化学•材料最新文献

The detection of noble gas radioisotopes following a suspected underground nuclear explosion is the surest indicator that nuclear detonation has occurred. However, the accurate interpretation and attribution of radioisotopic signatures is only possible with a complete understanding of transport processes occurring between the nuclear cavity and surface. In the far-field, diffusive forces contributing to gas transport are impacted by temperature gradients and subsurface lithology. In the current study, we investigate diffusive transport of xenon (Xe), krypton (Kr), and sulfur hexafluoride (SF₆) through intact Bandelier tuff at elevated temperatures using a newly developed high temperature diffusion cell. Diffusion coefficients determined using Finite Element Heat and Mass transfer code simulations and the Parameter ESTimation tool range from 2.6-3.1 × 10^-6 m²/s at 20 °C, 3.4-5.1 × 10^-6 m²/s at 40 °C, and 4.3-7.0 × 10^-6 m²/s at 70 °C. Sorption was found to be an important transport mechanism at ambient temperatures (20 °C). Most critically, our study shows that empirical porosity-based diffusion estimates for these gases through tuff captured neither the magnitude nor trends relative to a nonsorbing sandstone. These new insights highlight the importance of experimental transport investigations and will be used to improve models for subsurface gas propagation relevant to proliferation detection and environmental contamination.

Producing H₂O₂ through a selective, two-electron (2e) oxygen reduction reaction (ORR) is challenging, especially when it serves as an advanced oxidation process (AOP) for cost-effective water decontamination. Herein, we attain a 2e-selectivity H₂O₂ production using a carbon nanotube electrified membrane with ibuprofen (IBU) molecules laden (IBU@CNT-EM) in an ultrafast, single-pass electrofiltration process. The IBU@CNT-EM can generate H₂O₂ at a rate of 25.62 mol g_CNT^-1 h^-1 L^-1 in the permeate with a residence time of 1.81 s. We demonstrated that an interwoven, hydrophilic-hydrophobic membrane nanostructure offers an excellent air-to-water transport platform for ORR acceleration. The electron transfer number of the ORR for IBU@CNT at neutral pH was confirmed as 2.71, elucidating a near-2e selectivity to H₂O₂. Density functional theory (DFT) studies validated an exceptional charge distribution of the IBU@CNT for the O₂ adsorption. The adsorption energies of the O₂ and *OOH intermediates are proportional to the H₂O₂ selectivity (64.39%), higher than that of the CNT (37.81%). With the simple and durable production of H₂O₂ by IBU@CNT-EM electrofiltration, the permeate can actuate Fenton oxidation to efficiently decompose emerging pollutants and inactivate bacteria. Our study introduces a new paradigm for developing high-performance H₂O₂-production membranes for water treatment by reusing environmental functional materials.

Organophosphate esters (OPEs) have been observed in the remote Arctic Ocean, yet the influence of hydrodynamics and seasonal sea ice variations on the occurrence and transport of waterborne OPEs remains unclear. This study comprehensively examines OPEs in surface seawater of the central Arctic Ocean during the summer of 2020, integrating surface ocean current and sea ice concentration data. The results confirm significant spatiotemporal variations of the OPEs, with the total concentration of seven major OPEs averaging 780 ± 970 pg/L. Chlorinated OPEs, particularly tris(1-chloro-2-propyl) phosphate (TCPP), were dominant. The significant impact of hydrodynamics on the OPE transport is demonstrated by higher OPE concentrations in regions with strong surface currents, especially at the edge of the Beaufort Gyre and the confluence of the Beaufort Gyre and the Transpolar Drift. Furthermore, OPE levels were generally higher in drifting-ice-covered regions compared to ice-free regions, attributed to the volatilization of dissolved OPEs formerly trapped below the sea ice or newly released from melting snow and sea ice. Notably, TCPP decreased by only 19% in the ice-free area, while the more volatile triphenyl phosphate decreased by 63% compared with the partial ice region.

Resource demand by soil microorganisms critically influences microbial metabolism and then influences ecosystem resilience and multifunctionality. The ecological remediation of abandoned tailings is a topic of broad interest, yet our understanding of microbial metabolic status in restored soils, particularly at the aggregate scale, remains limited. This study investigated microbial resources within soil aggregates from revegetated tailings and applied a vector model of ecoenzymatic stoichiometry to examine how different vegetation patterns (grassland, forest, or bare land control) impact microbial resource limitation. Five-year vegetation restoration significantly elevated carbon (C) and nitrogen (N) concentrations and their stoichiometric ratios in soil aggregates (approximately 2-fold), although these increases were not translated to in the microbial biomass and its stoichiometry. The activities of C- and phosphorus (P)-acquiring extracellular enzymes in these aggregates increased substantially postvegetation, with the most pronounced escalation in macroaggregates (>0.25 mm). The vector model results indicated soil microbial metabolism was colimited by C and P, most acutely in microaggregates (<0.25 mm). This colimitation was exacerbated by monotypic vegetation cover but mitigated under diversified vegetation cover. Soil nutrient stoichiometric ratios in vegetation restoration controlled microbial resource limitation, overshadowing the impact of heavy metals. Our findings underscore that optimizing resource allocation within soil aggregates through strategic revegetation can enhance microbial metabolism in tailings, which advocates for the implementation of diverse vegetation covers as a viable strategy to improve the ecological development of degraded landscapes.

In this work, effects of ozone (O₃) addition on ethylene-oxygen (C₂H₄-O₂) mixtures are computationally studied through the explosion limit profiles. The results show that the addition of minute quantities of ozone (with a mole fraction of 0.06% in the oxidizer) shifts the explosion limit of the C₂H₄-O₃-O₂ mixtures to the low-temperature regime. Further increases in the ozone concentration gradually strengthen the negative temperature coefficient (NTC) behavior at the second limit. That is because the explosion limit is primarily controlled by the ethylene ozonolysis reaction, and both the sensitivity analysis and chemical reaction rate perturbation method reveal specific kinetic reasons. Furthermore, it is shown that with the increasing equivalence ratio, the explosion limit curve with minute ozone addition rotates counterclockwise around a crossover point, while the explosion limit curve becomes complicated and the NTC behavior appears on the second limit with larger quantities of ozone addition. Furthermore, the effects of dilutions of nitrogen (N₂), argon (Ar), carbon dioxide (CO₂), and water (H₂O) on the explosion limits are also studied. To elucidate the different wall elimination effects of different explosion limit regimes, the impacts of surface reactions of six radicals (H, O, OH, HO₂, H₂O₂, and HCO) have been examined and the dominant radicals are found to be H and HO₂. The H radicals significantly influence the first explosion limit, while the HO₂ radicals impact the entire explosion limit.

Solvent polarity control as an efficient methodology to regulate the chiroptical properties, including spectral shape, width, intensity, wavelength, etc., has emerged as a novel frontier in optical materials design. However, the underling relationship connecting polarity to the optical property remains unclear. Herein, using state-of-the-art computations and the FC|VG model, the solvent effect on the chiroptical properties of bora[6]helicene was accurately and systematically computed to shed light on this issue. It is found that the vibronic coupling is crucial in explaining the spectral shape, width, and relative intensity of different peaks. Moreover, the intensity and position of the emission (EMI) and circularly polarized luminescence (CPL) are closely related to the polarity of the solvent. Intriguingly, we got a series of good linear relationships between polarity and EMI|CPL (|r| ≥ 0.95). Thus, this parameter can be used as a potential descriptor to estimate the intensity and position of EMI|CPL, leading to new strategies for designing fully colored fluorescent materials.