A Low‐Temperature Molecular Precursor Approach to Copper‐Based Nano‐Sized Digenite Mineral for Efficient Electrocatalytic Oxygen Evolution Reaction

In the urge of designing noble metal‐free and sustainable electrocatalysts for oxygen evolution reaction (OER), herein, a mineral Digenite Cu₉S₅ has been prepared from a molecular copper(I) precursor, [{(PyHS)₂Cu^I(PyHS)}₂](OTf)₂ ( 1 ), and utilized as an anode material in electrocatalytic OER for the first time. A hot injection of 1 yielded a pure phase and highly crystalline Cu₉S₅, which was then electrophoretically deposited (EPD) on a highly conducting nickel foam (NF) substrate. When assessed as an electrode for OER, the Cu₉S₅/NF displayed an overpotential of merely 298±3 mV at a current density of 10 mA cm^?2 in alkaline media. The overpotential recorded here supersedes the value obtained for the best reported Cu‐based as well as the benchmark precious‐metal‐based RuO₂ and IrO₂ electrocatalysts. In addition, the choronoamperometric OER indicated the superior stability of Cu₉S₅/NF, rendering its suitability as the sustainable anode material for practical feasibility. The excellent catalytic activity of Cu₉S₅ can be attributed to the formation of a crystalline CuO overlayer on the conductive Cu₉S₅ that behaves as active species to facilitate OER. This study delivers a distinct molecular precursor approach to produce highly active copper‐based catalysts that could be used as an efficient and durable OER electro(pre)catalysts relying on non‐precious metals.     

Unusual Surface Latent Heat Flux Variations and Their Critical Dynamics Revealed before Strong Earthquakes

We focus on the possible thermal channel of the well-known Lithosphere–Atmosphere–Ionosphere Coupling (LAIC) mechanism to identify the behavior of thermal anomalies during and prior to strong seismic events. For this, we investigate the variation of Surface Latent Heat Flux (SLHF) as resulting from satellite observables. We demonstrate a spatio-temporal variation in the SLHF before and after a set of strong seismic events occurred in Kathmandu, Nepal, and Kumamoto, Japan, having magnitudes of 7.8, 7.3, and 7.0, respectively. Before the studied earthquake cases, significant enhancements in the SLHF were identified near the epicenters. Additionally, in order to check whether critical dynamics, as the signature of a complex phenomenon such as earthquake preparation, are reflected in the SLHF data, we performed a criticality analysis using the natural time analysis method. The approach to criticality was detected within one week before each mainshock.     

Evaluation of defect induced surface heterogeneity in Metal-Organic Framework materials with alkali dopants employing adsorption isotherm modelling

In this article, an assessment of surface structural heterogeneity in porous metal organic framework (MOF) structure has been demonstrated by employing the methane and carbon-dioxide adsorption isotherms data. The virgin MIL-101-(Cr) MOF was synthesized by the hydrothermal method and defects were induced in the MOF structure by doping with various alkali (K, Na, Li) cations. The synthesized MOFs were characterized by XRD, SEM, EDX and BET measurement techniques. In order to understand the defect induced surface heterogeneity by alkali cation dopants, the surface energy distributions for CH₄ and CO₂ adsorptions on MOFs were measured by Dubinin – Astakhov model equation. The surface heterogeneity is mainly controlled by the limiting uptakes of adsorbates, the polarizability of adsorbates and the adsorbate-adsorbent interaction energy.     

Anaerobic-anoxic-aerobic sequential degradation of synthetic wastewaters

This study was conducted in a continuous three-stage system of anaerobic (R1)-anoxic(R2)-aerobic (R3) reactors with synthetic wastewater containing phenol (1000 mg/L), chemical oxygen demand (COD) (3000 mg/L), CN⁻ (30 mg/L), SCN⁻(400 mg/L), and NH ₄ ⁺ -N (600 mg/L) as principal pollutants and well-acclimated heterogeneous microbial cultures. The final effluent was partially returned to R2 with a recycle ratio of 1. Anaerobic stage served to detoxify the feed by removing up to 80% of cyanide. Complete SCN⁻ removal and denitrification could be achieved in the anoxic stage by utilizing phenol as an internal source of carbon. Nitrification efficiency of 93% was obtained in the aerobic reactor. The results demonstrated that the three-stage system can give the desired final treated effluent quality (0 mg/L of phenol, 0.2 mg/L of CN⁻, 210 mg/L of COD, and 20 mg/L of NH ₄ ⁺ -N) and that the NO ₃ ⁻ -N concentration can be lowered by a higher recycle ratio.     

On the survival of peptide cations after electron capture: Role of internal hydrogen bonding and microsolvation

Electron capture by both bare and microsolvated small peptide dications was investigated by colliding these ions with sodium vapor in an accelerator mass spectrometer to provide insight into processes that occur on the microsecond time frame. Survival of the intact peptide monocation after electron capture depends strongly on molecular size. For dipeptides, no intact reduced species were observed; the predominant ions correspond to loss of hydrogen and ammonia. In contrast, the intact reduced species was observed for larger peptides. Calculated structures indicate that the diprotonated dipeptide ions form largely extended structures with low probability of internal ionic hydrogen bonding (i.e., charge solvation) whereas internal ionic H-bonding occurs extensively for larger peptide dications. Solvation of the peptide ions with between one to seven methanol molecules reduces the total extent of H loss even for dipeptides where intact reduced species can survive more than a microsecond after electron capture. The yield of ions corresponding to cleavage of NCalpha bonds (c+ and z+* ions) does not depend strongly on peptide size but decreases with the extent of microsolvation for the dipeptide dications. H-bonding appears to play an important role for the survival of the intact reduced ions but less so for the formation of c+ and z+* ions. Our results indicate that electron capture predominantly occurs at the ammonium groups (at least 70 to 80%), and provides important new insights into the electron capture dissociation process.     

Ion beam synthesis of metal-quantum dots for photonic applications

Although electronics technologies have made great advances in device speed, optical devices can function in the time domain inaccessible to electronics. In the time domain less than 1 ps, optical devices have no competition. Photonic or optical devices are designed to switch and process light signals without converting them to electronic form. The major advantages that these devices offer are speed and preservation of bandwidth. The switching is accomplished through changes in refractive index of the material that are proportional to the light intensity. The third-order optical susceptibility, χ⁽³⁾, known as the optical Kerr susceptibility which is related to the non-linear part of the total refractive index, is the nonlinearity which provides this particular feature. Future opportunities in photonic switching and information processing will depend critically on the development of improved photonic materials with enhanced Kerr susceptibilities, as these materials are still in a relatively early stage of development. Different glass systems are now under investigation to increase their nonlinearity by introducing a variety of modifiers into the glass-network. Ion implantation is an attractive method for inducing colloid formation at a high local concentration unattainable by the melt-glass fabrication process and for confining the non-linearities to specific patterned regions in a variety of host matrices. Recent works on metal-ion implanted colloid generation in bulk fused silica glasses have shown that these nanocluster-glass composites under favourable circumstances have significant enhancement of χ⁽³⁾ with picosecond to femtosecond temporal responses.     

Automated leukocyte recognition using fuzzy divergence

This paper aims at introducing an automated approach to leukocyte recognition using fuzzy divergence and modified thresholding techniques. The recognition is done through the segmentation of nuclei where Gamma, Gaussian and Cauchy type of fuzzy membership functions are studied for the image pixels. It is in fact found that Cauchy leads better segmentation as compared to others. In addition, image thresholding is modified for better recognition. Results are studied and discussed.     

AC Conduction and Time–Temperature Superposition Scaling in a Reduced Graphene Oxide–Zinc Sulfide Nanocomposite

We report, herein, the results of an in depth study and concomitant analysis of the AC conduction [σ′(ω): f=20 Hz to 2 MHz] mechanism in a reduced graphene oxide–zinc sulfide (RGO–ZnS) composite. The magnitude of the real part of the complex impedance decreases with increase in both frequency and temperature, whereas the imaginary part shows an asymptotic maximum that shifts to higher frequencies with increasing temperature. On the other hand, the conductivity isotherm reveals a frequency‐independent conductivity at lower frequencies subsequent to a dispersive conductivity at higher frequencies, which follows a power law [σ′(ω)∝ω^s] within a temperature range of 297 to 393 K. Temperature‐independent frequency exponent ′s′ indicates the occurrence of phonon‐assisted simple quantum tunnelling of electrons between the defects present in RGO. Finally, this sample follows the “time–temperature superposition principle”, as confirmed from the universal scaling of conductivity isotherms. These outcomes not only pave the way for increasing our elemental understanding of the transport mechanism in the RGO system, but will also motivate the investigation of the transport mechanism in other order–disorder systems.