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1.
Angew Chem Int Ed Engl ; : e202416866, 2024 Oct 04.
Artigo em Inglês | MEDLINE | ID: mdl-39363721

RESUMO

In this study, a high-performance inorganic-organic hybrid hole transporting layer (HTL) was developed using ethanol-soluble alkoxide precursors and a self-assembled monolayer (SAM). Three metal oxides-vanadium oxide (VOx), niobium oxide (Nb2O5), and tantalum oxide (Ta2O5)-were synthesized through successive low-temperature (100 °C) thermal annealing (TA) and UV-ozone (UVO) treatments of their respective precursors: vanadium oxytriethoxide (EtO-V), niobium ethoxide (EtO-Nb), and tantalum ethoxide (EtO-Ta). Among these, the Nb2O5 film exhibited excellent transmittance, a high work function, and good conductivity, along with a more compact and uniform structure featuring fewer interfacial defects, which facilitated efficient charge extraction and transport. Furthermore, the deposition of a SAM of (2-(9H-carbazol-9-yl)ethyl)phosphonic acid (2PACz) on top of Nb2O5 further passivated defects, enhancing interfacial contact with the photoactive layer. The resulting inorganic-organic hybrid HTL of Nb2O5/2PACz demonstrated excellent compatibility with various photoactive blends, achieving impressive power conversion efficiencies of 19.44%, 19.18%, and 20.12% for the PM6:L8-BO, PM6:BTP-eC9, and D18:BTP-eC9 based organic solar cells, respectively. 20.12% is the best performance for bulk heterojunction organic solar cells with binary components as the photoactive layer.

3.
Sci Total Environ ; 941: 173678, 2024 Sep 01.
Artigo em Inglês | MEDLINE | ID: mdl-38848919

RESUMO

The incomplete degradation of antibiotics in water can produce intermediates that carry environmental risks and thus warrant concerns. In this study, the degradation of high concentrations of antibiotic sulfadiazine (SDZ) by advanced oxidation processes that leverage different reactive oxide species was systematically evaluated in terms of the influence of different degradation intermediates on the propagation of antibiotic resistance genes (ARGs). The ozone, persulfate, and photocatalytic oxidation systems for SDZ degradation are dominated by ozone, direct electron transfer, and singlet oxygen, hole, and superoxide radicals, respectively. These processes produce 15 intermediates via six degradation pathways. Notably, it was determined that three specific intermediates produced by the ozone and persulfate systems were more toxic than SDZ. In contrast, the photocatalytic system did not produce any intermediates with toxicity exceeding that of SDZ. Microcosm experiments combined with metagenomics confirmed significant changes in microbiota community structure after treatment with SDZ and its intermediates, including significant changes in the abundance of Flavobacterium, Dungenella, Archangium, and Comamonas. This treatment also led to the emergence of sulfonamide ARGs. The total abundance of sulfonamide ARGs was found to be positively correlated with residual SDZ concentration, with the lowest total abundance observed in the photocatalytic system. Additionally, the correlation analysis unveiled microbiota carrying sulfonamide ARGs.


Assuntos
Antibacterianos , Resistência Microbiana a Medicamentos , Oxirredução , Sulfadiazina , Poluentes Químicos da Água , Poluentes Químicos da Água/toxicidade , Resistência Microbiana a Medicamentos/genética , Antibacterianos/toxicidade , Biodegradação Ambiental
4.
Glob Chang Biol ; 30(4): e17283, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-38663017

RESUMO

Stratospheric ozone, which has been depleted in recent decades by the release of anthropogenic gases, is critical for shielding the biosphere against ultraviolet-B (UV-B) radiation. Although the ozone layer is expected to recover before the end of the 21st century, a hole over Antarctica continues to appear each year. Ozone depletion usually peaks between September and October, when fortunately, most Antarctic terrestrial vegetation and soil biota is frozen, dormant and protected under snow cover. Similarly, much marine life is protected by sea ice cover. The ozone hole used to close before the onset of Antarctic summer, meaning that most biota were not exposed to severe springtime UV-B fluxes. However, in recent years, ozone depletion has persisted into December, which marks the beginning of austral summer. Early summertime ozone depletion is concerning: high incident UV-B radiation coincident with snowmelt and emergence of vegetation will mean biota is more exposed. The start of summer is also peak breeding season for many animals, thus extreme UV-B exposure (UV index up to 14) may come at a vulnerable time in their life cycle. Climate change, including changing wind patterns and strength, and particularly declining sea ice, are likely to compound UV-B exposure of Antarctic organisms, through earlier ice and snowmelt, heatwaves and droughts. Antarctic field research conducted decades ago tended to study UV impacts in isolation and more research that considers multiple climate impacts, and the true magnitude and timing of current UV increases is needed.


Assuntos
Biota , Mudança Climática , Camada de Gelo , Perda de Ozônio , Neve , Regiões Antárticas , Animais , Raios Ultravioleta , Estações do Ano , Ozônio Estratosférico/análise
5.
Chemosphere ; 354: 141687, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-38484990

RESUMO

Biogas obtained from livestock manure is used as fuel for solid oxide fuel cells. Although H2S is a typical biogas, it is a fatal disadvantage for fuel-cell power generation and, thus, must be removed. In this study, we proposed an effective method for sulfide removal from water using a multi-hole dielectric barrier discharge (DBD) system. In this system, active species, such as ozone, ultraviolet rays, hydroxyl radicals, and hydrogen peroxide, were simultaneously generated. Under optimal conditions, dissolved sulfide (initial concentration: 120 mg/L) was completely degraded within 10 min in air plasma and 6 min in oxygen plasma. Changes in the physical properties of the sulfide-treated water were confirmed by measuring the pH, oxidation-reduction potential, and dissolved oxygen. Results of the by-product analysis showed that sulfide was converted into sulfate by reacting with a large amount of ozone, and the active species were emitted from the multi-hole DBD system. In summary, multi-hole DBD technology has demonstrated merit as a water-contaminant purification technology and for the removal of dissolved sulfide.


Assuntos
Ozônio , Poluentes Químicos da Água , Água , Biocombustíveis , Poluentes Químicos da Água/análise , Oxigênio/análise , Ozônio/química
6.
Materials (Basel) ; 17(6)2024 Mar 19.
Artigo em Inglês | MEDLINE | ID: mdl-38541549

RESUMO

Organic semiconductors (OSCs), especially small molecule semiconductors, have received increasing attention due to their good designability and variability. Phase transitions and interfacial properties have a decisive influence on device performance. Here, 2-Dodecyl-7-phenyl[1]benzothieno[3,2-b][1]benzothiophene (Ph-BTBT-12) devices are treated with low-power laser annealing, which is able to avoid the influence of the dewetting effect on the hole mobility of organic semiconductor materials. Ultraviolet ozone treatment and self-assembled monolayer treatment can improve the performance and stability of the device. Moreover, after low-temperature thermal annealing, the hole mobility of the device can even reach as high as 4.80 cm2 V-1 s-1, and we tested the optical response of the device to the ultraviolet wavelength and found that its maximum optical responsivity was 8.2 AW-1.

7.
Int J Mol Sci ; 25(2)2024 Jan 19.
Artigo em Inglês | MEDLINE | ID: mdl-38279235

RESUMO

The presence of the ozone hole increases the amount of UV radiation reaching a plant's surface, and UV-B radiation is an abiotic stress capable of affecting plant growth. Rhododendron chrysanthum Pall. (R. chrysanthum) grows in alpine regions, where strong UV-B radiation is present, and has been able to adapt to strong UV-B radiation over a long period of evolution. We investigated the response of R. chrysanthum leaves to UV-B radiation using widely targeted metabolomics and transcriptomics. Although phytohormones have been studied for many years in plant growth and development and adaptation to environmental stresses, this paper is innovative in terms of the species studied and the methods used. Using unique species and the latest research methods, this paper was able to add information to this topic for the species R. chrysanthum. We treated R. chrysanthum grown in a simulated alpine environment, with group M receiving no UV-B radiation and groups N and Q (externally applied abscisic acid treatment) receiving UV-B radiation for 2 days (8 h per day). The results of the MN group showed significant changes in phenolic acid accumulation and differential expression of genes related to phenolic acid synthesis in leaves of R. chrysanthum after UV-B radiation. We combined transcriptomics and metabolomics data to map the metabolic regulatory network of phenolic acids under UV-B stress in order to investigate the response of such secondary metabolites to stress. L-phenylalanine, L-tyrosine and phenylpyruvic acid contents in R. chrysanthum were significantly increased after UV-B radiation. Simultaneously, the levels of 3-hydroxyphenylacetic acid, 2-phenylethanol, anthranilate, 2-hydroxycinnamic acid, 3-hydroxycinnamic acid, α-hydroxycinnamic acid and 2-hydroxy-3-phenylpropanoic acid in this pathway were elevated in response to UV-B stress. In contrast, the study in the NQ group found that externally applied abscisic acid (ABA) in R. chrysanthum had greater tolerance to UV-B radiation, and phenolic acid accumulation under the influence of ABA also showed greater differences. The contents of 2-phenylethanol, 1-o-p-coumaroyl-ß-d-glucose, 2-hydroxy-3-phenylpropanoic acid, 3-(4-hydroxyphenyl)-propionic acid and 3-o-feruloylquinic ac-id-o-glucoside were significantly elevated in R. chrysanthum after external application of ABA to protect against UV-B stress. Taken together, these studies of the three groups indicated that ABA can influence phenolic acid production to promote the response of R. chrysanthum to UV-B stress, which provided a theoretical reference for the study of its complex molecular regulatory mechanism.


Assuntos
Glucose , Hidroxibenzoatos , Álcool Feniletílico , Fenilpropionatos , Rhododendron , Ácido Abscísico/metabolismo , Rhododendron/genética , Ácidos Cumáricos , Raios Ultravioleta
8.
J Chem Theory Comput ; 20(2): 873-881, 2024 Jan 23.
Artigo em Inglês | MEDLINE | ID: mdl-38175153

RESUMO

X-ray absorption spectra (XAS) of biradicaloid species are often thought to represent a challenge to theoretical methods. This has led to the testing of recently developed multireference techniques on the XAS of ozone, but reproduction of the experimental spectral profile has proven difficult. We utilize a minimal model consisting of a single configuration state function (CSF) per excited state to model core-level excitations of ozone, with the orbitals of each CSF optimized using the restricted open-shell Kohn-Sham (ROKS) method. This protocol leads to semiquantitative agreement with experimental XAS. In fact, we find that low-lying core-hole excited states in biradicaloids can be approximated with individual CSFs, despite the presence of multireference character in the ground state. We also report that the 1s → π* and 1s → σ* transitions have quite distinct widths for O3. This reveals the importance of sampling over a representative range of geometries from the vibrational ground state for properly assessing the accuracy of electronic structure methods against experiments instead of the popular procedure of uniformly broadening stick spectra at the equilibrium geometry.

9.
Small ; 20(14): e2306666, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-37990400

RESUMO

Carrier-selective passivating contacts using transition metal oxides (TMOs) have attracted great attention for crystalline silicon (c-Si) heterojunction solar cells recently. Among them, tantalum oxide (Ta2O5) exhibits outstanding advantages, such as a wide bandgap, good surface passivation, and a small conduction band offset with c-Si, which is typically used as an electron-selective contact layer. Interestingly, it is first demonstrated that solution-processed Ta2O5 films exhibit a high hole selectivity, which blocks electrons and promotes hole transport simultaneously. Through the ozone pre-treatment of Ta2O5/p-Si interface and optimization of the film thickness (≈9 nm), the interfacial recombination is suppressed and the contact resistivity is reduced from 178.0 to 29.3 mΩ cm2. Moreover, the Sn4+ doping increases both the work function and oxygen vacancies of the film, contributing to the improved hole-selective contact performance. As a result, the photoelectric conversion efficiencies of Ta2O5/p-Si heterojunction solar cells are significantly improved from 14.84% to 18.47%, with a high thermal stability up to 300 °C. The work has provided a feasible strategy to explore new features of TMOs for carrier-selective contact applications, that is, bipolar carrier transport properties.

10.
Nanomaterials (Basel) ; 13(23)2023 Nov 27.
Artigo em Inglês | MEDLINE | ID: mdl-38063730

RESUMO

Ultraviolet-ozone (UV-O3) treatment is a simple but effective technique for surface cleaning, surface sterilization, doping, and oxidation, and is applicable to a wide range of materials. In this study, we investigated how UV-O3 treatment affects the optical and electrical properties of molybdenum disulfide (MoS2), with and without the presence of a dielectric substrate. We performed detailed photoluminescence (PL) measurements on 1-7 layers of MoS2 with up to 8 min of UV-O3 exposure. Density functional theory (DFT) calculations were carried out to provide insight into oxygen-MoS2 interaction mechanisms. Our results showed that the influence of UV-O3 treatment on PL depends on whether the substrate is present, as well as the number of layers. Additionally, 4 min of UV-O3 treatment was found to be optimal to produce p-type MoS2, while maintaining above 80% of the PL intensity and the emission wavelength, compared to pristine flakes (intrinsically n-type). UV-O3 treatment for more than 6 min not only caused a reduction in the electron density but also deteriorated the hole-dominated transport. It is revealed that the substrate plays a critical role in the manipulation of the electrical and optical properties of MoS2, which should be considered in future device fabrication and applications.

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