Synthesis and in situ sulfidation of molybdenum carbide MXene using fluorine-free etchant for electrocatalytic hydrogen evolution reactions.

Synthesizing MXenes from Mn+1AXn (MAX) phases using hazardous hydrogen fluoride is a common and effective method. However, fluorine termination on the basal planes and edges of the resulting MXenes is undesirable for the electrocatalytic hydrogen evolution reaction (HER), while oxygen (O), hydroxyl (OH), and sulfur (S) termination favors this reaction. Herein, we unveil a simple fluorine-free exfoliation and two-step vulcanization method for synthesizing molybdenum sulfide-modified molybdenum carbide (MoS2/Mo2CTx MXene, T = OH, O, S) for the HER in alkaline medium. Microwave-assisted hydrothermal treatment of the MAX phase (Mo3AlC2) with sodium hydroxide-sodium sulfide as an etching solution and thioacetamide as a source of sulfide ions enabled the selective dissolution of the aluminum (Al) layer and sulfidation of the surface Mo atoms to form amorphous MoS2. Thus, the vulcanization of Mo2CTx MXene resulted in the formation of MoS2/Mo2CTx MXene. The MoS2 formed on the surface of Mo2CTx provided enhanced stability by preventing oxidation. MoS2/Mo2CTx exhibited enhanced electrocatalytic activity toward the HER, mainly due to the O, OH, and amorphous MoS2 functionalities. The MoS2 sites on the surface exhibited an overpotential of 110 ± 7 mV at a current density of 10 mA cm-2 as a result of enhanced charge transfer and mass transfer. Thus, the sulfidation method demonstrated herein is capable of producing amorphous MoS2 structures on Mo2CTx MXene, which could be applied for the surface modification of other molybdenum-based nanomaterials or electrocatalysts to improve stability and enhance electrocatalytic activity.

Self-redox reaction driven in situ formation of Cu2O/Ti3C2Tx nanosheets boost the photocatalytic eradication of multi-drug resistant bacteria from infected wound.

BACKGROUND: MXenes with interesting optical and electrical properties have been attractive in biomedical applications such as antibacterial and anticancer agents, but their low photogeneration efficiency of reactive oxygen species (ROS) and poor stability are major concerns against microbial resistance. METHODS: Water-dispersible single layer Ti3C2Tx-based MXene through etching tightly stacked MAX phase precursor using a minimally intensive layer delamination method. After addition of Cu(II) ions, the adsorbed Cu(II) ions underwent self-redox reactions with the surface oxygenated moieties of MXene, leading to in situ formation of Cu2O species to yield Cu2O/Ti3C2Tx nanosheets (heterostructures). RESULTS: Under NIR irradiation, the Cu2O enhanced generation of electron-hole pairs, which boosted the photocatalytic production of superoxide and subsequent transformation into hydrogen peroxide. Broad-spectrum antimicrobial performance of Cu2O/Ti3C2Tx nanosheets with sharp edges is attributed to the direct contact-induced membrane disruption, localized photothermal therapy, and in situ generated cytotoxic free radicals. The minimum inhibitory concentration of Cu2O/Ti3C2Tx nanosheets reduced at least tenfold upon NIR laser irradiation compared to pristine Cu2O/Ti3C2Tx nanosheets. The Cu2O/Ti3C2Tx nanosheets were topically administrated on the methicillin-resistant Staphylococcus aureus (MRSA) infected wounds on diabetic mice. CONCLUSION: Upon NIR illumination, Cu2O/Ti3C2Tx nanosheets eradicated MRSA and their associated biofilm to promote wound healing. The Cu2O/Ti3C2Tx nanosheets with superior catalytic and photothermal properties have a great scope as an effective antimicrobial modality for the treatment of infected wounds.

Hydrological drought characterization based on GNSS imaging of vertical crustal deformation across the contiguous United States.

Continuous Global Navigation Satellite System (GNSS) measurements allow us to track subtle elastic crustal deformation in the response to hydrological mass variations and provide an additional tool to independently characterize hydrological extremes (e.g., droughts and floods). In this study, we develop a time-varying GNSS imaging strategy that depends on the principal component analysis of GNSS-sensed vertical crustal displacement (VCD) in 2006-2020 and the monthly images of hydrology-induced deformation are generated for drought characterization across the contiguous United States. The first 12 principal components are selected in our time-varying imaging system, which account for 85% of the data variance. Considering that surface water loads are inversely correlated with the induced elastic vertical motions, we reverse the signs of the GNSS-imaged time series in all grids in subsequent studies (referred to as negative VCD (NVCD)). The GNSS-NVCD data generally correlate well with the water estimates from the Gravity Recovery and Climate Experiment (GRACE) and North American Land Data Assimilation System (NLDAS). Using the GNSS-imaged gridded NVCD products, we produce a GNSS-based drought severity index (GNSS-DSI) based on the climatological methodology, which is implemented by standardizing the GNSS NVCD anomalies that deviate from climatological normal. In most regions, strong linear correlations are accessible for GNSS-DSI relative to GRACE-DSI and the self-calibrating Palmer Drought Severity Index (scPDSI). The new drought monitoring tool, which is based solely on GNSS-measured vertical positions, is used for hydrological drought characterization (onset, end, duration, magnitude, intensity, and recovery); it succeeds in identifying well-documented historical droughts from the US drought monitor (USDM). Our study presents a new drought characterization framework using solely GNSS-measured hydrological loading displacements from a dense GNSS network, which has great potential to strengthen operational drought monitoring and assessment.

Synchronized and asynchronous modulation of seismicity by hydrological loading: A case study in Taiwan.

Delineation of physical factors that contribute to earthquake triggering is a challenging issue in seismology. We analyze hydrological modulation of seismicity in Taiwan using groundwater level data and GNSS time series. In western Taiwan, the seismicity rate reaches peak levels in February to April and drops to its lowest values in July to September, exhibiting a direct correlation with annual water unloading. The elastic hydrological load cycle may be the primary driving mechanism for the observed synchronized modulation of earthquakes, as also evidenced by deep earthquakes in eastern Taiwan. However, shallow earthquakes in eastern Taiwan (<18 km) are anticorrelated with water unloading, which is not well explained by either hydrological loading, fluid transport, or pore pressure changes and suggests other time-dependent processes. The moderate correlation between stacked monthly trends of large historic earthquakes and present-day seismicity implies a modestly higher seismic hazard during the time of low annual hydrological loading.

Infrared Spectroscopic and Kinetic Characterization on the Photolysis of Nitrite in Alcohol-Containing Aqueous Solutions.

Nitrite is regarded as a potential OH and NO precursor in aqueous solution upon ultraviolet photolysis. A step-scan Fourier-transform interferometer was employed to collect the transient infrared difference spectra upon excitation of the sodium nitrite aqueous solution in the presence of methanol and ethanol upon 355 nm pulsed excitation. The photolytic intermediates were proposed to be NO and NO2 via the direct dissociation from NO2- and the rapid reaction of OH and NO2-, respectively. Coupled with the theoretical calculations of the absolute energies and harmonic wavenumbers of relevant species using B3LYP density functional theory with the C-PCM model to account for the medium effect of H2O, a transient band at 1860-2030 cm-1 could be attributed to dissolved N2O3 isomers that could be quickly generated from NO + NO2. On the basis of the predicted thermodynamics, the reactions of alcohols with N2O3 were less thermodynamically favorable than that of water, resulting in a slightly decelerated depletion rate of N2O3 in alcohol-containing aqueous solution. Comparing the transient population of N2O3 in the absence and presence of CH3OH or C2H5OH, the upper-bound bimolecular rate coefficient of NO or NO2 with alcohols is reported as 7.3 × 103 M-1 s-1 for the first time. The spectroscopic and kinetic evidence of the reactivity of alcohols with NO, NO2, and N2O3 are provided to augment the roles of alcohols and NxOy in solution or in aqueous aerosol photochemistry.

Lower-crustal rheology and thermal gradient in the Taiwan orogenic belt illuminated by the 1999 Chi-Chi earthquake.

The strength of the lithosphere controls tectonic evolution and seismic cycles, but how rocks deform under stress in their natural settings is usually unclear. We constrain the rheological properties beneath the Taiwan orogenic belt using the stress perturbation following the 1999 Chi-Chi earthquake and fourteen-year postseismic geodetic observations. The evolution of stress and strain rate in the lower crust is best explained by a power-law Burgers rheology with rapid increases in effective viscosities from ~1017 to ~1019 Pa s within a year. The short-term modulation of the lower-crustal strength during the seismic cycle may alter the energy budget of mountain building. Incorporating the laboratory data and associated uncertainties, inferred thermal gradients suggest an eastward increase from 19.5±2.5°C/km in the Coastal Plain to 32±3°C/km in the Central Range. Geodetic observations may bridge the gap between laboratory and lithospheric scales to investigate crustal rheology and tectonic evolution.

Imaging the distribution of transient viscosity after the 2016 Mw 7.1 Kumamoto earthquake.

The deformation of mantle and crustal rocks in response to stress plays a crucial role in the distribution of seismic and volcanic hazards, controlling tectonic processes ranging from continental drift to earthquake triggering. However, the spatial variation of these dynamic properties is poorly understood as they are difficult to measure. We exploited the large stress perturbation incurred by the 2016 earthquake sequence in Kumamoto, Japan, to directly image localized and distributed deformation. The earthquakes illuminated distinct regions of low effective viscosity in the lower crust, notably beneath the Mount Aso and Mount Kuju volcanoes, surrounded by larger-scale variations of viscosity across the back-arc. This study demonstrates a new potential for geodesy to directly probe rock rheology in situ across many spatial and temporal scales.

Effects of antibacterial nanostructured composite films on vascular stents: hemodynamic behaviors, microstructural characteristics, and biomechanical properties.

The purpose of this research was to investigate stresses resulting from different thicknesses and compositions of hydrogenated Cu-incorporated diamond-like carbon (a-C:H/Cu) films at the interface between vascular stent and the artery using three-dimensional reversed finite element models (FEMs). Blood flow velocity variation in vessels with plaques was examined by angiography, and the a-C:H/Cu films were characterized by transmission electron microscopy to analyze surface morphology. FEMs were constructed using a computer-aided reverse design system, and the effects of antibacterial nanostructured composite films in the stress field were investigated. The maximum stress in the vascular stent occurred at the intersections of net-like structures. Data analysis indicated that the stress decreased by 15% in vascular stents with antibacterial nanostructured composite films compared to the control group, and the stress decreased with increasing film thickness. The present results confirmed that antibacterial nanostructured composite films improve the biomechanical properties of vascular stents and release abnormal stress to prevent restenosis. The results of the present study offer the clinical benefit of inducing superior biomechanical behavior in vascular stents.

Frictional afterslip following the 2005 Nias-Simeulue earthquake, Sumatra.

Continuously recording Global Positioning System stations near the 28 March 2005 rupture of the Sunda megathrust [moment magnitude (Mw) 8.7] show that the earthquake triggered aseismic frictional afterslip on the subduction megathrust, with a major fraction of this slip in the up-dip direction from the main rupture. Eleven months after the main shock, afterslip continues at rates several times the average interseismic rate, resulting in deformation equivalent to at least a M(w) 8.2 earthquake. In general, along-strike variations in frictional behavior appear to persist over multiple earthquake cycles. Aftershocks cluster along the boundary between the region of coseismic slip and the up-dip creeping zone. We observe that the cumulative number of aftershocks increases linearly with postseismic displacements; this finding suggests that the temporal evolution of aftershocks is governed by afterslip.

Deformation and slip along the Sunda megathrust in the great 2005 Nias-Simeulue earthquake.

Seismic rupture produced spectacular tectonic deformation above a 400-kilometer strip of the Sunda megathrust, offshore northern Sumatra, in March 2005. Measurements from coral microatolls and Global Positioning System stations reveal trench-parallel belts of uplift up to 3 meters high on the outer-arc islands above the rupture and a 1-meter-deep subsidence trough farther from the trench. Surface deformation reflects more than 11 meters of fault slip under the islands and a pronounced lessening of slip trenchward. A saddle in megathrust slip separates the northwestern edge of the 2005 rupture from the great 2004 Sumatra-Andaman rupture. The southeastern edge abuts a predominantly aseismic section of the megathrust near the equator.