RESUMEN
Although it is generally acknowledged that transition metals at high oxidation states represent superior oxygen evolution reaction (OER) activity, the preparation and stability of such a high-valence state are still a challenge, which requires relatively harsh reaction conditions and is unstable under ambient conditions. Herein, we report the formation of trivalent nickel (Ni3+) in laser-fabricated nickel oxides induced by polyaniline (PANI) under electrochemical activation via a significant charge transfer between Ni and N, as confirmed by X-ray photoelectron spectroscopy and density functional theory calculations. Thereafter, the presence of Ni3+ and the improved conductivity by PANI effectively increase the electrochemical OER activity of the samples together with excellent long-term stability. This work provides new insights for the rational manufacture of high-valence metal for electrochemical reactions.
RESUMEN
Interlayer charge-transfer (CT) in 2D atomically thin vertical stacks heterostructures offers an unparalleled new approach to regulation of device performance in optoelectronic and photonics applications. Despite the fact that the saturable absorption (SA) in 2D heterostructures involves highly efficient optical modulation in the space and time domain, the lack of explicit SA regulation mechanism at the nanoscale prevents this feature from realizing nanophotonic modulation. Here, the enhancement of SA response via CT in WS2/graphene vertical heterostructure is proposed and the related mechanism is demonstrated through simulations and experiments. Leveraging this mechanism, CT-induced SA enhancement can be expanded to a wide range of nonlinear optical modulation applications for 2D materials. The results suggest that CT between 2D heterostructures enables efficient nonlinear optical response regulation.
RESUMEN
The popular single-atom catalyst (SAC) Fe-N4 is generally believed to be an excellent oxygen reduction reaction (ORR) electrocatalyst, which is less active in the oxygen evolution reaction (OER). Herein, FeM-N6 configuration catalysts (M = Fe, Co, Ni, Cu, Ag, and Au) were constructed for the oxygen evolution reaction by embedding M dopants on Fe-N4 systems based on the density functional theory. The electronic structure analysis reveals that the Fe-M metal interactions play dominant roles in regulating the d orbital distributions of Fe sites, which in turn alter the catalytic OER performance. Subsequent thermodynamic results indicate that the potential-determining step (PDS) for all catalysts is the formation of OOH*, which exhibits a tendency of decreased overpotentials with enhanced metal interactions. Apart from these, the effects of axial ligands on the OER activity of the catalysts in practical conditions were considered. Generally, most of the axial ligands are found to be thermodynamically favorable for the OER process. Interestingly, a competitive relationship of the electrons from the d orbital of Fe sites was found between the axial ligand and the adsorbed intermediate species during the reaction, which raises the energy barrier for OH* to O* conversion and can even alter the PDS in certain cases. The present work sheds new light on the design of future high-performance OER catalysts.
RESUMEN
In this work, a series of morphology-controlled NiFeOOH nanosheets were directly developed through a one-step mild in-situ acid-etching hydrothermal process. Benefiting from the ultrathin interwoven geometric structure and most favorable electron transport structure, the NiFeOOH nanosheets synthesized under 120 °C (denoted as NiFe_120) exhibited the optimal electrochemical performance for urea oxidation reaction (UOR). An overpotential of merely 1.4â V was required to drive the current density of 100â mA cm-2 , and the electrochemical activity remains no change even after 5000â cycles' accelerated degradation test. Moreover, the assembled urea electrolysis set by using the NiFe_120 as bifunctional catalysts presented a reduced potential of 1.573â V at 10â mA cm-2 , which was much lower than that of overall water splitting. We believe this work will lay a foundation for developing high-performance urea oxidation catalysts for the large-scale production of hydrogen and purification of urea-rich sewage.
RESUMEN
The emergence of superconductivity in doped insulators such as cuprates and pnictides coincides with their doping-driven insulator-metal transitions. Above the critical doping threshold, a metallic state sets in at high temperatures, while superconductivity sets in at low temperatures. An unanswered question is whether the formation of Cooper pairsin a well-established metal will inevitably transform the host material into a superconductor, as manifested by a resistance drop. Here, this question is addressed by investigating the electrical transport in nanoscale rings (full loops) and half loops manufactured from heavily boron-doped diamond. It is shown that in contrast to the diamond half-loops (DHLs) exhibiting a metal-superconductor transition, the diamond nanorings (DNRs) demonstrate a sharp resistance increase up to 430% and a giant negative "magnetoresistance" below the superconducting transition temperature of the starting material. The finding of the unconventional giant negative "magnetoresistance", as distinct from existing categories of magnetoresistance, that is, the conventional giant magnetoresistance in magnetic multilayers, the colossal magnetoresistance in perovskites, and the geometric magnetoresistance in semiconductor-metal hybrids, reveals the transformation of the DNRs from metals to bosonic semiconductors upon the formation of Cooper pairs. DNRs like these could be used to manipulate Cooper pairs in superconducting quantum devices.
RESUMEN
Population pharmacokinetic (PopPK) models of posaconazole have been established to promote the precision dosing. However, the performance of these models extrapolated to other centers has not been evaluated. This study aimed to conduct an external evaluation of published posaconazole PopPK models to evaluate their predictive performance. Posaconazole PopPK models screened from the PubMed and MEDLINE databases were evaluated using an external dataset of 213 trough concentration samples collected from 97 patients. Their predictive performance was evaluated by prediction-based diagnosis (prediction error), simulation-based diagnosis (visual predictive check), and Bayesian forecasting. In addition, external cohorts with and without proton pump inhibitor were used to evaluate the models respectively. Ten models suitable for the external dataset were finally included into the study. In prediction-based diagnostics, none of the models met pre-determined criteria for predictive indexes. Only M4, M6, and M10 demonstrated favorable simulations in visual predictive check. The prediction performance of M5, M7, M8, and M9 evaluated using the cohort without proton pump inhibitor showed a significant improvement compared to that evaluated using the whole cohort. Consistent with our expectations, Bayesian forecasting significantly improved the predictive per-formance of the models with two or three prior observations. In general, the applicability of these published posaconazole PopPK models extrapolated to our center was unsatisfactory. Prospective studies combined with therapeutic drug monitoring are needed to establish a PopPK model for posaconazole in the Chinese population to promote individualized dosing.
RESUMEN
In this paper, a Ni and diamond-like carbon (DLC)-modified TiO2 nanotube composite electrode was prepared as a glucose sensor using a combination of an anodizing process, electrodeposition, and magnetron sputtering. The composition and morphology of the electrodes were analyzed by a scanning electron microscope and energy dispersive X-ray detector, and the electrochemical glucose oxidation performance of the electrodes was evaluated by cyclic voltammetry and chronoamperometry. The results show that the Ni-coated DLC-modified TiO2 electrode has better electrocatalytic oxidation performance for glucose than pure TiO2 and electrodeposited Ni on a TiO2 electrode, which can be attributed to the synergistic effect between Ni and carbon. The glucose test results indicate a good linear correlation in a glucose concentration range of 0.99-22.97 mM, with a sensitivity of 1063.78 µA·mM-1·cm-2 and a detection limit of 0.53 µM. The results suggest that the obtained Ni-DLC/TiO2 electrode has great application potential in the field of non-enzymatic glucose sensors.
Asunto(s)
Técnicas Biosensibles , Nanotubos , Técnicas Biosensibles/métodos , Carbono/química , Técnicas Electroquímicas/métodos , Electrodos , Glucosa , TitanioRESUMEN
As an extension of single-atom catalysts, despite the increased opportunities to optimize the hydrogen evolution reaction (HER) activity with the variation of the composition, dual-metal-atom catalysts, i.e., dimers, are deeply trapped in a design blind spot due to the lack of the essential recognition of the intrinsic catalytic mechanism at the atomic level. Herein, based on first-principles calculations, a series of platinum-transition metal dimers were constructed on nitrogen-doped graphene (PtM-NDG, M = Fe, Co, Ni, Cu) to reveal the effects of the internal (i.e., M atom) and external (i.e., NDG substrate) environments on the HER activity. Computational results show that the original over-adsorption of hydrogen intermediate (H*) of PtM dimer is weakened after the introduction of NDG, and the optimal active site migrates from the Pt in PtM dimer to the Pt-M bridge in PtM-NDG, triggered by the redistribution of the charge density of the metal atoms. In particular, the M atom switches from tuning the d-band center of the Pt atom to indirectly assist the adsorption behavior of Pt in the PtM dimer to the direct participation in the bonding with H* in PtM-NDG via its own d-band to regulate the distribution of σ and σ*, which enables fine modulation of the bond strength with H*. Moreover, the overall hydrogen evolution performance of PtM-NDG is mainly determined by the d-band center of the M atom. Furthermore, PtFe-NDG with the lowest energy barrier of the rate-determining step stands out in the process of H2 desorption and water dissociation. The present work deepens our understanding of the effects of the metal dopant and substrate on the catalytic performance of platinum.
RESUMEN
Although there is a general consensus that the electrocatalysts will undergo reconstruction to generate (oxy)hydroxides as real active sites during the electrochemical oxygen evolution reaction (OER), the understanding of this process is still far from satisfactory. In particular, the reconstruction process of most of these electrocatalysts is either slow or occurs only on the surface, which thus restrains the OER performance of the electrocatalysts. Herein, we reveal a fast and deep reconstruction of the coprecipitated Fe phosphates on nickel foam, via in situ Raman spectroscopy together with electron microscopy, X-ray photoelectron spectroscopy, and electrochemical tests. The generated NiFe (oxy)hydroxide nanosheets after reconstruction behave as the real active sites for the OER in the alkaline condition, with a low overpotential and excellent durability. The present work provides deep insights on the reconstruction dynamics of OER electrocatalysts.
RESUMEN
Aim: In China, warfarin is usually prescribed with Chuanxiong Rhizoma for treating thromboembolism diseases. However, the reason for their combination is still being determined. The present study explored the pharmacokinetics interactions of warfarin, Chuanxiong Rhizoma, and gut microbiota in the rat model of middle cerebral artery occlusion (MCAO). Methods: A total of 48 rats were randomly divided into six groups: MCAO rats orally administered warfarin (W group), pseudo germ-free MCAO rats orally administered warfarin (W-f group), MCAO rats co-administered Chuanxiong Rhizoma and warfarin (C + W group), pseudo germ-free MCAO rats co-administered Chuanxiong Rhizoma and warfarin (C + W-f group), MCAO rats co-administered warfarin and senkyunolide I (S + W group); pseudo germ-free MCAO rats co-administered warfarin and senkyunolide I (S + W-f group). After treatment, all animals' blood and stool samples were collected at different time points. The stool samples were used for 16S rRNA sequencing analysis. Ultra-performance liquid chromatography coupled to tandem mass spectrometry (UPLC-MS/MS) method was established to quantify warfarin, internal standards, and the main bioactive components of Chuanxiong in blood samples. The main pharmacokinetics parameters of warfarin were calculated by DAS 2.1.1 software. Results: The relative abundance of Allobaculum and Dubosiella in the pseudo germ-free groups (W-f, C + W-f, S + W-f) was lower than that in the other three groups (W, C + W, S + W). The relative abundance of Lactobacillus in the W-f group was higher than that of the W group, while the relative abundance of Akkermansia decreased. The relative abundance of Ruminococcaceae_UCG-014 and Ruminococcaceae_NK4A214_group in the S + W-f group was lower than in the S + W group. Compared to the W group, the AUC0-t and Cmax of warfarin in the W-f group increased significantly to 51.26% and 34.58%, respectively. The AUC0-t and Cmax in the C + W group promoted 71.20% and 65.75% more than the W group. Compared to the W group, the AUC0-t and Cmax increased to 64.98% and 64.39% in the S + W group. Conclusion: Chuanxiong Rhizoma and senkyunolide I (the most abundant metabolites of Chuanxiong Rhizoma aqueous extract) might affect the pharmacokinetics features of warfarin in MCAO rats through, at least partly, gut microbiota.
RESUMEN
The saturable absorption properties of BiOI nanosheets with exposed {110} facets prepared by the chemical vapor transport were investigated by Z-scan with femtosecond pulse laser. The nonlinear absorption coefficient at 400 nm is stronger and more sensitive to photoexcitation than its nonlinear response at 800 nm. The small saturation intensity could have been achieved, which is one order of magnitude smaller than that of black phosphorus nanosheets, while the Imχ(3) are determined to be -4.35×10-12esu close to theoretical prediction. According to time-resolved photoluminescence spectrum results, this strong saturated absorption at 400 nm may be attributed to the interband recombination process, whose lifetime was 230 ps.
RESUMEN
Due to the wide use of iron in all kinds of areas, the design and construction of direct, fast, and highly sensitive sensor for Fe3+ are highly desirable and important. In the present work, a kind of fluorescent MXene quantum dots (MQDs) was synthesized via an intermittent ultrasound process using N,N-dimethyl formamide as solvent. The prepared MQDs were characterized via a combination of UV-Vis absorption, fluorescence spectra, X-ray photoelectron energy spectra, and Fourier-transform infrared spectroscopy. Based on the electrostatic-induced aggregation quenching mechanism, the fluorescent MQDs probes exhibited excellent sensing performance for the detection of Fe3+, with a sensitivity of 0.6377 mM-1 and the detection limit of 1.4 µM, superior to those reported in studies. The present MQDs-based probes demonstrate the potential promising applications as the sensing device of Fe3+.
RESUMEN
Metallic nanocrystals with specific morphologies are of great interest to various applications, in particular for nanocages with well-defined and controllable surface due to high surface-to-volume ratio with high utilization efficiency of atoms. In the present work, Ru decahedral nanocages were synthesized via a combination of seed-mediated growth and chemical etching approach over Pd decahedra seeds. To be specific, the Pd decahedra were synthesized via a standard procedure, on which the Ru out layers were grown by seed-mediated growth with a few nanometers. Subsequently, Ru decahedral nanocages were formed with selective chemical etching of Pd cores in acidic aqueous solution. The present work suggests an effective strategy towards synthesis of hollow nanocages.
Asunto(s)
Nanopartículas del Metal , AguaRESUMEN
Size-selected 3 nm gas-phase Au clusters dispersed by cluster beam deposition (CBD) on a conducting fluorine-doped tin oxide template show strong enhancement in mass activity for the methanol electro-oxidation (MEO) reaction compared to previously reported nanostructured gold electrodes. Density functional theory-based modeling on the corresponding Au clusters guided by experiments attributes this high MEO activity to the high density of exposed under-coordinated Au atoms at their faceted surface. In the description of the activity trends, vertices and edges are the most active sites due to their favorable CO and OH adsorption energies. The faceted structures occurring in this size range, partly preserved upon deposition, may also prevent destructive restructuring during the oxidation-reduction cycle. These results highlight the benefits of using CBD in fine-tuning material properties on the nanoscale and designing high-performance fuel cell electrodes with less material usage.
RESUMEN
The picosecond dynamics of excited charge carriers in the silicon substrate of THz metamaterial antennas was studied at different wavelengths. Time-resolved THz pump-THz probe spectroscopy was performed with light from a tunable free electron laser in the 9.3-16.7 THz frequency range using fluences of 2-12 J/m2. Depending on the excitation wavelength with respect to the resonance center, transient transmission increase, decrease, or a combination of both was observed. The transient transmission changes can be explained by local electric field enhancement, which induces impact ionization in the silicon substrate, increasing the local number of charge carriers by several orders of magnitude, and their subsequent diffusion and recombination. The studied metamaterials can be integrated with common semiconductor devices and can potentially be used in sensing applications and THz energy harvesting.
RESUMEN
The development of simple and effective methods for the rapid preparation of electrocatalysts for overall water splitting from earth-abundant elements is an important and challenging task. A facile and ultrafast two-step method was developed to prepare a Ni/NiO@CoFe layered double hydroxide hierarchical nanostructure (NCF) within a few minutes by femtosecond laser ablation and electrodeposition. In 1 m KOH solution, the optimized NCF catalysts show a low overpotential of 230â mV for the oxygen evolution reaction (OER) at a current density of 10â mA cm-2 with a low Tafel slope of 34.3â mV dec-1 , indicating fast and efficient OER kinetics. Owing to the synergistic effect between NiO and CoFe layered double hydroxide, the hydrogen evolution reaction performance of the NCF was also improved. The synthesized electrocatalysts were further utilized in overall water splitting with a potential of only 1.56â V at a current density of 10â mA cm-2 and excellent durability, better than that of the commercial RuO2 (+)//Pt/C(-) system. The present work provides new insights on the rapid and facile preparation of efficient electrocatalysts for overall water splitting on a large scale.
RESUMEN
Highly efficient and low-cost non-noble metal based electrocatalysts for oxygen evolution reaction (OER) have attracted more and more attention in recent years. However, the current research has been focused on the construction of novel OER electrocatalysts themselves, little attention has been paid to the modification of the substrates. In this work, a different strategy is proposed via laser ablation to fabricate the Cu foams with rich micro/nano-structures as OER substrates. Later, the precipitation conversion method was utilized to grow cobalt hydroxide on the laser fabricated Cu foams. The as-produced Cu/Cu oxides/Co(OH)2 electrocatalysts exhibit high OER activity in 1 M KOH, requiring an overpotential of only 259 mV at a current density of 50 mA cm-2 with excellent mild-term durability. The improved catalytic performance of the prepared samples can be attributed to the increased surface area, rich active sites, and the superhydrophilicity of the laser produced micro/nano-structures.
RESUMEN
This study presents a new van der Waals (vdW) heterostructure composed of monolayer black phosphorus (BP) and monolayer graphitic SiC (g-SiC). Using first-principles calculations, the structural and electronic properties of the BP/SiC heterostructure were investigated. It was found that by stacking BP with SiC, weak type-I band alignment can be achieved with a band gap of 0.705 eV, where the direct band gap as well as linear dichroism features were well preserved. The electrostatic potential drop in the heterojunction was calculated to be 4.044 eV. By applying perpendicular electric field, the band alignment can be altered to either type-I or type-II, and the band gap can be effectively controlled by field intensity, hence making the heterostructure suitable for various applications.
RESUMEN
Small cobalt clusters [Formula: see text] and their single chromium atom doped counterparts Co n-1Cr+ (n = 3-5) were studied mass spectrometrically by measuring the infrared multiple photon dissociation (IRMPD) spectra of the corresponding argon tagged complexes. The geometric and electronic structures of the [Formula: see text] and Co n-1Cr+ (n = 3-5) clusters as well as their Ar complexes were optimized by density functional theory (DFT) calculations. The obtained lowest energy structures were confirmed by comparing the IRMPD spectra of [Formula: see text] and [Formula: see text] (n = 3-5, m = 3 and 4) with the corresponding calculated IR spectra. The calculations reveal that the doped Co n-1Cr+ clusters retain the geometric structures of the most stable [Formula: see text] clusters. However, the coupling of the local magnetic moments within the clusters is altered in a size-dependent way: the Cr atom is ferromagnetically coupled in Co2Cr+ and Co3Cr+, while it is antiferromagnetically coupled in Co4Cr+.
RESUMEN
Marks decahedral nanoparticles have attracted significant attention in recent years. In this work, a method of synthesizing Marks decahedron via etching regular decahedral nanoparticles is proposed and verified by Pd nanoparticles, which shows a high yield of Marks decahedron. The present work suggests that one can tune the concave size of Marks decahedral via controlling the etching time and the amount of Poly(vinyl pyrrolidone) (PVP). The thermal stability of Marks nanoparticles is explained by Bond-Energy model, which predicts the largest groove to be the most stable configuration. Moreover, the present method can be extended to synthesize Marks decahedral nanoparticles of other elements, and is of great significance for further studies and applications of Mark decahedral nanoparticles.