypt
Egypt is one of the largest countries in the Middle East and North Africa region with a population of a total of 106 million (as of July 2022). Increasing urbanization, population growth, and increasing temperatures will likely continue to drive demand for electricity from air conditioning, with corresponding negative impacts on the peak load, air quality, and greenhouse gas emissions from refrigerant use and energy consumption. Since 2003, Egypt has adopted a standards and labeling program for various appliances, and has improved its room air conditioner (RAC) energy efficiency requirements in 2016 and 2017. However, its market is still dominated by inefficient fixed-speed drive (FSD) RACs due to a price-sensitive market. Seasonal metrics such as Cooling Season Performance Factor (CSPF) measure the energy efficiency of FSD and variable-speed drive (VSD) RACs on the same scale. Leading markets, most notably China, have already adopted a new MEPS in 2020 and 2022, which align largely with the United for Efficiency (U4E) Model Regulations Guidelines. India has also adopted a CSPF metric. Both India and China are now experiencing (1) increased demand and consumption of higher efficiency VSD RACs, as well as (2) a corresponding drop in prices from the economies of scale of production of these higher efficiency RACs. Because China is a leading manufacturer in the global air conditioner (AC) market, its adoption of the model U4E regulations have effectively raised the energy efficiency of the ACs in the global market. To achieve the benefits of taking a similar approach to Egypt’s market, we offer the following recommendations: 1. Adopt a common metric to measure the efficiency of both FSD and VSD RACs 2. Raise the stringency of MEPS to the level of the U4E Model Regulation Guidelines 3. Restructure the labeling program from the “A++” labeling scheme to a simpler A through E or a star-rating program 4. Strengthen the compliance regime governing the Egyptian AC MEPS 5. Assist small and medium AC manufacturers in Egypt to transition manufacturing lines to produce low-cost, high-efficiency VSD RACs. Adopting these recommendations would reduce Egypt’s electricity consumption to 11 TWh in 2030 and 89 TWh in 2050—with corresponding carbon dioxide (CO2) emissions reductions and avoided generation capacity requirements compared to the baseline.
29 ENERGY PLANNING, POLICY, AND ECONOMY↗
Using a systems biology approach to describe the role of dissimilatory phosphite oxidation in the global phosphorus cycle
We investigated the role of redox reactions in the global phosphorous (P) cycle. We identified novel microbial processes responsible for oxidation of reduced phosphorous in the form of phosphite producing bioavailable phosphate. We identified central tenets that define microbial dissimilatory phosphite oxidation (DPO) and the breadth of the taxonomy of DPO microorganisms (DPOM). We demonstrated that this metabolism is vertically evolved from 3.8 GYA contemporaneously with anoxygenic phototrophy. We further demonstrate its occurrence on extant Earth as a primary mechanism driving a phosphorous redox cycle. Finally, we showed that this metabolism is environmentally maintained by the newly described autotrophic Phosphitivorax genus which rely on the reductive glycine pathway for carbon fixation. Our results demonstrate that these species are involved in a complex nutrient-dependent symbiotic relationship with their community in which they provide the fixed carbon to support the heterotrophic community and in return receive prerequisite corrinoids to maintain their activities.
54 ENVIRONMENTAL SCIENCES↗
Production of high purity silicon carbide Patent
Producing high purity silicon carbide on carbon base by hydrogen reduction of silicon tetrachloride
Jewell, R. A.↗
Apparatus for producing high purity silicon carbide crystals Patent
Device for producing high purity silicon carbide on carbon base by hydrogen reduction of silicon tetrachloride
Jewell, R. A.↗
Interpretation of high-resolution spectra of Venus. I
High resolution Venus spectra, obtaining band spectra growth curve of C13O16O18 isotope of carbon dioxide, comparing data reduction methods
Young, L. G.↗
Blood gases in hibernating and active ground squirrels - HbO2 affinity at 6 and 38 C
Venous and arterial blood gases in hibernating and normothermic ground squirrels, showing venous oxygen and carbon dioxide partial pressures reduction in hibernation
Musacchia, X. J.↗
Oxygen recovery for the 90-day Space Station simulator test
Oxygen generation system for 90-day space station simulator, considering carbon dioxide removal and reduction and water electrolysis
Harkee, J. F.↗
Methods for reducing pollutant emissions from jet aircraft
Pollutant emissions from jet aircraft and combustion research aimed at reducing these emissions are defined. The problem of smoke formation and results achieved in smoke reduction from commercial combustors are discussed. Expermental results of parametric tests performed on both conventional and experimental combustors over a range of combustor-inlet conditions are presented. Combustor design techniques for reducing pollutant emissions are discussed. Improved fuel atomization resulting from the use of air-assist fuel nozzles has brought about significant reductions in hydrocarbon and carbon monoxide emissions at idle. Diffuser tests have shown that the combustor-inlet airflow profile can be controlled through the use of diffuser-wall bleed and that it may thus be possible to reduce emissions by controlling combustor airflow distribution. Emissions of nitric oxide from a shortlength annular swirl-can combustor were significantly lower than those from a conventional combustor operating at similar conditions.
Butze, H. F.↗