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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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Directed Energy Transfer through DNA-templated J-aggregates
Strongly coupled molecular dye aggregates have unique optoelectronic properties that often resemble those of light harvesting complexes found in nature. The exciton dynamics in coupled dye aggregates could enhance the long-range transfer of optical excitation energy with high efficiency. In principle, dye aggregates could serve as important components in molecular-scale photonic devices, however, rational design of these coupled dye aggregates with precise control over their organization, interactions and dynamics remains a challenge. DNA nanotechnology has recently been used to build an excitonic circuit by organizing pseudoisocyanine (PIC) dyes forming J-aggregates on the templates of poly(dA)-poly(dT) DNA duplexes. Here, the excitonic properties of the PIC J-aggregates on DNA are characterized spectroscopically in detail using poly(dA)-poly(dT) tract lengths of 24 and 48 base pairs. The excitonic properties of these DNA templated dye assemblies depend on the length and sequence of the DNA template. The incorporation of a gap of two GC base pairs between two segments of poly(dA)-poly(dT) DNA markedly reduces the delocalization of excitation in the J-aggregates.Using a quantum dot (QD) as the light absorber and energy donor and using Alexa Fluor 647 (AF647) as the energy acceptor, with a DNA-templated J-aggregate in between, significant energy transfer from QD to AF647 is observed over a distance far longer than possible without the aggregate bridge. By comparing the efficiency of energy transfer through a continuous J-aggregate with the efficiency when the aggregate has a discontinuity in the middle, the effects of energy transfer within the aggregate bridge between the donor and acceptor are evaluated.
Intrinsic Chemical Reactivity of Silicon Electrode Materials: Gas Evolution
In this work, we explore how the chemical reactivity toward an aprotic battery electrolyte changes as a function of lithium salt and silicon surface termination chemistry. The reactions are highly correlated, where one decomposition reaction leads to a subsequent decomposition reaction. We report the data show that the presence of silicon hydrides (SiH$_x$) promotes the formation of CO gas, while surface oxides SiO$_x$ drive the formation of CO 2 . The extent and rate of oxidation depend on the surface basicity of the SiO 2 surface species. The most acidic surfaces seem to hinder CO 2 generation but not the decomposition of the salt. Indeed, the presence of F-containing salts (LiPF 6 and LiTFSI) promotes the reactions between carbonate electrolyte and silicon surfaces. Surfaces with high Li content seem to be the most passivating to gassing reactions, pointing to a pathway to stabilize the interfaces during cell formation and assembly.
Mitigating Calendar Aging in Si-NMC Batteries with Advanced Dual-Salt Glyme Electrolytes
In addressing the critical challenge of calendar aging in silicon (Si)-based lithium-ion batteries, this study introduces a groundbreaking strategy utilizing glyme-type dual-salt electrolytes (lithium bis(trifluoromethanesulfonyl)imide [LiTFSI] and lithium difluoro(oxalato)borate [LiDFOB]). These electrolytes are demonstrated to significantly mitigate parasitic reactions and capacity loss in Si-NMC (lithium nickel manganese cobalt oxide) full cells, especially when compared with traditional carbonate-based electrolytes. Further, our exhaustive mechanistic analysis reveals that such electrolytes not only preserve the integrity of the Si anode but also improve the cathode/electrolyte interphases (CEI) through the formation of a conformal coating on the high-voltage cathode surface. This dual-salt approach, enhanced by the addition of a phosphate additive, effectively decelerates calendar aging, marking a substantial advance in the quest for durable and reliable Si-based energy storage technologies. The findings underscore the vital role of electrolyte composition in extending the calendar life of Si batteries, offering an alternative avenue toward maximizing the performance and longevity of next-generation Li-Si batteries.
Silyl Radical Abstraction in the Functionalization of Plasma-Synthesized Silicon Nanocrystals
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Semiconductor-to-metal transition in rutile TiO 2 induced by tensile strain
Here, we report the first observation of a reversible, degenerate doping of titanium dioxide with strain, which is referred to as a semiconductor-to-metal transition. Application of tensile strain to a ~50 nm film of rutile TiO 2 thermally grown on a superelastic nitinol (NiTi intermetallic) substrate causes reversible degenerate doping as evidenced by electrochemistry, X-ray photoelectron spectroscopy (XPS), and conducting atomic force microscopy (CAFM). Cyclic voltammetry and impedance measurements show behavior characteristic of a highly doped n -type semiconductor for unstrained TiO 2 transitioning to metallic behavior under tensile strain. The transition reverses when strain is removed. Valence band XPS spectra show that samples strained to 5% exhibit metallic-like intensity near the Fermi level. Strain also induces a distinct transition in CAFM current-voltage curves from rectifying (typical of an n -type semiconductor) to ohmic (metal-like) behavior. We propose that strain raises the energy distribution of oxygen vacancies ( n -type dopants) near the conduction band and causes an increase in carrier concentration. As the carrier concentration is increased, the width of the depletion region is reduced, which then permits electron tunneling through the space charge barrier resulting in the observed metallic behavior.
Characterization of Silicon Nanocrystal Surfaces by Multidimensional Solid-State NMR Spectroscopy
The chemical and photophysical properties of silicon nanocrystals (Si NCs) are strongly dependent on the chemical composition and structure of their surfaces. Here we use fast magic angle spinning (MAS) and proton detection to enable the rapid acquisition of dipolar and scalar 2D 1 H– 29 Si heteronuclear correlation (HETCOR) solid-state NMR spectra and reveal a molecular picture of hydride-terminated and alkyl-functionalized surfaces of Si NCs produced in a nonthermal plasma. 2D 1 H– 29 Si HETCOR and dipolar 2D 1 H– 1 H multiple-quantum correlation spectra illustrate that resonances from surface mono-, di-, and trihydride groups cannot be resolved, contrary to previous literature assignments. Instead the 2D NMR spectra illustrate that there is large distribution of 1 H and 29 Si chemical shifts for the surface hydride species in both the as-synthesized and functionalized Si NCs. However, proton-detected 1 H– 29 Si refocused INEPT experiments can be used to unambiguously differentiate NMR signals from the different surface hydrides. Varying the 29 Si evolution time in refocused INEPT experiments and fitting the oscillation of the NMR signals allows for the relative populations of the different surface hydrides to be estimated. This analysis confirms that monohydride species are the predominant surface species on the as-synthesized Si NCs. A reduction in the populations of the di- and trihydrides is observed upon functionalization with alkyl groups, consistent with our previous hypothesis that the trihydride, or silyl (*SiH 3 ), group is primarily responsible for initiating surface functionalization reactions. Density functional theory (DFT) calculations were used to obtain quantum chemical structural models of the Si NC surface and reproduce the observed 1 H and 29 Si chemical shifts. Furthermore, the approaches outlined here will be useful to obtain a more detailed picture of surface structures for Si NCs and other hydride-passivated nanomaterials.
Morphological Control of In x Ga 1– x P Nanocrystals Synthesized in a Nonthermal Plasma
Here, we explore the growth of In x Ga 1– x P nanocrystals (x = 1, InP; x = 0, GaP; and 1 > x > 0, alloys) in a nonthermal plasma. By tuning the reactor conditions, we gain control over the morphology of the final product, producing either 10 nm diameter hollow nanocrystals or smaller 3 nm solid nanocrystals. We observe the gas-phase chemistry in the plasma reactor using plasma emission spectroscopy to understand the growth mechanism of the hollow versus solid morphology. We also connect this plasma chemistry to the subsequent native surface chemistry of the nanocrystals, which is dominated by the presence of both dative- and lattice-bound phosphine species. The dative phosphines react readily with oleylamine in an L-type ligand exchange reaction, evolving phosphines and allowing the particles to be dispersed in nonpolar solvents. Subsequent treatment by HF causes the solid InP 1.5 and In 0.5 Ga 0.5 P 1.3 to become photoluminescent, whereas the hollow particles remain nonemissive.
Nonthermal Plasma-Synthesized Phosphorus–Boron co-Doped Si Nanocrystals: A New Approach to Nontoxic NIR-Emitters
We report on the successful creation of nonthermal plasma-synthesized phorphorus and boron co-doped Si nanocrystals (PB:Si NCs) with diameters ( D NC ) ranging from 2.9 to 7.3 nm. Peak photoluminescence (PL) emission energies for all PB:Si NC diameters are ca. 400-500 meV lower than the excitonic emission values in intrinsic Si NCs, which can be attributed to prevalent donor-acceptor (D-A) transitions within the co-doped system. This D-A transition model is further evidenced by PL lifetimes within the range of 40-80 us, faster than what is observed for intrinsic Si NCs. By reducing the level of confinement within PB:Si NCs (i.e., D NC > 4 nm), we are able to red-shift the near-infrared (NIR)-emitting D-A transitions to below the band gap of bulk Si (1.12 eV). We quantify the PL quantum yield (PLQY) for a range of DNC and show that the plasma method can achieve reasonably high PLQY values (12% for D NC = 2.9 nm), even without any optimization of the synthesis or surface chemistry. We posit that perfect charge compensation cannot explain these results and propose a model in which dominant n-type doping accounts for the observations. Furthermore, these results demonstrate that nonthermal plasma synthesis is a viable pathway for preparing PB:Si NCs featuring NIR sub-band gap D-A transitions with relatively high quantum yields. More generally, this study provides insight into how doping affects energy and charge transfer within quantum-confined systems.
Thirdhand Smoke: New Evidence, Challenges, and Future Directions
Thirdhand smoke (THS) is the contamination that persists after secondhand tobacco smoke has been emitted into air. It refers to the tobacco-related gases and particles that become embedded in materials, such as the carpet, walls, furniture, blankets, and toys. THS is not strictly smoke, but chemicals that adhere to surfaces from which they can be released back into the air, undergo chemical transformations and/or accumulate. Currently, the hazards of THS are not as well documented as the hazards of secondhand smoke (SHS). In this paper, we describe the distribution and chemical changes that occur as SHS is transformed into THS, studies of environmental contamination by THS, human exposure studies, toxicology studies using animal models and in vitro systems, possible approaches for avoiding exposure, remediation of THS contamination, and priorities for further research.
Phosphonic Acids for Interfacial Engineering of Transparent Conductive Oxides
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Modeling Soot Oxidation and Gasification with Bayesian Statistics
This paper presents a statistical method for model calibration using data collected from literature. The method is used to calibrate parameters for global models of soot consumption in combustion systems. This consumption is broken into two different submodels: first for oxidation where soot particles are attacked by certain oxidizing agents; second for gasification where soot particles are attacked by H 2 O or CO 2 molecules. Rate data were collected from 19 studies in the literature and evaluated using Bayesian statistics to calibrate the model parameters. Bayesian statistics are valued in their ability to quantify uncertainty in modeling. The calibrated consumption model with quantified uncertainty is presented here along with a discussion of associated implications. The oxidation results are found to be consistent with previous studies. Significant variation is found in the CO 2 gasification rates.
Methane Catalytic Pyrolysis by Microwave and Thermal Heating over Carbon Nanotube-Supported Catalysts: Productivity, Kinetics, and Energy Efficiency
Methane catalytic pyrolysis, which is the reaction to produce hydrogen and carbon without emitting CO 2 , represents an approach for decarbonization using natural gas as an energy resource. In this work, the endothermic pyrolysis reaction was carried out under two heating scenarios: convective thermal heating and microwave-driven irradiative heating. The pyrolysis reaction was conducted at 550-600 °C over carbon nanotube-supported Ni-Pd and Ni-Cu catalysts. On both catalysts, an enhanced methane conversion rate was observed under microwave irradiation. The enhanced catalytic activity was hypothetically caused by the presence of free electrons in the carbon atoms within CNT that enabled the CNT support to absorb microwave energy effectively and to be heated efficiently by microwave. The microwave catalytic pyrolysis has shown improvement in kinetics, where the apparent activation energy dropped from 45.5 kJ/mol under conventional convective heating to 24.8 kJ/mol under microwave irradiation. When the methane conversion rate is increased by 37 %, the microwave power consumption only changed by 10.8 %. The research demonstrated the potential of transforming natural gas to clean hydrogen and value-added carbon in a more energy-efficient way. Process simulation and techno-economic analysis showed that potentially hydrogen minimum selling price of about $1 /kg H 2 could be achieved.
Overcoming Oxidation State-Dependent Spectral Interferences: Online Monitoring of U(VI) Reduction to U(IV) via Raman and UV–vis Spectroscopy
Analytical characterization of chemical processes is an essential component of both industrial processes and fundamental studies. Applicable techniques abound, but optical spectroscopy has the unique combination of being easily incorporated into on-line (in-situ) monitoring probes and can also provide abundant chemical information (concentration, oxidation state, speciation). However, this abundance of chemical information can make applying optical spectroscopy to complex chemical processes challenging. This is particularly evident in the bulk electrolysis of U(VI) to U(IV), an essential preparatory step in some nuclear fuel recycling schemes. Starting and product materials have interfering spectral signatures in both electronic and vibrational spectroscopies, making accurate and real-time analysis difficult to achieve. In this paper, we discuss the application of optical spectroscopy to the on-line monitoring of a bulk electrolysis process and the methods utilized to analyze data as well as characterize the efficiency and mechanism of U(IV) generation.