Gap Region Research Articles

Hydroxyl-Binding Induced Hydrogen Bond Network Connectivity on Ru-based Catalysts for Efficient Alkaline Hydrogen Oxidation Electrocatalysis.

Understanding the role of adsorbed intermediates at the polarized catalyst-electrolyte interface on the structure of electrical double layer (EDL) is essential for developing highly efficient electrocatalysts. Here, we prepared a series of unconventional face-centered-cubic (fcc) phase Ru-based catalysts (i.e. fcc-Ru, fcc-RuCr, and fcc-RuCrW) by rational tuning the binding energetics of hydroxyl intermediate to engineer the electrochemical interface and boost the performance of alkaline hydrogen oxidation reaction (HOR). The introduction of oxyphilic metals Cr and W can regulate the orbital occupation of Ru, promote the adsorption of hydroxyl species, resulting in an anomalous behavior that HOR performance under alkaline media exceeds acidic media. Experimental results and theoretical calculations unravel that the modulated adsorption of hydroxyl species on the electrode surface are responsible for the reconstruction of interfacial water structure and dynamic evolution of free water molecules from nearest to the electrode surface to above the gap region in the EDL, thereby leading to significantly increased water connectivity and hydrogen bond network. Our work reveals a new understanding of the surface intermediates in controlling the dynamic process of interfacial water and hydrogen bonding network in HOR electrocatalysis, and will guide rational design of advanced electrocatalysts through electrochemical interfacial engineering.

Hydroxyl‐Binding Induced Hydrogen Bond Network Connectivity on Ru‐based Catalysts for Efficient Alkaline Hydrogen Oxidation Electrocatalysis

Understanding the role of adsorbed intermediates at the polarized catalyst‐electrolyte interface on the structure of electrical double layer (EDL) is essential for developing highly efficient electrocatalysts. Here, we prepared a series of unconventional face‐centered‐cubic (fcc) phase Ru‐based catalysts (i.e. fcc‐Ru, fcc‐RuCr, and fcc‐RuCrW) by rational tuning the binding energetics of hydroxyl intermediate to engineer the electrochemical interface and boost the performance of alkaline hydrogen oxidation reaction (HOR). The introduction of oxyphilic metals Cr and W can regulate the orbital occupation of Ru, promote the adsorption of hydroxyl species, resulting in an anomalous behavior that HOR performance under alkaline media exceeds acidic media. Experimental results and theoretical calculations unravel that the modulated adsorption of hydroxyl species on the electrode surface are responsible for the reconstruction of interfacial water structure and dynamic evolution of free water molecules from nearest to the electrode surface to above the gap region in the EDL, thereby leading to significantly increased water connectivity and hydrogen bond network. Our work reveals a new understanding of the surface intermediates in controlling the dynamic process of interfacial water and hydrogen bonding network in HOR electrocatalysis, and will guide rational design of advanced electrocatalysts through electrochemical interfacial engineering.

The role of flow field dynamics in enhancing volatile organic compound conversion in a surface dielectric barrier discharge system

Abstract This study investigates the correlation between flow fields induced by a surface dielectric barrier discharge (SDBD) system and its application for the volatile organic compound (VOC) gas conversion process. As a benchmark molecule, the conversion of n-butane is monitored using flame ionization detectors, while the flow field is analysed using planar particle image velocimetry. Two individual setups are developed to facilitate both conversion measurement and investigation of induced fluid dynamics. Varying the gap distance between two SDBD electrode plates for three different n-butane mole fractions reveals local peaks in relative conversion around gap distances of 16 mm to 22 mm, indicating additional spatially dependent effects. The lowest n-butane mole fractions exhibit the highest relative conversion, while the highest n-butane mole fraction conversion yields the greatest number of converted molecules per unit time. Despite maintaining constant energy density, the relative conversion exhibits a gradual decrease with increasing distances. The results of the induced flow fields reveal distinct vortex structures at the top and bottom electrodes, which evolve in size and shape as the gap distances increase. These vortices exhibit gas velocity magnitudes approximately seven times higher than the applied external gas flow velocity. Vorticity and turbulent kinetic energy analyses provide insights into these structures' characteristics and their impact on gas mixing. A comparison of line profiles through the centre of the vortices shows peaks in the middle gap region for the same gap distances, correlating with the observed peaks in conversion. These findings demonstrate a correlation between induced flow dynamics and the gas conversion process, bridging plasma actuator studies with the domain of chemical plasma gas conversion.

Two-phase flow evolution and interfacial area transport downstream of the mixing-vane spacer grid in rod bundle channels

This study investigated the axial two-phase flow evolution and interfacial area transport characteristics downstream of the mixing vane spacer grid (MVSG) in a tight lattice rod bundle channel with a subchannel hydraulic diameter of Dh = 17.27 mm. The experiment was conducted under the air-water two-phase flow at room temperature and atmospheric pressure. The phase distributions of 6 positions downstream of MVSG (Z/Dh = 9.15, 14.94, 20.73, 26.52, 32.31, and 61.26) were measured utilizing a self-developed double-layer wire-mesh sensor (WMS). 42 cases were obtained, involving the bubbly flow, cap-bubbly flow, and slug flow. Void fraction, bubble velocity, interfacial area concentration (IAC), and bubble size distribution (BSD) databases were built. Under the group-1 (G-1) flow, due to the swirling flow generated by MVSG, the G-1 bubbles were drawn from the bundle surface and the gap region into the subchannel center to form a spindle core-peak distribution. BSD results demonstrate that the swirling flow promotes bubbles’ coalescence. The one-dimensional (1-D) void fraction and IAC downstream of the MVSG decrease first and then recover, which contrasts with the non-mixing vane spacer grid (N-MVSG) effect. It was attributed to the increment of the bubbles’ velocity after MVSG due to the bubbles’ migration to the channel center and coalescence. Under the group-2 (G-2) flow, MVSG intensifies the core peak distribution of void fraction, and the void fraction profile is also spindle-shaped. The obvious bubbles’ break-up occurs at Z/Dh = 14.94 attributed to the swirling decay. The 1-D void fraction and IAC transport indicate, that with the liquid-velocity increment, the MVSG effect is different from the N-MVSG effect, which is mainly achieved by affecting the G-1 bubbles’ dynamic behaviors. The model evaluation utilizing the interfacial area transport equation (IATE) closing bubble interaction source/sink terms indicates that the advection effect dominates the IAC evolution and the contribution of the pressure effect is weak. The remarkable bubbles’ coalescence occurs under the high liquid velocity. In future studies, the additional bubble break-up and coalescence source/sink term model considering the MVSG effect should be developed based on these cases to improve the IATE prediction ability.

Impact of extracorporeal blood pump gap sizes on the performance and hemocompatibility under off-design operation.

Hemocompatibility remains the dominant challenge in rotary blood pumps, and more information on the relationship between individual pump design features, hemodynamics, and blood trauma in various operation conditions is necessary. The study evaluated the variation of gap sizes in extracorporeal blood pumps concerning their influence on blood compatibility, particularly during off-design conditions. We developed a parametric generic blood pump framework for in-silico and in-vitro design feature analysis. Thirty-six designs with varying axial and radial gap sizes between 0.5 mm and 3 mm were generated. CFD was applied to calculate and compare device hemodynamics and evaluate the performance and hemocompatibility during off-design and target operation conditions. The following quantities were analyzed: pressure difference, hemolysis potential, residence times, hydraulic efficiency, and recirculation ratio. The in-vitro prototype showed excellent agreement with in-silico predictions regarding hydraulic performance (R2 = 0.996 with a RMSE = 2.07). Our results show a modest impact of gap size variations ±10% on key metrics. Domain-resolved analyses revealed a significant contribution of the gap regions to the device's overall hemolytic performance, with an increasing contribution for off-design flow rates. Overall elevated hemolysis levels were identified if at least one gap size was held minimal. We introduced and showed the feasibility of a parametric rotary blood pump framework to systematically investigate design feature impact. Results suggest, larger and uniformly sized gaps being overall beneficial regarding hemocompatibility.

Design and experimental validation of a finite-size labyrinthine metamaterial for vibro-acoustics: enabling upscaling towards large-scale structures.

In this article, we present the design and experimental validation of a labyrinthine metamaterial for vibro-acoustic applications. Based on a two-dimensional unit cell, different designs of finite-size metamaterial specimens in a sandwich configuration including two plates are proposed. The design phase includes an optimization based on Bloch-Floquet analysis with the aims of maximizing the band gap and extruding the specimens in the third dimension while keeping the absorption properties almost unaffected. By manufacturing and experimentally testing finite-sized specimens, we assess their capacity to mitigate vibrations in vibro-impact tests. The experiments confirm a band gap in the low- to mid-frequency range. Numerical models are employed to validate the experiments and to examine additional vibro-acoustic load cases. The metamaterial's performances are compared with benchmark solutions, usually employed for noise and vibration mitigation, showing a comparable efficacy in the band gap region. To eventually improve the metamaterial's performance, we optimize its interaction with the air and test different types of connections between the metamaterial and the homogeneous plates. This finally leads to metamaterial samples largely exceeding the benchmark performances in the band gap region and reveals the potential of interfaces for performance optimization of composed structures.This article is part of the theme issue 'Current developments in elastic and acoustic metamaterials science (Part 1)'.

Fast Reduction of 4-Nitrophenol and Photoelectrochemical Hydrogen Production by Self-Reduced Bi/Ti3C2Tx/Bi2S3 Nanocomposite: A Combined Experimental and Theoretical Study.

The distinctive properties of 2D MXenes have garnered significant interest across various fields, including wastewater treatment and photo/electro-catalysis. The integration of inexpensive semiconductor nanostructures with 2D MXenes offers a promising strategy for applications such as wastewater treatment and photoelectrochemical hydrogen production. In this study, we employed an in situ hydrothermal method to immobilize 1D Bi2S3 nanorods and self-reduced metallic bismuth nanoparticles (Bi NPs) onto Ti3C2Tx MXene nanosheets, resulting in the formation of a Bi/Bi2S3/Ti3C2Tx (0D/1D/2D) composite catalyst, which demonstrates an outstanding efficacy in both the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) and photoelectrochemical hydrogen production. Remarkably, a 4-NP reduction efficiency of 100% was achieved only in 4 min with a reduction rate of 1.14 min-1, which is outstanding, and it is ∼3.8 times faster than pristine Bi2S3 nanorods (0.3 min-1). Furthermore, the photoelectrochemical assessment reveals that the Bi/Bi2S3/Ti3C2Tx catalyst displays remarkable hydrogen evolution reaction (HER) efficiency in an alkaline electrolyte. It exhibits a significantly lower overpotential and Tafel slope of 73 mV and 84 mV/dec, respectively, compared to pristine Bi2S3 nanorods, which are found to be 129 mV and 145 mV/dec under light illumination. The superior reduction performance of 4-NP and charge transfer mechanism is further investigated through density functional theory (DFT) calculations, alongside validation using various microscopic and spectroscopic techniques. Interestingly, the DFT analysis revealed modifications in the partial density of states of Bi2S3 within the band gap region due to the successful anchoring of Ti3C2Tx nanosheets and metallic Bi NPs, facilitating efficient charge transport and separation across the local junctions. Ultraviolet photoelectron spectroscopy provided insights into band alignment and interfacial charge transfer across the Bi/Bi2S3/Ti3C2Tx junction on a microscopic scale. This work is significant for the development of MXene-based hybrid catalysts, and it provides a deeper understanding of the reduction mechanism of organic pollutants and superior charge transport in the hybrid system for photoelectrochemical hydrogen production.

Au Nanoparticles@Si Nanowire Oligomer Arrays for SERS: Dimers Are Best.

We report the synthesis of vertically aligned silicon nanowire (VA-SiNW) oligomer arrays coated with Au nanoparticle (NP) monolayers via a combination of colloidal lithography, metal-assisted chemical etching, and directed NP assembly. Arrays of SiNW monomers (i.e., isolated NWs), dimers, and tetramers are synthesized, decorated with AuNPs, and tested for their performance in surface-enhanced Raman spectroscopy. The ∼20 nm AuNPs easily enter within the ca. 40 nm gaps of the SiNW oligomers, thus reaching the hot spot region. At 785 nm excitation, the AuNPs@SiNW dimer arrays provide the highest Raman signal, in agreement with electromagnetic simulations showing a high electric field enhancement at the Au/Si interface within the dimer gap region.

Elucidating Black α-CsPbI3 Perovskite Stabilization via PPD Bication-Conjugated Molecule Surface Passivation: Ab Initio Simulations.

The cubic α-CsPbI3 phase stands out as one of the most promising perovskite compounds for solar cell applications due to its suitable electronic band gap of 1.7 eV. However, it exhibits structural instability under operational conditions, often transforming into the hexagonal non-perovskite δ-CsPbI3 phase, which is unsuitable for solar cell applications because of the large band gap (e.g., ∼2.9 eV). Thus, there is growing interest in identifying possible mechanisms for increasing the stability of the cubic α-CsPbI3 phase. Here, we report a theoretical investigation, based on density functional theory calculations, of the surface passivation of the α-, γ-, and δ-CsPbI3(100) surfaces using the C6H4(NH3)2 [p-phenylenediamine (PPD)] and Cs species as passivation agents. Our calculations and analyses corroborate recent experimental findings, showing that PPD passivation effectively stabilizes the cubic α-CsPbI3 perovskite against the cubic-to-hexagonal phase transition. The PPD molecule exhibits covalent-dominating bonds with the substrate, which makes it more resistant to distortion than the ionic bonds dominant in perovskite bulks. By contrasting these results with the natural Cs passivation, we highlight the superior stability of the PPD passivation, as evidenced by the negative surface formation energies, unlike the positive values observed for the Cs passivation. This disparity is due to the covalent characteristics of the molecule/surface interaction of PPD, as opposed to the purely ionic interaction seen with the Cs passivation. Notably, the PPD passivation maintains the optoelectronic properties of the perovskites because the electronic states derived from the PPD molecules are localized far from the band gap region, which is crucial for optoelectronic applications.

Heterogeneous Structure and Dynamics of Water in a Hydrated Collagen Microfibril.

Collagen type I is well-known for its outstanding mechanical properties which it inherits from its hierarchical structure. Collagen type I fibrils may be viewed as a heterogeneous material made of protein, macromolecules (such as glycosaminoglycans and proteoglycans) and water. Water content modulates the properties of these fibrils. Yet, the properties of water and the fine interactions of water with the protein constituent of these heterofibrils have only received limited attention. Here, we propose to model collagen type I fibrils as a hydrated structure made of tropocollagen molecules assembled in a microfibril crystal. We perform large-scale all-atom molecular dynamics simulations of the hydration of collagen fibrils beyond the onset of disassembly. We found that the structural and dynamic properties of water vary strongly with the level of hydration of the microfibril. More importantly, we found that the properties vary spatially within the 67 nm D-spacing periodic structure. Alteration of the structural and dynamical properties of the collagen microfibril occur first in the gap region. Overall, we identify that the change in the role of water molecules from glue to lubricant between tropocollagen molecules arises around 100% hydration while the microfibril begins to disassemble beyond 130% water content. Our findings are supported by a decrease in hydrogen bonding, recovery of bulk water properties and amorphization of the tropocollagen molecules packing. Our simulations reveal the structure and dynamics of hydrated collagen fibrils with unprecedented spatial resolution from physiological conditions to disassembly. Beyond the process of self-assembly and the emergence of mechanical properties of collagen type I fibrils, our results may also provide new insights into mineralization of collagen fibrils.

Light-induced insulator–metal transition in Sr2IrO4 reveals the nature of the insulating ground state

Sr2IrO4 has attracted considerable attention due to its structural and electronic similarities to La2CuO4, the parent compound of high-Tc superconducting cuprates. It was proposed as a strong spin-orbit-coupled Jeff = 1/2 Mott insulator, but the Mott nature of its insulating ground state has not been conclusively established. Here, we use ultrafast laser pulses to realize an insulator-metal transition in Sr2IrO4 and probe the resulting dynamics using time- and angle-resolved photoemission spectroscopy. We observe a gap closure and the formation of weakly renormalized electronic bands in the gap region. Comparing these observations to the expected temperature and doping evolution of Mott gaps and Hubbard bands provides clear evidence that the insulating state does not originate from Mott correlations. We instead propose a correlated band insulator picture, where antiferromagnetic correlations play a key role in the gap opening. More broadly, our results demonstrate that energy-momentum-resolved nonequilibrium dynamics can be used to clarify the nature of equilibrium states in correlated materials.

A Model for Pair Production Limit Cycles in Pulsar Magnetospheres

It was recently proposed that the electric field oscillation as a result of self-consistent e ± pair production may be the source of coherent radio emission from pulsars. Direct particle-in-cell simulations of this process have shown that the screening of the parallel electric field by this pair cascade manifests as a limit cycle, as the parallel electric field is recurrently induced when pairs produced in the cascade escape from the gap region. In this work, we develop a simplified time-dependent kinetic model of e ± pair cascades in pulsar magnetospheres that can reproduce the limit-cycle behavior of pair production and electric field screening. This model includes the effects of a magnetospheric current, the escape of e ±, as well as the dynamic dependence of pair production rate on the plasma density and energy. Using this simple theoretical model, we show that the power spectrum of electric field oscillations averaged over many limit cycles is compatible with the observed pulsar radio spectrum.

3D Surface-Enhanced Raman Scattering Substrate Based on an Array of Self-Assembled Au@SiO2 Microspheres

A quasi-periodic array of 3D gold-nanoparticle-capped SiO2 microspheres (Au@SiO2) was designed and prepared with a facile approach to enhance the Raman signal intensity of adsorbed biomolecules. Through adjusting the thickness and annealing of Au thin films initially deposited on arrays of self-assembled SiO2 microspheres, we were able to control the diameter of Au nanoparticles and their interparticle spacing to produce two types of plasmonic near-field hot spots, locating at the gaps of such densely arranged Au nanoparticles on individual SiO2 microspheres and in the gap regions of neighboring SiO2 microspheres, respectively. Such double near-field enhancement mechanism leads to a surface-enhanced Raman scattering (SERS) enhancement factor up to 3 × 106 for Rhodamine 6G molecules. The SERS signal intensity was highly uniform with a relative standard deviation of 4.5%. This 3D SERS substrate has significant potential for various applications in the field of SERS detection of analytes and wearable biosensing.

What Drove the Carrington Event? An Analysis of Currents and Geospace Regions

AbstractThe 1859 Carrington event is the most intense geomagnetic storm in recorded history, and the literature provides numerous explanations for what drove the negative H perturbation on the Earth. There is debate on what dominated the event. Our analysis shows a combination of causes of similar orders of magnitude. Previous analyses generally rely upon the observed H perturbation at Colaba, India; historic newspaper reports; and empirical models. We expand the analysis using two Space Weather Modeling Framework simulations to examine what drove the event. We compute contributions from currents and geospace regions to the northward B field on Earth's surface, BN. We examine magnetospheric currents parallel and perpendicular to the local B field, ionospheric currents, and gap region field–aligned currents (FACs). We also evaluate contributions from the magnetosheath, near–Earth, and neutral sheet regions. A combination of currents and geospace regions significantly contribute to BN on the Earth's surface, changing as the storm evolves. At storm onset, magnetospheric currents and gap–region FACs dominate in the equatorial region. At auroral latitudes, gap–region FACs and ionospheric currents are the largest contributors. At storm peak, azimuthal magnetospheric currents and gap–region FACs dominate at equatorial latitudes. Gap–region FACs and ionospheric currents dominate in the auroral zone, down to mid‐latitudes. Both the magnetosheath and FACs contribute at storm peak, but are less significant than that from the near–Earth ring current. During recovery, the near–Earth ring current is the largest contributor at equatorial latitudes. Ionospheric currents and gap–region FACs dominate in the auroral zone.

Coherent control of nonreciprocal optical properties of the defect modes in 1D defective photonic crystals with atomic doping

We investigate the spectral properties of photonic crystals, lacking parity-time (PT) symmetry, using scattering matrix formalism. We show using the symmetry properties of matrices that a defective photonic crystal, doped with three-level atoms, breaks PT symmetry. For the two defect modes lying in the band gap region, both the reflection and the absorption become nonreciprocal, while the transmission remains reciprocal. We show that the relevant energy spectra do not exhibit exceptional points, thereby invalidating its necessity to achieve non-reciprocity in reflection and absorption. We further demonstrate how this non-reciprocity can be coherently controlled using the driving field and dissipation rates of the atoms.

Roaming in acetaldehyde.

We investigate roaming in the photodissociation of acetaldehyde (CH3CHO), providing insights into the contrasting roaming dynamics observed for this molecule compared to formaldehyde. We carry out trajectory studies for full-dimensional acetaldehyde, supplemented with an analysis of a two-degree-of-freedom restricted model and obtain evidence for two distinct roaming pathways. Trajectories exhibit roaming at both shorter (9-11.5 au) and larger (14.5-22.9 au) maximum CH3-HCO separations, characterized by differing amounts of HCO rotation. No roaming trajectories were found in the intervening gap region. The roaming dynamics near 14.5-22.9 au are well-reproduced by the restricted model and involve passage through a centrifugal barrier, analogous to formaldehyde roaming. However, the shorter-range 9-11.5 au roaming appears unique to acetaldehyde and is likely facilitated by repulsive interactions absent in the simplified models. Phase space analysis reveals that this additional roaming pathway is inaccessible in the reduced dimensionality system. The findings suggest that acetaldehyde's increased propensity for roaming compared to formaldehyde may arise from the presence of multiple distinct roaming mechanisms rather than solely the higher roaming fragment mass.

Reynolds number sensitivity of the vortex dynamics around a long-span rail-cum-road bridge girder with three separated boxes

The novel separated three-box girder is gradually adopted for very long-span cable-stayed bridges due to its excellent flutter stability. Due to its special design of cross section, it exhibits notable Reynolds number effects in the flow patterns and vortex dynamics when subject to incoming flow. To explore its Reynolds number sensitivity, this paper performs a three-dimensional large eddy simulation (LES) on the flow around a static long-span rail-cum-road bridge girder with three separated boxes at different Reynolds numbers. The overall centre height H of the bridge model is chosen as the characteristic length, and the investigated Reynolds number regime falls into the regime of 1e2≤Re≤2.8e4. Through the analysis of the flow characteristics of three distinct regions in the flow field(the windward leading edge region, the gap region and the wake region), a successive transition of the wake flow, gap flow, and leading edge shear flow is observed with increasing Reynolds number. The surrounding flow patterns are divided by different Reynolds number regimes as: laminar separation at the trailing edge (Re<5e2); simultaneous instability of the gap shear layer and the wake (5e2≤Re<1e3); restabilisation of the upstream gap shear layer (1e3≤Re<3e3); secondary instability of the upstream gap shear layer and transition of the wake (3e3≤Re<8e3); transition of the separated shear layer at the leading edge (8e3≤Re≤2.8e4). This paper reveals in detail the complex vortex dynamics in the surrounding flow field of the special cross section with three separated boxes.

32‐2: Multi AI Approaches for Improving OLED Display Pattern Repair in Manufacturing Processes

The increasing resolution and complexity of OLED (organic light-emitting diode) panels have led to a rise in defects during the manufacturing process. Repairing these defects is crucial for enhancing the competitiveness of OLED manufacturing. The skill level of inspection operators has traditionally been the foundation of the repair system. However, an Image Processing-based Rule Base Auto Repair System has partially replaced the reliance on inspection operators. Yet, it falls short of completely replacing them without additional verification and re-repair. To overcome the challenges of detecting overlap areas between layers and detecting defects in gap regions, which are major causes of reduced accuracy in repair area detection, we explored the use of DL (deep learning) techniques. In this proposal, we introduced segmentation techniques commonly used in autonomous driving and medical fields to improve the performance of layer detection for repair targets. By developing a DL Auto Repair Process based on accurate segmentation detection of repair targets, we established a stable system by combining classification DL and detection DL. The proposed technology has led to the development of an Auto Repair System that eliminates the need for inspection operators for the specific defects. The proposed method has been successfully applied in real manufacturing processes

Two-photon absorption induced optical limiting action of Ag-doped lanthanum molybdate decorated reduced graphene oxide nanocomposites

In this research, we aimed to investigate the linear and non-linear optical properties of Ag-La2(MoO4)3@RGO nanocomposites. For this purpose, Graphene Oxide (GO) was synthesized by Modified Hummer’s method after which GO was chemically reduced to Reduced graphene oxide (RGO). The nanocomposite Ag-doped La2(MoO4)3 is prepared by a simple and facile co-precipitation method. The prepared nanocomposite was characterized by Fourier transform infrared (FTIR), Ultraviolet-Visible (UV-Vis) absorption, X-ray diffraction (XRD), Scanning electron microscope (SEM), and energy dispersive X-ray spectroscopy (EDX). XRD and EDX analysis indicated the reduction of GO and successful synthesis of Ag-doped La2(MoO4)3 nanocomposite. FESEM images portray the presence of thin layers of graphene sheets and Ag-doped La2(MoO4)3 on the sheets of reduced graphene oxide. Ground state absorption studies show that the reduction of graphene oxide causes a hypsochromic shift in the absorption maxima of the graphene layers. The photoluminescence of Ag- La2(MoO4)3@RGO demonstrates the utmost emission in the UV range caused by the valence band and conduction band's direct transitions in the band gap region. Z-scan method using Nd: YAG laser exposes that both nanocomposite and specific counterparts hold reverse saturable absorption behaviour. The source of optical limiting action is attributed to the excited state absorption process, emerging from the influence of the plasmon resonance state of Ag nanoparticles. Strong nonlinear absorption and lower onset limiting threshold make the Ag-La2(MoO4)3@RGO nanocomposite desirable material for laser safety devices.

Defect-induced modifications in electronic and thermoelectric properties of pentagonal PdX2 (X = Se, S) monolayers

The point defects induced in crystalline solids during the growth process unintentionally or doped intentionally after the growth process significantly modify their properties. The intentionally controlled doping of point defects in crystalline solids has been widely used to tune their properties. In this paper, we investigate the effect of vacancy and substitutional point defects on the electronic and thermoelectric properties of pentagonal PdX2 (X = Se, S) monolayers using the density functional theory (DFT) and semi-classical Boltzmann transport theory. We find that the point defects in pentagonal PdX2 (X = Se, S) monolayers modify their electronic structures. The contributions of d orbitals of Pd atoms and p orbitals of Se/S atoms are significantly affected due to the presence of point defects in the lattice. The defect states are appeared within the band gap region which effectively reduces the band gap of the monolayer. These defect states could be helpful in tuning the electrical and optical properties of the monolayer. The defect states appear within the band gaps of defective monolayer structures which effectively modifies the electronic properties of these monolayer structures. The transport calculations show that the presence of the point defects in the lattice reduces the thermoelectric performance of these PdX2 monolayers. Both the Seebeck coefficient and electrical conductivity show deteriorated behaviour under the influence of point defects in the lattice. Thus, the influence of these defects must be carefully taken into account while fabricating these materials for practical applications.