Electrocatalytic study of the hydrogen evolution reaction on MoS2/BP and MoSSe/BP in acidic media.

Molecular hydrogen (H2) production by the electrochemical hydrogen evolution reaction (HER) is being actively explored for non-precious metal-based electrocatalysts that are earth-abundant and low cost like MoS2. Although it is acid-stable, its applicability is limited by catalytically inactive basal planes, poor electrical transport and inefficient charge transfer at the interface. Therefore, the present work examines its bilayer van der Waals heterostructure (vdW HTS). The second constituent monolayer boron phosphide (BP) is advantageous as an electrode material owing to its chemical stability in both oxygen and water environments. Here, we have performed first-principles based calculations under the framework of density functional theory (DFT) for the HER in an electrochemical double layer model with the BP monolayer, MoS2/BP and MoSSe/BP vdW HTSs. The climbing image nudged elastic band method (CI-NEB) has been employed to determine the minimum energy pathways for Tafel and Heyrovsky reactions. The calculations reveal that the Tafel reaction shows no reaction barrier. Thereafter, for the Heyrovsky reaction, we obtained a low reaction barrier in the vdW HTSs as compared to that in the BP monolayer. Subsequently, we have observed no significant difference in the reaction profile of MoS2/BP and MoSSe/BP vdW HTSs in the case of 2 × 2 supercell configuration. However, in the case of 3 × 3 and 4 × 4 configurations, MoSSe/BP shows a feasible Heyrovsky reaction with no reaction barrier. The coverages with 1/4H+ concentration (conc.) deduced high coverage with low conc. and low coverage with high conc. to be apt for the HER via the Heyrovsky reaction path. Finally, on observing the activation barrier of the Heyrovsky pathway along with that of second H adsorption at the surface, the Heyrovsky path is expected to be favoured.

Exploring strong and weak topological states on isostructural substitutions in TlBiSe[Formula: see text].

Topological Insulators (TIs) are unique materials where insulating bulk hosts linearly dispersing surface states protected by the Time-Reversal Symmetry. These states lead to dissipationless current flow, which makes this class of materials highly promising for spintronic applications. Here, we predict TIs by employing state-of-the-art first-principles based methodologies, viz., density functional theory and many-body perturbation theory (G[Formula: see text]W[Formula: see text]) combined with spin-orbit coupling effects. For this, we take a well-known 3D TI, TlBiSe[Formula: see text] and perform complete substitution with suitable materials at different sites to check if the obtained isostructural materials exhibit topological properties. Subsequently, we scan these materials based on SOC-induced parity inversion at Time-Reversal Invariant Momenta. Later, to confirm the topological nature of selected materials, we plot their surface states along with calculation of Z[Formula: see text] invariants. Our results show that GaBiSe[Formula: see text] is a strong Topological Insulator, besides, we report six weak Topological Insulators, viz., PbBiSe[Formula: see text], SnBiSe[Formula: see text], SbBiSe[Formula: see text], Bi[Formula: see text]Se[Formula: see text], TlSnSe[Formula: see text] and PbSbSe[Formula: see text]. We have further verified that all the reported TIs are dynamically stable, showing all real phonon modes of vibration.

Vacancy-Ordered Double Perovskites Cs2BI6 (B = Pt, Pd, Te, Sn): An Emerging Class of Thermoelectric Materials.

Vacancy-ordered double perovskites (A2BX6), being one of the environmentally friendly and stable alternatives to lead halide perovskites, have garnered considerable research attention in the scientific community. However, their thermal transport has not been explored much, despite their potential applications. Here, we explore Cs2BI6 (B = Pt, Pd, Te, Sn) as potential thermoelectric materials using state-of-the-art first-principles-based methodologies, viz., density functional theory combined with many-body perturbation theory (G0W0) and spin-orbit coupling. The absence of polyhedral connectivity in vacancy-ordered perovskites gives rise to additional degrees of freedom, leading to lattice anharmonicity. The presence of anharmonic lattice dynamics leads to strong electron-phonon coupling, which is well-captured by the Fröhlich mesoscopic model. The lattice anharmonicity is further studied using ab initio molecular dynamics and the electron localization function. The maximum anharmonicity is observed in Cs2PtI6, followed by Cs2PdI6, Cs2TeI6, and Cs2SnI6. Also, the computed average thermoelectric figure of merit (zT) for Cs2PtI6, Cs2PdI6, Cs2TeI6, and Cs2SnI6 is 0.88, 0.85, 0.95, and 0.78, respectively, which reveals their promising renewable energy applications.

Ferrocene-derived Fe-metalated porous organic polymer for the core planarity-triggered detoxification of chemical warfare agents.

Herein, we demonstrate the successful construction of two Fe-metalated porous organic polymers having planar (Fe-Tt-POP) and non-planar (Fe-Rb-POP) geometry via the ternary copolymerization strategy for the catalytic oxidative decontamination of different sulfur-based mustard gas simulants (HD). Fe-Tt-POP exhibits superior catalytic performance for the oxidation of thioanisole (TA) in comparison with Fe-Rb-POP. Interestingly, this activity difference can be further explored by in situ operando DRIFTS and DFT computational studies.

Taxonomic revision of Teleogryllus mitratus (Burmeister, 1838) and T. occipitalis (Serville, 1838) in India, with the description of Teleogryllus rohinae Jaiswara amp; Jain sp. nov. and a key for Teleogryllus species from India (Orthoptera: Gryllidae).

The genus Teleogryllus is known from 52 species distributed worldwide, of which India is home to 11 species. We update Teleogryllus diversity by describing a new species, T. rohinae Jaiswara Jain sp. nov., from Kerala, India. In addition, we revise the description of the two widespread Teleogryllus species, i.e., T. mitratus (Burmeister, 1838) and T. occipitalis (Serville, 1838) and describe their female genital structures for the first time. Finally, we provide updated identification keys for all Indian Teleogryllus species.

Exploring Exciton and Polaron Dominated Photophysical Phenomena in Ruddlesden-Popper Phases of Ban+1ZrnS3n+1 (n = 1-3) from Many Body Perturbation Theory.

Ruddlesden-Popper (RP) phases of Ban+1ZrnS3n+1 are an evolving class of chalcogenide perovskites in the field of optoelectronics, especially in solar cells. However, detailed studies regarding its optical, excitonic, polaronic, and transport properties are hitherto unknown. Here, we have explored the excitonic and polaronic effect using several first-principles based methodologies under the framework of Many Body Perturbation Theory. Unlike its bulk counterpart, the optical and excitonic anisotropy are observed in Ban+1ZrnS3n+1 (n = 1-3) RP phases. As per the Wannier-Mott approach, the ionic contribution to the dielectric constant is important, but it gets decreased on increasing n in Ban+1ZrnS3n+1. The exciton binding energy is found to be dependent on the presence of large electron-phonon coupling. We further observed maximum charge carrier mobility in the Ba2ZrS4 phase. As per our analysis, the optical phonon modes are observed to dominate the acoustic phonon modes, leading to a decrease in polaron mobility on increasing n in Ban+1ZrnS3n+1 (n = 1-3).

MoS2 and Janus (MoSSe) based 2D van der Waals heterostructures: emerging direct Z-scheme photocatalysts.

Two-dimensional (2D) materials, viz. transition metal dichalcogenides (TMD) and transition metal oxides (TMO), offer a platform that allows the creation of heterostructures with a variety of properties. The optoelectronic industry has observed an upheaval in the research arena of MoS2 based van der Waals (vdW) heterostructures (HTSs) and Janus structures. Therefore, interest towards these structures is backed by the ability to select their electronic and optical properties. The present study investigates the photocatalytic abilites of bilayer, MoS2 and Janus (MoSSe) based vdW HTSs, viz. MoS2/TMO, MoS2/TMD, MoSSe/TMO and MoSSe/TMD, by a first-principles based approach under the framework of (hybrid) density functional theory (DFT) and many body perturbation theory (GW approximation). We have considered HfS2, ZrS2, TiS2 and WS2, and HfO2, T-SnO2 and T-PtO2 from the families of TMDs and TMOs, respectively. The photocatalytic properties of these vdW HTSs are thoroughly investigated and compared with their respective individual monolayers by visualizing their band edge alignments, electron-hole recombination and optical properties. Strikingly, we observe that, despite most of the individual monolayers not performing optimally as photocatalysts, type II band edge alignment is noticed in vdW HTSs and they appear to be efficient photocatalysts via the Z-scheme. Moreover, these vdW HTSs have also shown promising optical responses in the visible region. Finally, electron-hole recombination, H2O adsorption and hydrogen evolution reaction (HER) results establish that MoSSe/HfS2, MoSSe/TiS2, MoS2/T-SnO2 and MoSSe/ZrS2 are probable highly efficient Z-scheme photocatalysts.

Effect of temperature on life-history traits and mating calls of a field cricket, Acanthogryllus asiaticus.

Ectotherms are sensitive to changes in ambient temperature that impact their physiology and development. To compensate for the effects of variation in temperature, ectotherms exhibit short or long-term physiological plasticity. An extensive body of literature exists towards understanding these effects and the solutions ectotherms have evolved. However, to what extent rearing temperature during early life stages impacts the behaviour expressed in adulthood is less clearly understood. In the present study, we aimed to examine the effects of developmental temperature on life-history traits and mating call features in a tropical field cricket, Acanthogryllus asiaticus. We raised A. asiaticus at two different developmental conditions: 25 °C and 30 °C. We found developmental time and adult lifespan of individuals reared at 30 °C to be shorter than those reared at 25 °C. Increased developmental temperature influenced various body size parameters differentially. Males raised at 30 °C were found to be larger and heavier than those raised at 25 °C, making A. asiaticus an exception to the temperature-size rule. We found a significant effect of change in immediate ambient temperature on different call features of both field-caught and lab-bred individuals. Developmental temperature also affected mating call features wherein individuals raised at higher temperature produced faster calls with a higher peak frequency compared to those raised at lower temperature. In addition, an interactive effect of both developmental and immediate temperature was found on mating call features. Our study highlights the importance of understanding how environmental temperature shapes life-history and sexual communication in crickets.

Feeding in murky waters: acclimatization and landmarks improve foraging efficiency of zebrafish (Danio rerio) in turbid waters.

Fish inhabiting human-dominated ecosystems are prone to altered sensory environments in which they must live and function. Increased turbidity is one such change that they must deal with. We tested whether an increase in water turbidity and the presence of visual landmarks (coloured stones) affect the foraging efficiency of wild zebrafish. We also tested the influence of extended exposure to differing turbidity levels on the subsequent foraging efficiency of acclimatized individuals. Feeding latency (time taken to find food) increased significantly with increase in turbidity levels from a minimum of 4 s to ca 300 s. However, extended exposure of fish to varying levels of turbidity decreased feeding latencies in acclimatized conditions, indicating that acclimatization to the immediate visual environment plays an important role in determining foraging success. Most significantly, we found that feeding latencies in turbid conditions decreased significantly if visual landmarks were present. This demonstrates that zebrafish use visual landmark cues to navigate to foraging sites when visibility is impaired. This study has important implications on the role of behavioural plasticity and spatial learning in animals that allow them to cope with altered sensory environments such as episodes of enhanced turbidity that could be natural or anthropogenic.

Low-pass filters and differential tympanal tuning in a paleotropical bushcricket with an unusually low frequency call.

Low-frequency sounds are advantageous for long-range acoustic signal transmission, but for small animals they constitute a challenge for signal detection and localization. The efficient detection of sound in insects is enhanced by mechanical resonance either in the tracheal or tympanal system before subsequent neuronal amplification. Making small structures resonant at low sound frequencies poses challenges for insects and has not been adequately studied. Similarly, detecting the direction of long-wavelength sound using interaural signal amplitude and/or phase differences is difficult for small animals. Pseudophylline bushcrickets predominantly call at high, often ultrasonic frequencies, but a few paleotropical species use lower frequencies. We investigated the mechanical frequency tuning of the tympana of one such species, Onomarchus uninotatus, a large bushcricket that produces a narrow bandwidth call at an unusually low carrier frequency of 3.2 kHz. Onomarchus uninotatus, like most bushcrickets, has two large tympanal membranes on each fore-tibia. We found that both these membranes vibrate like hinged flaps anchored at the dorsal wall and do not show higher modes of vibration in the frequency range investigated (1.5-20 kHz). The anterior tympanal membrane acts as a low-pass filter, attenuating sounds at frequencies above 3.5 kHz, in contrast to the high-pass filter characteristic of other bushcricket tympana. Responses to higher frequencies are partitioned to the posterior tympanal membrane, which shows maximal sensitivity at several broad frequency ranges, peaking at 3.1, 7.4 and 14.4 kHz. This partitioning between the two tympanal membranes constitutes an unusual feature of peripheral auditory processing in insects. The complex tracheal shape of O. uninotatus also deviates from the known tube or horn shapes associated with simple band-pass or high-pass amplification of tracheal input to the tympana. Interestingly, while the anterior tympanal membrane shows directional sensitivity at conspecific call frequencies, the posterior tympanal membrane is not directional at conspecific frequencies and instead shows directionality at higher frequencies.