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1.
Proc Natl Acad Sci U S A ; 120(52): e2309786120, 2023 Dec 26.
Artículo en Inglés | MEDLINE | ID: mdl-38109550

RESUMEN

Many sub-Neptune exoplanets have been believed to be composed of a thick hydrogen-dominated atmosphere and a high-temperature heavier-element-dominant core. From an assumption that there is no chemical reaction between hydrogen and silicates/metals at the atmosphere-interior boundary, the cores of sub-Neptunes have been modeled with molten silicates and metals (magma) in previous studies. In large sub-Neptunes, pressure at the atmosphere-magma boundary can reach tens of gigapascals where hydrogen is a dense liquid. A recent experiment showed that hydrogen can induce the reduction of Fe[Formula: see text] in (Mg,Fe)O to Fe[Formula: see text] metal at the pressure-temperature conditions relevant to the atmosphere-interior boundary. However, it is unclear whether Mg, one of the abundant heavy elements in the planetary interiors, remains oxidized or can be reduced by H. Our experiments in the laser-heated diamond-anvil cell found that heating of MgO + Fe to 3,500 to 4,900 K (close to or above their melting temperatures) in an H medium leads to the formation of Mg[Formula: see text]FeH[Formula: see text] and H[Formula: see text]O at 8 to 13 GPa. At 26 to 29 GPa, the behavior of the system changes, and Mg-H in an H fluid and H[Formula: see text]O were detected with separate FeH[Formula: see text]. The observations indicate the dissociation of the Mg-O bond by H and subsequent production of hydride and water. Therefore, the atmosphere-magma interaction can lead to a fundamentally different mineralogy for sub-Neptune exoplanets compared with rocky planets. The change in the chemical reaction at the higher pressures can also affect the size demographics (i.e., "radius cliff") and the atmosphere chemistry of sub-Neptune exoplanets.

2.
Ear Hear ; 45(3): 658-665, 2024.
Artículo en Inglés | MEDLINE | ID: mdl-38178304

RESUMEN

OBJECTIVES: Otitis media is one of the most important causes of hearing loss at an early age. Effective vaccination with the routine 7-valent pneumococcal conjugate vaccine (PCV-7) was introduced in 2000. It has been gradually replaced by the pneumococcal nontypeable Haemophilus influenzae protein D conjugate vaccine or the higher-valent 13-valent PCV (PCV-13) since 2010. Data on the change in otitis media burden in recent years are sparse at the global, regional, and national levels. DESIGN: The Global Burden of Disease 2019 study was used to evaluate the prevalence, incidence, mortality, disability-adjusted life year (DALY) rates, and the average annual percentage changes (AAPCs) in otitis media in geographic populations worldwide from 1990 to 2019. These global trends were further analyzed by subgroup (age, sex, and sociodemographic index [SDI]). RESULTS: Globally, the all-age rate of prevalence (AAPC = -0.7, 95% confidence interval [CI] = -0.7 to -0.8), DALYs (AAPC = -1.0, 95% CI = -1.1 to -1.0), and mortality (AAPC = -6.8, 95% CI = -7.3 to -6.4) from otitis media decreased constantly between 1990 and 2019. The all-age rate of incidence decreased sharply between 2000 and 2009 with an AAPC of -1.2 (95% CI = -1.4 to -0.9) and continued the downward trend between 2010 and 2019 (AAPC = -0.2, 95% CI = -0.3 to -0.1). In 2019, children aged 1 to 4 years old had the highest incidence at 29,127.3 per 100,000 population, while young adults under 30 years old accounted for 91.3% of the incident cases. Individuals living in middle-SDI countries had the largest increase in the incidence of otitis media, with an AAPC of 0.3 (95% CI = 0.3 to 0.3) between 1990 and 2019. The incidence and DALYs from otitis media decreased with increasing SDI. Regionally, the largest increase in incidence was observed in high-income Asia Pacific, Eastern Europe, and Western Sub-Saharan Africa between 1990 and 2019. Nationally, the largest increase in the incidence of otitis media was observed in the Republic of Korea, with an AAPC of 0.8 (95% CI = 0.6 to 1.1) in the same time period. CONCLUSIONS: There have been successful previous endeavors to reduce DALYs and mortality attributed to otitis media on a global scale. The worldwide incidence of otitis media experienced a sharp decline following the introduction of PCV-7 in 2000, and this downward trend persisted in subsequent years with the adoption of PCV-13/pneumococcal nontypeable Haemophilus influenzae protein D conjugate vaccine. Continual epidemiological surveillance of otitis media's global trends, pathogen distribution, and resistance patterns remains imperative.


Asunto(s)
Otitis Media , Niño , Adulto Joven , Humanos , Lactante , Preescolar , Adulto , Vacunas Conjugadas , Otitis Media/epidemiología , Incidencia , Investigación , República de Corea , Años de Vida Ajustados por Calidad de Vida
3.
Small ; 19(26): e2302295, 2023 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-37194952

RESUMEN

Although the electrocatalytic nitrate reduction reaction (NO3 - RR) is an attractive NH3 synthesis route, it suffers from low yield due to the lack of efficient catalysts. Here, this work reports a novel grain boundary (GB)-rich Sn-Cu catalyst, derived from in situ electroreduction of Sn-doped CuO nanoflower, for effectively electrochemical converting NO3 - to NH3 . The optimized Sn1% -Cu electrode achieves a high NH3 yield rate of 1.98 mmol h-1 cm-2 with an industrial-level current density of -425 mA cm-2 at -0.55 V versus a reversible hydrogen electrode (RHE) and a maximum Faradaic efficiency of 98.2% at -0.51 V versus RHE, outperforming the pure Cu electrode. In situ Raman and attenuated total reflection Fourier transform infrared spectroscopies reveal the reaction pathway of NO3 - RR to NH3 by monitoring the adsorption property of reaction intermediates. Density functional theory calculations clarify that the high-density GB active sites and the competitive hydrogen evolution reaction (HER) suppression induced by Sn doping synergistically promote highly active and selective NH3 synthesis from NO3 - RR. This work paves an avenue for efficient NH3 synthesis over Cu catalyst by in situ reconstruction of GB sites with heteroatom doping.

4.
Environ Sci Technol ; 57(1): 666-673, 2023 01 10.
Artículo en Inglés | MEDLINE | ID: mdl-36445010

RESUMEN

Ammunition wastewater contains toxic nitrated explosives like RDX and oxyanions like nitrate and perchlorate. Its treatment is challenged by low efficiency due to contaminant recalcitrance and high cost due to multiple processes needed for separately removing different contaminant types. This paper reports a H2-based low-energy strategy featuring the treatment of explosives via catalytic denitration followed by microbial mineralization coupled with oxyanion reduction. After a nitrate- and perchlorate-reducing biofilm incapable of RDX biodegradation was coated with palladium nanoparticles (Pd0NPs), RDX was rapidly denitrated with a specific catalytic activity of 8.7 gcat-1 min-1, while biological reductions of nitrate and perchlorate remained efficient. In the subsequent 30-day continuous test, >99% of RDX, nitrate, and perchlorate were coremoved, and their effluent concentrations were below their respective regulation levels. Detected intermediates and shallow metagenome analysis suggest that the intermediates after Pd-catalytic denitration of RDX ultimately were enzymatically utilized by the nitrate- and perchlorate-reducing bacteria as additional electron donor sources.


Asunto(s)
Sustancias Explosivas , Nanopartículas del Metal , Contaminantes Químicos del Agua , Purificación del Agua , Sustancias Explosivas/análisis , Sustancias Explosivas/metabolismo , Percloratos/análisis , Percloratos/metabolismo , Nitratos/análisis , Nitratos/metabolismo , Contaminantes Químicos del Agua/análisis , Paladio/análisis , Reactores Biológicos/microbiología
5.
Microsc Microanal ; 29(4): 1307-1314, 2023 Jul 25.
Artículo en Inglés | MEDLINE | ID: mdl-37488821

RESUMEN

Photonic modes in dielectric nanostructures, e.g., wide gap semiconductor like CeO2 (ceria), have the potential for various applications such as information transmission and sensing technology. To fully understand the properties of such phenomenon at the nanoscale, electron energy-loss spectroscopy (EELS) in a scanning transmission electron microscope was employed to detect and explore photonic modes in well-defined ceria nanocubes. To facilitate the interpretation of the observations, EELS simulations were performed with finite-element methods. The simulations allow the electric and magnetic field distributions associated with different modes to be determined. A simple analytical eigenfunction model was also used to estimate the energy of the photonic modes. In addition, by comparing various spectra taken at different location relative to the cube, the effect of the surrounding environment on the modes could be sensed. This work gives a high-resolution description of the photonic modes' properties in nanostructures, while demonstrating the advantage of EELS in characterizing optical phenomena locally.

6.
Angew Chem Int Ed Engl ; 62(20): e202214322, 2023 May 08.
Artículo en Inglés | MEDLINE | ID: mdl-36696269

RESUMEN

The development of facile methodologies to afford robust supported metal nanocatalysts under mild conditions is highly desirable yet challenging, particularly via strong metal-support interactions (SMSI) construction. State-of-the-art approaches capable of generating SMSI encapsulation mainly focus on high temperature annealing in reductive/oxidative atmosphere. Herein, ultra-stable metal nanocatalysts based on SMSI construction were produced by leveraging the instantaneous high-energy input from ultrasonication under ambient conditions in H2 O, which could rapidly afford abundant active intermediates, Ti3+ ions, and oxygen vacancies within the scaffolds to induce the SMSI overlayer formation. The encapsulation degree could be tuned and controlled via the reducibility of the solvents and the ultrasonication parameters. This facile and efficient approach could be further extended to diverse metal oxide supports and noble metal NPs leading to enhanced performance in hydrogenation reactions and CO2 conversion.

7.
Environ Sci Technol ; 56(24): 18030-18040, 2022 12 20.
Artículo en Inglés | MEDLINE | ID: mdl-36383359

RESUMEN

More food production required to feed humans will require intensive use of herbicides to protect against weeds. The widespread application and persistence of herbicides pose environmental risks for nontarget species. Elemental-palladium nanoparticles (Pd0NPs) are known to catalyze reductive dehalogenation of halogenated organic pollutants. In this study, the reductive conversion of 2,4-dichlorophenoxyacetic acid (2,4-D) was evaluated in a H2-based membrane catalyst-film reactor (H2-MCfR), in which Pd0NPs were in situ-synthesized as the catalyst film and used to activate H2 on the surface of H2-delivery membranes. Batch kinetic experiments showed that 99% of 2,4-D was removed and converted to phenoxyacetic acid (POA) within 90 min with a Pd0 surface loading of 20 mg Pd/m2, achieving a catalyst specific activity of 6.6 ± 0.5 L/g-Pd-min. Continuous operation of the H2-MCfR loaded with 20 mg Pd/m2 sustained >99% removal of 50 µM 2,4-D for 20 days. A higher Pd0 surface loading, 1030 mg Pd/m2, also enabled hydrosaturation and hydrolysis of POA to cyclohexanone and glycolic acid. Density functional theory identified the reaction mechanisms and pathways, which involved reductive hydrodechlorination, hydrosaturation, and hydrolysis. Molecular electrostatic potential calculations and Fukui indices suggested that reductive dehalogenation could increase the bioavailability of herbicides. Furthermore, three other halogenated herbicides─atrazine, dicamba, and bromoxynil─were reductively dehalogenated in the H2-MCfR. This study documents a promising method for the removal and detoxification of halogenated herbicides in aqueous environments.


Asunto(s)
Herbicidas , Nanopartículas del Metal , Humanos , Paladio/metabolismo , Catálisis , Ácido 2,4-Diclorofenoxiacético
8.
Sensors (Basel) ; 22(19)2022 Oct 09.
Artículo en Inglés | MEDLINE | ID: mdl-36236759

RESUMEN

The fusion of light detection and ranging (LiDAR) and inertial measurement unit (IMU) sensing information can effectively improve the environment modeling and localization accuracy of navigation systems. To realize the spatiotemporal unification of data collected by the IMU and the LiDAR, a two-step spatiotemporal calibration method combining coarse and fine is proposed. The method mainly includes two aspects: (1) Modeling continuous-time trajectories of IMU attitude motion using B-spline basis functions; the motion of the LiDAR is estimated by using the normal distributions transform (NDT) point cloud registration algorithm, taking the Hausdorff distance between the local trajectories as the cost function and combining it with the hand-eye calibration method to solve the initial value of the spatiotemporal relationship between the two sensors' coordinate systems, and then using the measurement data of the IMU to correct the LiDAR distortion. (2) According to the IMU preintegration, and the point, line, and plane features of the lidar point cloud, the corresponding nonlinear optimization objective function is constructed. Combined with the corrected LiDAR data and the initial value of the spatiotemporal calibration of the coordinate systems, the target is optimized under the nonlinear graph optimization framework. The rationality, accuracy, and robustness of the proposed algorithm are verified by simulation analysis and actual test experiments. The results show that the accuracy of the proposed algorithm in the spatial coordinate system relationship calibration was better than 0.08° (3δ) and 5 mm (3δ), respectively, and the time deviation calibration accuracy was better than 0.1 ms and had strong environmental adaptability. This can meet the high-precision calibration requirements of multisensor spatiotemporal parameters of field robot navigation systems.

9.
J Am Chem Soc ; 143(23): 8521-8526, 2021 Jun 16.
Artículo en Inglés | MEDLINE | ID: mdl-34081447

RESUMEN

Strong metal-support interaction (SMSI) construction is a pivotal strategy to afford thermally robust nanocatalysts in industrial catalysis, but thermally induced reactions (>300 °C) in specific gaseous atmospheres are generally required in traditional procedures. In this work, a photochemistry-driven methodology was demonstrated for SMSI construction under ambient conditions. Encapsulation of Pd nanoparticles with a TiOx overlayer, the presence of Ti3+ species, and suppression of CO adsorption were achieved upon UV irradiation. The key lies in the generation of separated photoinduced reductive electrons (e-) and oxidative holes (h+), which subsequently trigger the formation of Ti3+ species/oxygen vacancies (Ov) and then interfacial Pd-Ov-Ti3+ sites, affording a Pd/TiO2 SMSI with enhanced catalytic hydrogenation efficiency. The as-constructed SMSI layer was reversible, and the photodriven procedure could be extended to Pd/ZnO and Pt/TiO2.

10.
Small ; 17(16): e2004579, 2021 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-33464724

RESUMEN

The development of novel single atom catalyst (SAC) is highly desirable in organic synthesis to achieve the maximized atomic efficiency. Here, a Co-based SAC on nitrogen-doped graphene (SACo@NG) with high Co content of 4.1 wt% is reported. Various characterization results suggest that the monodispersed Co atoms are coordinated with N atoms to form robust and highly effective catalytic centers to activate peroxymonosulfate (PMS) for organic selective oxidation. The catalytic performance of the SACo@NG/PMS system is conducted on the selective oxidation of benzyl alcohol (BzOH) showing high efficiency with over 90% conversion and benzaldehyde selectivity within 180 min under mild conditions. Both radical and non-radical processes occurred in the selective oxidation of BzOH, but the non-radical oxidation plays the dominant role which is accomplished by the adsorption of BzOH/PMS on the surface of SACo@NG and the subsequent electron transfer through the carbon matrix. This work provides new insights to the preparation of efficient transition metal-based single atom catalysts and their potential applications in PMS mediated selective oxidation of alcohols.

11.
Nat Mater ; 19(8): 867-873, 2020 Aug.
Artículo en Inglés | MEDLINE | ID: mdl-32152562

RESUMEN

The electronic, optical and chemical properties of two-dimensional transition metal dichalcogenides strongly depend on their three-dimensional atomic structure and crystal defects. Using Re-doped MoS2 as a model system, here we present scanning atomic electron tomography as a method to determine three-dimensional atomic positions as well as positions of crystal defects such as dopants, vacancies and ripples with a precision down to 4 pm. We measure the three-dimensional bond distortion and local strain tensor induced by single dopants. By directly providing these experimental three-dimensional atomic coordinates to density functional theory, we obtain more accurate electronic band structures than derived from conventional density functional theory calculations that relies on relaxed three-dimensional atomic coordinates. We anticipate that scanning atomic electron tomography not only will be generally applicable to determine the three-dimensional atomic coordinates of two-dimensional materials, but also will enable ab initio calculations to better predict the physical, chemical and electronic properties of these materials.

12.
Inorg Chem ; 60(14): 10398-10414, 2021 Jul 19.
Artículo en Inglés | MEDLINE | ID: mdl-34236171

RESUMEN

A series of V-substituted α-MnO2 (KxMn8-yVyO16·nH2O, y = 0, 0.2, 0.34, 0.75) samples were successfully synthesized without crystalline or amorphous impurities, as evidenced by X-ray diffraction (XRD) and Raman spectroscopy. Transmission electron microscopy (TEM) revealed a morphological evolution from nanorods to nanoplatelets as V-substitution increased, while electron-energy loss spectroscopy (EELS) confirmed uniform distribution of vanadium within the materials. Rietveld refinement of synchrotron XRD showed an increase in bond lengths and a larger range of bond angles with increasing V-substitution. X-ray absorption spectroscopy (XAS) of the as-prepared materials revealed the V valence to be >4+ and the Mn valence to decrease with increasing V content. Upon electrochemical lithiation, increasing amounts of V were found to preserve the Mn-Mnedge relationship at higher depths of discharge, indicating enhanced structural stability. Electrochemical testing showed the y = 0.75 V-substituted sample to deliver the highest capacity and capacity retention after 50 cycles. The experimental findings were consistent with the predictions of density functional theory (DFT), where the V centers impart structural stability to the manganese oxide framework upon lithiation. The enhanced electrochemistry of the y = 0.75 V-substituted sample is also attributed to its smaller crystallite size in the form of a nanoplatelet morphology, which promotes facile ion access via reduced Li-ion diffusion path lengths.

13.
J Gastroenterol Hepatol ; 36(3): 721-730, 2021 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-32720371

RESUMEN

BACKGROUND AND AIM: Esophageal carcinoma has been regarded as one of the top 10 common malignancies globally. Esophageal squamous cell carcinoma (ESCC) is an important subtype of esophageal carcinoma with approximately 20% survival rate. Long noncoding RNAs were documented to regulate the occurrence or progression of several tumors. However, neither the biological role nor the molecular mechanism of LINC00467 has been explored. This research is aimed to investigating the regulatory mechanism of LINC00467 in ESCC. METHODS: In this study, a series of experiments including reverse transcription-quantitative polymerase chain reaction, Cell Counting Kit-8, luciferase reporter, western blot, and RNA immunoprecipitation were designed and conducted to explore the potential function and mechanism of LINC00467 in ESCC. RESULTS: According to experimental results, we found out upregulated LINC00467 improved cell proliferation, but hindered cell apoptosis. In mechanism, miR-485-5p was predicted, screened out, and validated to combine with LINC00467, which displayed lower expression in ESCC. Additionally, miR-485-5p negatively regulated and directly targeted DPAGT1. Rescue assays suggested that DPAGT1 amplification was able to recover the influence of LINC00467 deficiency on cell proliferation and apoptosis. Furthermore, knockdown of LINC00467 suppressed tumor growth in vivo. CONCLUSION: We proved that LINC00467 acted as an oncogene in ESCC by accelerating cell proliferation and preventing cell apoptosis via miR-485-5p/DPAGT1 axis. This may provide a potential diagnostic marker for ESCC treatment.


Asunto(s)
Apoptosis/genética , Proliferación Celular/genética , Neoplasias Esofágicas/genética , Neoplasias Esofágicas/patología , Carcinoma de Células Escamosas de Esófago/genética , Carcinoma de Células Escamosas de Esófago/patología , MicroARNs/metabolismo , N-Acetilglucosaminiltransferasas/metabolismo , Oncogenes , ARN Largo no Codificante/fisiología , Biomarcadores de Tumor/metabolismo , Línea Celular Tumoral , Neoplasias Esofágicas/diagnóstico , Carcinoma de Células Escamosas de Esófago/diagnóstico , Humanos
14.
Nano Lett ; 20(7): 5482-5489, 2020 Jul 08.
Artículo en Inglés | MEDLINE | ID: mdl-32515969

RESUMEN

Single-atom site catalysts (SACs) have aroused enormous attention and brought about new opportunities for many applications. Herein, we report a versatile strategy to rhodium (Rh) SAC by a facile cation exchange reaction. Remarkably, the Rh SAC modified CuO nanowire arrays on copper foam (Rh SAC-CuO NAs/CF) show unprecedented alkaline oxygen evolution reaction (OER) activity with a high current density of 84.5 mA cm-2@1.5 V vs reversible hydrogen electrode (RHE), 9.7 times that of Ir/C/CF. More strikingly, when used as an anode and a cathode for overall water splitting, the Rh SAC-CuO NAs/CF can achieve 10 mA cm-2 at only 1.51 V. Density functional theory calculations reveal that the high OER and HER intrinsic catalytic activities result from moderate adsorption energy of intermediates on Rh SAC. Finally, we demonstrate the general synthesis of different single-atom noble-metal catalysts on CuO NAs (M SAC-CuO NAs/CF, where M = Ru, Ir, Os, and Au).

15.
Nano Lett ; 20(2): 1252-1261, 2020 Feb 12.
Artículo en Inglés | MEDLINE | ID: mdl-31887051

RESUMEN

Lithium-sulfur (Li-S) batteries are promising next-generation energy storage technologies due to their high theoretical energy density, environmental friendliness, and low cost. However, low conductivity of sulfur species, dissolution of polysulfides, poor conversion from sulfur reduction, and lithium sulfide (Li2S) oxidation reactions during discharge-charge processes hinder their practical applications. Herein, under the guidance of density functional theory calculations, we have successfully synthesized large-scale single atom vanadium catalysts seeded on graphene to achieve high sulfur content (80 wt % sulfur), fast kinetic (a capacity of 645 mAh g-1 at 3 C rate), and long-life Li-S batteries. Both forward (sulfur reduction) and reverse reactions (Li2S oxidation) are significantly improved by the single atom catalysts. This finding is confirmed by experimental results and consistent with theoretical calculations. The ability of single metal atoms to effectively trap the dissolved lithium polysulfides (LiPSs) and catalytically convert the LiPSs/Li2S during cycling significantly improved sulfur utilization, rate capability, and cycling life. Our work demonstrates an efficient design pathway for single atom catalysts and provides solutions for the development of high energy/power density Li-S batteries.

16.
Angew Chem Int Ed Engl ; 60(18): 9953-9958, 2021 Apr 26.
Artículo en Inglés | MEDLINE | ID: mdl-33524205

RESUMEN

The successful integration or hybridization of perovskite oxides with their halide cousins would enable the formation of both multi-anionic and multi-cationic solid solutions with unique metal-ion sites and synergistic properties that could potentially surpass the performance of classic perovskites. However, such solid solutions had not been produced previously owing to their distinct formation energies and different synthesis conditions. Solid solutions combining perovskite oxides with fluorides were produced in this study by mechanochemical synthesis. The obtained perovskite oxide-halide solid solutions had highly mixed elements and valences, uniform element distributions, and single-phase crystalline structures. The solid solution with an optimized combination of oxides and fluorides exhibited enhanced catalytic performance in the oxygen evolution reaction.

17.
J Am Chem Soc ; 142(2): 962-972, 2020 01 15.
Artículo en Inglés | MEDLINE | ID: mdl-31852179

RESUMEN

The pursuit of efficient hydrogenation nanocatalysts with a desirable selectivity toward intricate substrates is state-of-the-art research but remains a formidable challenge. Herein, we report a series of novel PdCdx nanocubes (NCs) for ultraselective hydrogenation reactions with flexible tuning features. Obtaining a desirable conversion level of the substrates (e.g., 4-nitrophenylacetylene (NPA), 4-nitrobenzaldehyde (NBAD), and 4-nitrostyrene (NS)) and competitive selectivity for all potential hydrogenation products have been achieved one by one under optimized hydrogenation conditions. The performance of these PdCdx NCs displays an evident dependence on both the composition and the use of Cd and a need for a distinct hydrogen source (H2 or HCOONH4). Additionally, for the selectivity of hydrogen to be suitably high, the morphology of the NCs has a very well-defined effect. Density functional theory calculations confirmed the variation of adsorption energy for the substrate and hydrogenation products by carefully controlled introduction of Cd, leading to a desirable level of selectivity for all potential hydrogenation products. The PdCdx NCs also exhibit excellent reusability with negligible activity/selectivity decay and structural/composition changes after consecutive reactions. The present study provides an advanced strategy for the rational design of superior hydrogenation nanocatalysts to achieve a practical application for desirable and selective hydrogenation reaction efficiency.

18.
Inorg Chem ; 59(6): 3783-3793, 2020 Mar 16.
Artículo en Inglés | MEDLINE | ID: mdl-32129071

RESUMEN

A series of tunnel structured V-substituted silver hollandite (Ag1.2VxMn8-xO16, x = 0-1.4) samples is prepared and characterized through a combination of synchrotron X-ray diffraction (XRD), synchrotron X-ray absorption spectroscopy (XAS), laboratory Raman spectroscopy, and electron microscopy measurements. The oxidation states of the individual transition metals are characterized using V and Mn K-edge XAS data indicating the vanadium centers exist as V5+, and the Mn oxidation state decreases with increased V substitution to balance the charge. Scanning transmission electron microscopy of reduced materials shows reduction-displacement of silver metal at high levels of lithiation. In lithium batteries, the V-substituted tunneled manganese oxide materials reveal previously unseen reversible nonaqueous Ag electrochemistry and exhibit up to 2.5× higher Li storage capacity relative to their unsubstituted counterparts. The highest capacity was observed for the Ag1.2(V0.8Mn7.2)O16·0.8H2O material with an intermediate level of V substitution, likely due to a combination of the atomic composition, the morphology of the particle, and the homogeneous distribution of the active material within the electrode structure where factors over multiple length scales contribute to the electrochemistry.

19.
J Am Chem Soc ; 141(35): 13977-13986, 2019 Sep 04.
Artículo en Inglés | MEDLINE | ID: mdl-31436416

RESUMEN

The chemical reactivity and/or the diffusion of Ag atoms or ions during thermal processing can cause irreversible structural damage, hindering the application of Ag nanowires (NWs) in transparent conducting films and other applications that make use of the material's nanoscale properties. Here, we describe a simple and effective method for growing monolayer SnO2 on the surface of Ag nanowires under ambient conditions, which protects the Ag nanowires from chemical and structural damage. Our results show that Sn2+ and Ag atoms undergo a redox reaction in the presence of water. First-principle simulations suggest a reasonable mechanism for SnO2 formation, showing that the interfacial polarization of the silver by the SnO2 can significantly reduce the affinity of Ag to O2, thereby greatly reducing the oxidation of the silver. The corresponding values (for example, before coating: 17.2 Ω/sq at 86.4%, after coating: 19.0 Ω/sq at 86.6%) show that the deposition of monolayer SnO2 enables the preservation of high transparency and conductivity of Ag. In sharp contrast to the large-scale degradation of pure Ag-NW films including the significant reduction of its electrical conductivity when subjected to a series of harsh corrosion environments, monolayer SnO2 coated Ag-NW films survive structurally and retain their electrical conductivity. Consequently, the thermal, electrical, and chemical stability properties we report here, and the simplicity of the technology used to achieve them, are among the very best reported for transparent conductor materials to date.

20.
J Am Chem Soc ; 141(22): 8928-8936, 2019 Jun 05.
Artículo en Inglés | MEDLINE | ID: mdl-31090414

RESUMEN

The failure to achieve stable Ohmic contacts in two-dimensional material devices currently limits their promised performance and integration. Here we demonstrate that a phase transformation in a region of a layered semiconductor, PdSe2, can form a contiguous metallic Pd17Se15 phase, leading to the formation of seamless Ohmic contacts for field-effect transistors. This phase transition is driven by defects created by exposure to an argon plasma. Cross-sectional scanning transmission electron microscopy is combined with theoretical calculations to elucidate how plasma-induced Se vacancies mediate the phase transformation. The resulting Pd17Se15 phase is stable and shares the same native chemical bonds with the original PdSe2 phase, thereby forming an atomically sharp Pd17Se15/PdSe2 interface. These Pd17Se15 contacts exhibit a low contact resistance of ∼0.75 kΩ µm and Schottky barrier height of ∼3.3 meV, enabling nearly a 20-fold increase of carrier mobility in PdSe2 transistors compared to that of traditional Ti/Au contacts. This finding opens new possibilities in the development of better electrical contacts for practical applications of 2D materials.

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