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Interconverting electrical and chemical energy efficiently and cost-effectively provides a massive opportunity to generate renewable hydrogen, create net-zero fuels and chemicals, capture and convert carbon dioxide (CO2), and create innovative sustainable industrial processes.
Not provided.Photoinduced electron transfer (PET) is a phenomenon whereby the absorption of light by a chemical species provides an energetic driving force for an electron-transfer reaction. This mechanism is relevant in many areas of chemistry, including the study of natural and artificial photosynthesis, photovoltaics and photosensitive materials. In recent years, research in the area of photoredox catalysis has enabled the use of PET for the catalytic generation of both neutral and charged organic free-radical species. These technologies have enabled previously inaccessible chemical transformations and have been widely used in both academic and industrial settings. Such reactions are often catalysed by visible-light-absorbing organic molecules or transition-metal complexes of ruthenium, iridium, chromium or copper. Although various closed-shell organic molecules have been shown to behave as competent electron-transfer catalysts in photoredox reactions, there are only limited reports of PET reactions involving neutral organic radicals as excited-state donors or acceptors. This is unsurprising because the lifetimes of doublet excited states of neutral organic radicals are typically several orders of magnitude shorter than the singlet lifetimes of known transition-metal photoredox catalysts. Here we document the discovery, characterization and reactivity of a neutral acridine radical with a maximum excited-state oxidation potential of -3.36 volts versus a saturated calomel electrode, which is similarly reducing to elemental lithium, making this radical one of the most potent chemical reductants reported. Spectroscopic, computational and chemical studies indicate that the formation of a twisted intramolecular charge-transfer species enables the population of higher-energy doublet excited states, leading to the observed potent photoreducing behaviour. Finally, we demonstrate that this catalytically generated PET catalyst facilitates several chemical reactions that typically require alkali metal reductants and can be used in other organic transformations that require dissolving metal reductants.
A few unusual chondrules in the Mezoe-Madaras L3 chondrite contain the peralkaline mineral merrihueite, (K, Na)2(Fe, Mg)5Si12O30, formed by reaction of free silica in the chondrules with K, Na, Fe-rich nebular gas. Vapor fractionation was required to create chondrules poor in Al and rich in Si, and the fractionated condensate produced had to aggregate into protochondrules very promptly (on the order of hours or less) to prevent it from mixing with dust of more generalized composition in the nebula. The traditional paradigm for chondrule formation, involving a series of unrelated events (chemical fractionation of precursor dust; clumping of the dust; melting of the dust-clumps), is inadequate for making these chondrules. A rapid process, all stages of which are related, is required. We propose that this occurred during the cooling and contraction of the volume of hot gas created by a small transient high-energy event in the nebula, of unspecified nature. Microdroplets of silicate melt created by condensation from the cooling, contracting gas had velocity vectors directed toward the center of the volume. Coalescence occurred in the crowded central zone where the microdroplets converged. The Mezoe-Madaras merriihueite-bearing chondrules may have been formed by an atypically low-energy nebular event, which achieved the needed chemical fractionations by only partially vaporizing precursor dust. More commonplace chondrule types may have been created by the same basic process, but involving higher-energy events in which precursor dust was completely vaporized and recondensed.
Ultrafast deactivation of metal-to-ligand charge-transfer (MLCT) states into low-lying metal-centered states has long limited the utility of first-row transition-metal complexes in a broad range of applications, including photoredox catalysis. Here we bypass such limitations using a Fe II -pyridinium carbene complex to enable electron transfer reactivity directly from a higher-lying MLCT state. Time-resolved spectroscopic data revealed that the higher-energy MLCT manifold relaxes to lower-lying metal-centered states with a time constant of ca. 3 ps. The nature of the metal-centered (MC) excited state as a 3 MC (i.e., S = 1) was inferred from variable-temperature transient absorption studies. These experiments also revealed that the ground-state recovery process occurs at or very near the “Marcus barrierless regime”, thereby allowing for an estimate of its excited-state redox potential. The detailed picture of the energetics of this compound that emerged enabled fine-tuning of competing thermodynamic and kinetic pathways to effect electron transfer from the higher-energy MLCT excited state prior to relaxation to the ligand-field manifold. We believe these results open an unexplored landscape for the use of earth-abundant first-row transition-metal-based chromophores for applications in light-to-chemical energy conversion.
High energy photons (λ < 400 nm) are frequently used to initiate free radical polymerizations to form polymer networks, but are only effective for transparent objects. This phenomenon poses a major challenge to additive manufacturing of particle-reinforced composite networks since deep light penetration of short-wavelength photons limits the homogeneous modification of physicochemical and mechanical properties. Herein, the unconventional, yet versatile, multiexciton process of triplet–triplet annihilation upconversion (TTA-UC) is employed for curing opaque hydrogel composites created by direct-ink-write (DIW) 3D printing. TTA-UC converts low energy red light (λ max = 660 nm) for deep penetration into higher-energy blue light to initiate free radical polymerizations within opaque objects. Further, as proof-of-principle, hydrogels containing up to 15 wt.% TiO 2 filler particles and doped with TTA-UC chromophores are readily cured with red light, while composites without the chromophores and TiO 2 loadings as little as 1–2 wt.% remain uncured. Importantly, this method has wide potential to modify the chemical and mechanical properties of complex DIW 3D-printed composite polymer networks.
Iodine is a chemical element with atomic number 53. Iodine-127 is stable (non-radioactive) and commonly found in nature. Elemental iodine is a purple-colored solid at room temperature and pressure, but spontaneously sublimates (turns into vapor). Iodine is an essential element for life, and is required for proper functioning of the thyroid. Iodine is present in many foods, and is readily absorbed by the body and concentrated in the thyroid gland. A fraction of iodine ingested or inhaled is rapidly removed by the kidneys. The rest of the inhaled or ingested iodine is absorbed the by thyroid and retained for many months. Iodine has a biological half-life of approximately 120 days in health individuals. The biological half-life can be shorter in individuals with hyperthyroidism, and longer in individuals with hypothyroidism. Iodine has a number of radioactive isotopes, most of which have relatively short half-lives (days or weeks). Short half-life iodine isotopes are useful for a variety of medical applications, including imaging and cancer therapy. For example, Iodine-123 (half-life 13 hours) is commonly used for medical imaging of the thyroid, while iodine-131 (half-life 8 days) is used for suppressing thyroid function in individuals with hyperthyroidism or ablating (killing) thyroid cells to treat thyroid cancer. Iodine-125 (half-life 59 days) is produced in nuclear reactors, and has medical uses. Although iodine-125 can be used for thyroid imaging, Iodine-123 is more commonly used for that purpose because of its shorter half-life and higher-energy emissions. Iodine-125 is more commonly used for cancer treatment, and can be processed into small metal pellets (seeds) inserted directly into a tumor. Iodine-125 emits low-energy x-rays which can kill tumor cells and generally cannot escape the tumor, sparing other tissues. Medical iodine for imaging or treatment is typically administered orally in the form a pill or liquid solution. A typical adult thyroid scan using iodine-123 involves having the patient swallow between one and four 0.1 millicuries pills, with the exact dose dependent on the patient’s weight. This results in a whole-body committed effective dose of 80 – 320 mrem, and a thyroid equivalent dose of 1443 – 5772 mrem. Note that the whole-body effective dose relates to the overall cancer risk, while the larger equivalent dose to the thyroid only indicates that most of this risk is the result of exposure to the thyroid. These doses are considered safe, although the procedure is not recommended for pregnant or breastfeeding women. In contrast, the quantities of iodine-131 used for treatment of hyperthyroidism and thyroid cancers are much higher. For treatment of hyperthyroidism, 4 – 10 millicuries are administered, while for thyroid cancer the administration can range from 50 – 150 millicuries of I-131. In addition to medical exposures, large populations were exposed to radioiodine as result of the atomic bombings of Hiroshima and Nagasaki in Japan, and the Chernobyl nuclear accident. These populations have been carefully followed for many years to assess the effect of their radiation exposures on cancer risk. As a result, a great deal is known about the cancer risks associated with radioiodine exposure. Because iodine is concentrated in the thyroid, the principal risk of exposure to radioiodine is thyroid cancer. Children have the highest risk of thyroid cancer after exposure to radioactive iodine. According to a large study of Japanese atomic bomb survivors, an effective dose of one Sievert (100,000 mrem) has been observed to increase the risk of thyroid cancer by a factor of 9.5 in children aged zero to nine years old, by a factor of 3 in children aged 10 to 19 years old, and by barely detectable amounts in adults. Another way of quantifying the risk from radioiodine exposure is from risk coefficients, which provide the risk per unit intake of radionuclides in terms of both morbidity (any cancer) and mortality (death). Both morbidity (risk of cancer) and mortality (death) risks are shown in the table below. Note that because thyroid cancer is almost never fatal, the morbidity coefficients are much larger than the mortality coefficients.
Integration of diverse datasets on the Moon may render some paradigms of lunar science either better-defended or vulnerable. We will consider three paradigms commonly used for understanding the processes of lunar regolith evolution in light of new and accumulated data. Our premise is that all data-sets should converge to a single interpretation if a concept or model is to be accepted as a paradigm. If a convergence is lacking, the paradigm needs fresh scrutiny. SteadyState: Lunar regolith evolution is currently understood in terms of comminution, agglutination, and replenishment as described by McKay and coworkers). Briefly, the model envisages continued micrometeoritic bombardment to comminute exposed soil particles to finer sizes while continued agglutination consumes finer sizes to produce larger constructional particles. Eventually, a balance between these two opposing processes achieves a steady state; soils at steady state maintain their mean grain size (M(sub z)). Episodic higher-energy impacts excavate fresh coarse material from below the soil cover, disturb the steady state, and restart the process to achieve a new steady state. It follows that the thickness of the regolith at any site would control the frequency of replenishment; indeed, the thickness of the regolith at Apollo landing sites was predicted by McKay et al. from the average M(sub z) of local soils. However, replenishment may come also from disintegrating boulders and cobbles at the lunar surface, and rates of comminution and agglutination may depend on the properties of target material. Regression between M(sub z) and I(sub s)/Fe(sup 0) (a measure of maturity or total surface exposure) of Apollo soils at different sites shows the following relations and estimated M(sub z) at a high maturity of I(sub s)/Fe(sup 0)= 100. It is possible that Apollo 12 and 15 sites have the thickest regolith and the Apollo 16 site has the thinnest. It is also possible that Apollo 12 and 15 basalts are comminuted faster than Apollo 16 highland rocks and Apollo 14 and 17 soils are products of mixed parentage. If a soil becomes continually finer as it matures until agglutination catches up, and if comminution is differential-dependent on the physical properties of the constituents, then the composition of the bulk soil has to match the composition of some "fulcrum" grain size fraction, say X Grain size fractions >X and <X will complement each other; their mass balance is the bulk soil. It appears that the 10-20-micron size fraction may be the fulcrum. In general, trace-element chemistry and IR reflectance spectra of this size fraction are closest to that of the bulk soil, regardless of maturity that is surprising. Disaggregated products of regolith breccias may also show similar relationships. If the 10-20 gm is the fulcrum (i.e., X as above) for many soil properties (e.g., major element composition, FMR, solar-wind-implanted elements), then this may be the ultimate mean grain size of lunar soils at steady state. However, different properties of soils may find steady states at different grain size fractions. The steady state of solar-wind-implanted elements, on the other hand, will climb up the grain-size scale as agglutinates transfer surface-correlated components into volume correlated components until a saturation level is reached or the rates of replenishment and implantation become equal. The same will be the case with vapor-deposited reduced metals as they too are incorporated inside constructional particles. Properties that are directly affected by soil-maturation processes will thus have different pathways of achieving steady states. Maturity, i.e., cumulative surface exposure, of lunar soils is best quantified by the amount of nanophase superparamagnetic Fe(sup 0) (np-Fe(sup 0)) normalized to Fe content (=I(sub s)/Fe(sup 0). The majority consensus (paradigm?) for the production of np-Fe(sup 0) is associated with the production of agglutinates. Because large doses of solar-wind H are implanted in all lunar soils upon exposure, any melting (e.g., during agglutinate production) triggers a chemical reduction of Fe-bearing minerals resulting in np-Fe(sup 0) production. The quantity of np-Fe(sup 0) is thus dependent on melting events, (i.e., exposure), and limited by the Fe content of the soil. All freshly produced np-Fe(sup 0) resides in agglutinitic glass, as new TEM images show. Apparently, the correction procedure developed by Lucey et al. to estimate the Fe content of the lunar surface from IR-reflectance spectra depends on accepting the above. However, the process of producing np-Fe(sup 0) may be physical rather than chemical. All np-Fe(sup 0) could be deposits from a vapor produced by micrometeoritic impact on lunar soils. If metal-O bonds in target phases are broken, O being "most volatile" will escape leaving an O-deficient vapor to facilitate the production of np-Fe(sup 0). If so, the quantity of np-Fe(sup 0) is dependent on the vaporizing events, (i.e., exposure), and limited by the efficiency of breaking metal-O bonds and the escape of 0. To the extent that strengths of metal-O bonds are dependent on the local crystal field, production of np-Fe(sup 0) may be limited by the mineral composition of target soils and not by their total Fe content. According to this model, vapor-deposited np-Fe(sup 0) should be found at any retentive sites on lunar soil grains. Indeed, TEM images show np-Fe(sup 0) on plagioclase and ilmenite. Incorporation of such pre-irradiated np-Fe(sup 0)-bearing grains into agglutinates may account for eventual increased emplacement of np-Fe(sup 0) in agglutinates. Such a paradigm shift in understanding the origin of np-Fe(sup 0) will raise questions ranging from the unquestionable use of Is/FeO as the universal maturity parameter of lunar soils to global elemental maps of the Moon from remote-sensing data. Additional information is contained in the original.
P(NDI2OD-T2), commonly referred to as N2200, stands out as a promising electron-transporting (n-type) polymer for low-cost, flexible (photo)electrochemical applications due to its reversible two-electron reduction and high electron mobility. UV–vis spectroelectrochemistry in the tetrabutyl ammonium hexafluorophosphate/acetonitrile electrolyte shows two sets of chemically reversible redox signals in the cyclic voltammetry corresponding to the reduction of the neutral polymer film to polaronic and bipolaronic species. These electrochemical signatures suggest a distinct electronic reorganization upon reduction (polaron/bipolaron formation), highlighting the need for molecular-level insights into how charges are accommodated within the polymer backbone. While it has been previously hypothesized that charge predominantly localizes on the naphthalene diimide (NDI) unit during reductive charging, specific changes in atomic environments that confirm this localization have not been characterized in n-type polymers. Herein, we use near-edge X-ray absorption fine structure (NEXAFS) spectroscopy to probe electronic transitions in an electrochemically charged polymer to deduce charge localization. The O K-edge (1s) spectra exhibit two distinct π* peaks; the intensity of the lower-energy π* a peak that corresponds to an excitation to a largely localized carbonyl state decreases with reductive potentials relative to the higher-energy π* b peak. We corroborate this with Raman spectroscopy at different potentials, which shows a decrease in intensity on the C–C/C═C and C═O stretching bands of NDI as well as a red shift of the carbonyl band due to the formation of a polaron on the NDI. Additionally, new Raman active NDI signals associated with elongated C═O and C═C bonds are observed at lower energy during the formation of charged states. Together with theoretical calculations, these findings show that the injected charge spatially localizes on the NDI units and is dominantly distributed on the carbonyl groups. In conclusion, the combination of NEXAFS, optical and vibrational spectroscopies, and theoretical calculations is generalizable to other pi-conjugated polymers and can identify charge localization for the further development of organic semiconductors.
The automated kinetics workflow code, KinBot, was used to explore and characterize the regions of the C 7 H 7 potential energy surface that are relevant to combustion environments and especially soot inception. We first explored the lowest-energy region, which includes the benzyl, fulvenallene + H, and cyclopentadienyl + acetylene entry points. We then expanded the model to include two higher-energy entry points, vinylpropargyl + acetylene and vinylacetylene + propargyl. The automated search was able to uncover the pathways from the literature. In addition, three important new routes were discovered: a lower-energy pathway connecting benzyl with vinylcyclopentadienyl, a decomposition mechanism from benzyl that results in side-chain hydrogen atom loss to produce fulvenallene + H, and shorter and lower energy routes to the dimethylene-cyclopentenyl intermediates. We systematically reduced the extended model to a chemically relevant domain composed of 63 wells, 10 bimolecular products, 87 barriers, and 1 barrierless channel and constructed a master equation using the CCSD(T)-F12a/cc-pVTZ//ωB97X-D/6-311++G(d,p) level of theory to provide rate coefficients for chemical modeling. Our calculated rate coefficients show excellent agreement with measured ones. We also simulated concentration profiles and calculated branching fractions from the important entry points to provide an interpretation of this important chemical landscape.
We report herein the influence of skeletal connectivity on the conformation-dependent optical properties of cyclosilane homo- and copolymers. 1,3-Linked cyclosilanes were bathochromically shifted by 20 nm in solution relative to 1,4-linked cyclosilanes, an effect reproduced by quantum chemical calculations on oligomeric model systems. Polysilane optical properties are conformation-dependent, and 1,3-linked cyclosilanes were hypothesized to adopt a favorable conformation unavailable to 1,4-linked cyclosilanes constrained to an endocyclic gauche conformation. Copolymerization of the isomeric cyclosilanes 1,3Si 6 and 1,4Si 6 afforded linear statistical copolymers, as characterized by 1 H and 29 Si NMR spectroscopies. The distinct connectivity of each comonomer was found to give rise to tunable absorption spectra, where the position of the absorption band systematically increased with the increased corporation of 1,3Si 6 . Computational studies pointed to conformation-dependent changes in orbital symmetry in shifting the most intense transition from the low-energy highest occupied molecular orbital (HOMO) → lowest unoccupied molecular orbital (LUMO) transition to a higher-energy HOMO → LUMO + n transition. Here, the results of these studies demonstrate for the first time the role of silicon skeletal connectivity in controlling conformation and optoelectronic properties and provide new insight into the structure-based design of solution-processable silicon-based polymeric materials.
Triplet-triplet annihilation (TTA) enables photon upconversion by combining two lower-energy triplet excitons to produce a higher-energy singlet exciton. This mechanism enhances light-harvesting efficiency for solar energy conversion and enables the use of lower-energy photons in bioimaging and photoredox catalysis applications. The magnetic modulation of such high-energy excitons presents an exciting opportunity to develop molecular quantum information technologies. While the spin dynamics of triplet exciton pairs are sensitive to external magnetic fields, the magnetic field effects (MFEs) associated with these pairs are generally limited by spin statistics to at most 10% at low fields (<1 Tesla), making them challenging to apply in technological advancements. In contrast, MFEs on spin-correlated radical pairs (SCRPs) can be significantly greater, surpassing those on triplet pairs. By using SCRPs-based molecular qubits as triplet sensitizers in the sensitized TTA scheme, we can magnetically modulate TTA and consequently, the delayed fluorescence of annihilators. In our current system, we have achieved more than 70% magnetic modulation of delayed fluorescence, effectively harnessing and even amplifying magnetic modulation within SCRPs to influence high-energy excitons. In conclusion, this work opens new opportunities for advancing spin-controlled chemical reactions and molecular quantum information technologies.
While first-principles density functional theory modeling has become a vital tool to investigate defect properties in semiconductors, the lack of crystalline periodicity in pseudobinary random composition alloys, such as In 1−𝑥 Ga 𝑥 As, complicates such analyses. We present a simulation strategy to systematically take into account the variability in the local defect environment in order to predict statistical properties of neutral intrinsic defects in In 1−𝑥 Ga 𝑥 As. We use a comprehensive sampling from a modest-sized 64-atom special quasirandom structure (SQS) to define a statistically representative set of defects, and use a 512-atom hypercell, a 2 × 2 × 2 supercell of SQS supercells, to achieve cell-size convergence. We articulate an equivalent site principle and describe how it constrains atomic chemical reference energies in computation of defect formation energies in pseudobinary alloys. A simple protocol for estimating reference energies for the Ga and In atoms sharing the III site succeeds in obtaining the equivalence of defects at Ga-sites and In sites in the SQS supercell, (<30 meV differences in average formation energies). For III-site defects, such as the As antisite As III , the statistical variability in formation energies is modest, ≈ 0.1–0.2 eV. The variability in formation energy at As-site defects, such as the As vacancy 𝑣 As , can be much larger, >1 eV. The As antisite is shown to be a low-energy defect and the most likely to be present in as-grown materials, just as in GaAs. All other defects are higher-energy defects unlikely to be important in native material, but potentially important in radiation-damaged material. With a strong variability in defect energies, especially on the As-site, explicit consideration of statistical variability due to compositional randomness will be imperative for meaningful and quantitative comparisons to experiment.
The basic model of Lindhard and Scharff, known as the local plasma model, is used to study the effects on stopping power of the chemical and physical state of the medium. Unlike previous work with the local plasma model, in which individual electron shifts in the plasma frequency were estimated empirically, he Pines correction derived for a degenerate Fermi gas is shown herein to provide a reasonable estimate, even on the atomic scale. Thus, the model is moved to a complete theoretical base requiring no empirical adjustments, as characteristic of past applications. The principal remaining error is in the overestimation of the low-energy absorption properties that are characteristic of the plasma model in the region of the atomic discrete spectrum, although higher-energy phenomena are accurately represented, and even excitation-to-ionization ratios are given to fair accuracy. Mean excitation energies for covalent-bonded gases and solids, for ionic gases and crystals, and for metals are calculated using first-order models of the bonded states.