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The CO reduction reaction (CORR) for the production of high-value-added multi-carbon (C2+) products is currently being actively investigated, where searching for high-efficiency catalysts with moderate CO intermediate binding strength and low kinetic barrier for C–C coupling poses a significant challenge. In this study, we employed density functional theory computations to design four synergistic coupling dual sites catalysts for CORR to C2 products, namely, TM-P@melon, by co-doping transition metals (TM = Mn, Fe, Co, and Ni) and phosphorus (P) into the polymeric carbon nitride (i.e., melon-CN). Mn–P@melon and Ni–P@melon exhibit higher selectivity toward C2H5OH and C2H6, respectively, with limiting potentials (C–C coupling kinetic energy barriers) of −0.43 V (0.52 eV) and −0.17 V (0.26 eV), respectively. The introduction of TM and P atoms not only narrows the band gap of melon-CN but also favors the coupling of CO and *CHO, providing an active site for C–C coupling, thus facilitating the catalytic reaction. Our work provides rational insights for the design of stable, low-cost, and efficient CORR dual sites catalysts that facilitate the sustainable production of high-value C2 chemicals and fuels. [ABSTRACT FROM AUTHOR]

The technologically important Cu-chalcogenides, such as Cu2Se and CuInSe2, usually have relatively small band gaps. Achieving a reliable yet efficient description of the electronic properties has proven to be quite challenging for the popular exchange-correlation functionals of density functional theory, primarily due to the involvement of full-yet-shallow Cu-3d orbitals. In this study, we evaluate the applicability of several meta-generalized gradient approximation (GGA) functionals that have been recently developed. We find that the r2SCAN (regularized-restored strongly constrained and appropriately normed) functional significantly improves upon conventional local density approximation and GGA in terms of geometry and electronic band structure; however, there is still a notable discrepancy with experimental results due to the remaining delocalization error. This error is mitigated by combining r2SCAN with a Hubbard-like U correction applied to the Cu-3d orbitals. For predicting band gaps, both the TASK functional and the mBJ potential, when combined with the U correction, demonstrate similar accuracies with a mean absolute error of 0.17–0.19 eV. This accuracy is lower than that achieved with the many-body Hedin's GW approximation method but more accurate than that of hybrid functionals. Moreover, the r2SCAN+U approach well reproduces the phonon dispersion in CuInSe2, revealing a neglected computational problem in previous reports. We conclude that the meta-GGA+U approach represents a significant advancement by striking a balance between reliability and computational effort, and further efforts are still required to describe the Cu-3d orbitals more accurately. [ABSTRACT FROM AUTHOR]

The dynamics of molecular excitonic systems are complicated by a competition between electronic coupling (which drives delocalization) and vibrational-electronic (vibronic) interactions (which tend to encourage electronic localization). A particular challenge of molecular systems is that they typically possess a large number of independent vibrations, with frequencies often spanning the entire spectrum of relevant electronic energy gaps. Recent spectroscopic observations and numerical simulations on a water-soluble chlorophyll-binding protein (WSCP) reveal a transition between two regimes of vibronic behavior, a Redfield-like regime in which low-frequency vibrations respond to a delocalized excitonic state, and a Förster-like regime where high-frequency vibrations act as incoherent excitations on individual pigments. Although numerical simulations can reproduce these effects, there is a need for a simple, systematic theory that accurately describes the smooth transition between these two regimes in experimental spectra. Here we address this challenge by generalizing the variational polaron transform approach of [Bloemsma et al., Chem. Phys. 481, 250 (2016)] to include arbitrary bath densities for systems with or without symmetry. We benchmark this theory against both numerical matrix-diagonalization methods and experimental 77 K fluorescence spectra for two WSCP variants, obtaining quite satisfactory agreement in both cases. We apply this theory to offer an explanation for the large loss in apparent electronic coupling in the WSCP Q57K mutant and to examine the likely impact of the interplay between excitonic delocalization and vibrational localization on vibrational sideband shapes and apparent coupling strengths in high-resolution optical spectra for chlorophyll-protein complexes such as WSCP. [ABSTRACT FROM AUTHOR]

Experimental rate coefficients for the quenching of vibrational levels 0 and 1 of the N 2 + A 2 Π u state by N2 are presented. The experiments were performed using near-infrared observations of the N 2 + Meinel bands excited by electron impact at several pressures of the N2 target/quenching gas. The total removal rate coefficients were derived from a Stern–Volmer analysis of the Meinel band intensities as a function of N2 density and yielded rate coefficients of (2.5 ± 0.5 × 10−10) and (5.6 ± 0.6 × 10−10) cm3⋅molecule−1⋅s−1 for vibrational levels 0 and 1, respectively. It is shown that rate coefficients increase with increasing vibrational level and decreasing energy gap. Our results impact modeling studies of the disturbed atmosphere and ionosphere as the reduced quenching rate coefficients for the preferentially excited A-state vibrational levels <2 lower the quenching altitude in the atmosphere by one scale height, or about 6 km. [ABSTRACT FROM AUTHOR]

I applied photovoltaic cells equipped with singlet fission (SF) of molecular systems to dual-wavelength laser power converters (DW-LPCs) that efficiently convert two laser lights of different wavelengths to electricity. When the SF-DW-LPC is illuminated by eye-safe laser light of 1470 nm wavelength emitted from a laser diode, a single photon is converted to a single carrier. On the other hand, a single high-energy photon emitted from a high-power and low-cost laser diode of 808 nm is converted to two carriers by SF owing to its endothermic feature, even though the photon energy is slightly lower than twice the fundamental energy gap. Furthermore, the SF-DW-LPC operates as a highly efficient solar cell. These functions are required for optical wireless power transmission to moving objects including electric vehicles and flying drones. I modeled the photovoltaic process with SF and evaluated the limiting conversion efficiencies by detailed-balance calculations. Conversion efficiencies of the SF-DW-LPC for these two laser lights are competitive with those of the conventional single-junction LPCs dedicated to these wavelengths, respectively. The efficiency under solar light is close to that of the optimally designed SF solar cell. Furthermore, the SF-DW-LPC outperforms other types of DW-LPCs designed on the basis of intermediate band, triplet–triplet annihilation, and multiple exciton generation solar cells. Endothermic SF and carrier/energy extraction into the neighboring acceptors have already been demonstrated. However, molecular systems that apply to 1470 nm have not yet been realized, which is the top-priority issue to be solved to realize highly efficient SF-DW-LPCs. [ABSTRACT FROM AUTHOR]

Cobalt oxides are known for their excellent heat transfer properties. The main component of cobalt oxides is the CoO2 monolayer, which exhibits high-temperature superconductivity caused by strong electron–phonon coupling (EPC). We here systematically investigate the structural stability, electronic structure, and magnetism of the CoO2 monolayer using first-principles and Monte Carlo simulations. On this basis, we further study the changes in the spin energy gap, magnetic axis direction, and other properties of the CoO2 monolayer with the changes in carrier concentration. By appropriately doping the CoO2 monolayer with holes, the magnetic axis direction of the CoO2 monolayer can be reversed, thereby enhancing its potential application in the field of spin electronic devices. Monte Carlo simulation is used to study the regulation of different factors on the magnetothermal properties of the CoO2 monolayer. Through the analysis of physical parameters such as Curie temperature (TC) and bandgap, we find that the appropriate carrier concentration and magnetic field can not only regulate the magnetothermal properties of materials but also further improve the efficiency of materials in low-temperature environments. [ABSTRACT FROM AUTHOR]

Environmental effects in excitation energy transfer have mostly been modeled by baths of harmonic oscillators, but to what extent such modeling provides a reliable description of actual interactions between molecular systems and environments remains an open issue. We address this issue by investigating fluctuations in the excitation energies of the light harvesting 2 complex using a realistic all-atomistic simulation of the potential energy surface. Our analyses reveal that molecular motions exhibit significant anharmonic features, even for underdamped intramolecular vibrations. In particular, we find that the anharmonicity contributes to the broadening of spectral densities and substantial overlaps between neighboring peaks, which complicates the meaning of mode frequencies constituting a bath model. Thus, we develop a strategy to construct a minimally underdamped harmonic bath that has a clear connection to all-atomistic dynamics by utilizing actual normal modes of molecules but optimizing their frequencies such that the resulting bath model can best reproduce the all-atomistic simulation results. By subtracting the underdamped contribution from the entire fluctuations, we also show that identifying a residual spectral density representing all other contributions with overdamped behavior is possible. We find that this can be fitted well with a well-established analytic form of a spectral density function or, alternatively, modeled as explicit time dependent fluctuations with muti-exponential or power law type correlation functions. We provide an assessment and the implications of these possibilities. The approach presented here can also serve as a general strategy to construct a simplified bath model that can effectively represent the underlying all-atomistic bath dynamics. [ABSTRACT FROM AUTHOR]

Spin–orbit coupling induces a current density in the ground state, which consequently requires a generalization for meta-generalized gradient approximations. That is, the exchange–correlation energy has to be constructed as an explicit functional of the current density, and a generalized kinetic energy density has to be formed to satisfy theoretical constraints. Herein, we generalize our previously presented formalism of spin–orbit current density functional theory [Holzer et al., J. Chem. Phys. 157, 204102 (2022)] to non-magnetic and magnetic periodic systems of arbitrary dimension. In addition to the ground-state exchange–correlation potential, analytical derivatives such as geometry gradients and stress tensors are implemented. The importance of the current density is assessed for band gaps, lattice constants, magnetic transitions, and Rashba splittings. In the latter, the impact of the current density may be larger than the deviation between different density functional approximations. [ABSTRACT FROM AUTHOR]

Continuum- or discrete-polarizable models for the study of optoelectronic processes in embedded subsystems rely mostly on the restriction of the surrounding electronic dielectric response to its low frequency limit. Such a description hinges on the assumption that the electrons in the surrounding medium react instantaneously to any excitation in the central subsystem, thus treating the environment in the adiabatic limit. Exploiting a recently developed embedded GW formalism with an environment described at the fully ab initio level, we assess the merits of the adiabatic limit with respect to an environment where the full dynamics of the dielectric response are considered. Furthermore, we show how to properly take the static limit of the environment's susceptibility by introducing the so-called Coulomb-hole and screened-exchange contributions to the reaction field. As a first application, we consider a C60 molecule at the surface of a C60 crystal, namely, a case where the dynamics of the embedded and embedding subsystems are similar. The common adiabatic assumption, when properly treated, generates errors below 10% on the polarization energy associated with frontier energy levels and associated energy gaps. Finally, we consider a water molecule inside a metallic nanotube, the worst case for the environment's adiabatic limit. The error on the gap polarization energy remains below 10%, even though the error on the frontier orbital polarization energies can reach a few tenths of an electronvolt. [ABSTRACT FROM AUTHOR]

Optical eigenstates with a high quality (Q) factor provide substantial advantages for a broad spectrum of optical devices, particularly those demanding strong light–matter interactions. Recently, it has been demonstrated that ultrahigh- Q resonances can be realized in planar photonic structures by merging multiple bound states in the continuum (BICs) in the momentum space. Photonic lattices with thin-film geometry are known to support abundant TE-polarized and TM-polarized BICs. While prior research has explored the merging of TE-polarized BICs, this paper presents analytical and numerical results concerning the merging of TM-polarized BICs in laterally periodic one-dimensional photonic lattices. As the thickness of photonic lattices increases, TM-polarized accidental BICs descend along the dispersion curves and eventually merge at the upper edge of the second stop band. Employing coupled-mode analysis, we calculate the analytical merging thickness at which multiple TM-polarized BICs come together at the second-order Γ point. We confirm the merging of TM-polarized BICs through finite-element method simulations. Our results can be beneficial for achieving ultrahigh- Q resonances through the merging of BICs. [ABSTRACT FROM AUTHOR]

Pentacene is one of the most investigated organic semiconductors. It is well known that the motion of excitons in pentacene and other organic semiconductors is determined by inter-molecular exciton coupling based on charge-transfer processes. In the present study, we demonstrate the impact of the admixture of tetracene, which has a larger band gap and interrupts the pentacene–pentacene interaction, on the exciton behavior in pentacene. Using a combination of optical absorption and electron energy-loss spectroscopy, we show that both the Davydov splitting and the exciton band width in pentacene strongly decrease with increasing tetracene concentration, while the decrease of the exciton band width is substantially larger. [ABSTRACT FROM AUTHOR]

The second order cumulant method offers a promising pathway to predicting optical properties in condensed phase systems. It allows for the computation of linear absorption spectra from excitation energy fluctuations sampled along molecular dynamics (MD) trajectories, fully accounting for vibronic effects, direct solute–solvent interactions, and environmental polarization effects. However, the second order cumulant approximation only guarantees accurate line shapes for energy gap fluctuations obeying Gaussian statistics. A third order correction has recently been derived but often yields unphysical spectra or divergent line shapes for moderately non-Gaussian fluctuations due to the neglect of higher order terms in the cumulant expansion. In this work, we develop a corrected cumulant approach, where the collective effect of neglected higher order contributions is approximately accounted for through a dampening factor applied to the third order cumulant term. We show that this dampening factor can be expressed as a function of the skewness and kurtosis of energy gap fluctuations and can be parameterized from a large set of randomly sampled model Hamiltonians for which exact spectral line shapes are known. This approach is shown to systematically remove unphysical contributions in the form of negative absorbances from cumulant spectra in both model Hamiltonians and condensed phase systems sampled from MD and dramatically improves over the second order cumulant method in describing systems exhibiting Duschinsky mode mixing effects. We successfully apply the approach to the coumarin-153 dye in toluene, obtaining excellent agreement with experiment. [ABSTRACT FROM AUTHOR]

We present a systematic study of the electronic properties of dangling bonds (DBs) in a variety of semiconductors and examine the relationship between DBs and the charge neutrality level (CNL) in the context of band alignments of semiconductors. We use first-principles calculations based on density functional theory to assess the energetics of DBs in a set of diamond-structure group-IV and III–V or II–VI zinc-blende-structure semiconductors, considering both cation and anion-derived states. We examine the charge-state transition levels of DBs to assess whether they can serve as a CNL to align band structures, by comparing with offsets calculated from interface calculations. Our results show that this approach for evaluating the CNL yields quantitative results for band offsets and provides useful insights. We discuss the relation with alternative approaches for determination of CNLs based on branch-point energies or transition levels of interstitial hydrogen. [ABSTRACT FROM AUTHOR]

Two-dimensional (2D) piezoelectric nanomaterials have widely been studied recently due to their promise for various applications in technology. Investigation of vertical piezoelectricity will contribute to a deeper understanding of the intrinsic mechanism of piezoelectric effects in the 2D structures. In this paper, we report a first-principle study for the structural, electronic, piezoelectric, and transport properties of new-designed Janus WSi Z 3 H (Z = N, P, and As) monolayers. The structural stability of WSi Z 3 H is theoretically confirmed based on the energetic, phonon dispersion, and also elastic analyses. At the ground state, while WSiN 3 H is an indirect semiconductor, both WSiP 3 H and WSiAs 3 H are predicted to be direct semiconductors with smaller bandgaps. When the spin-orbit coupling effects are taken into account, a large valley spin splitting is observed at the K point of WSi Z 3 H materials. Interestingly, a giant Rashba spin splitting is found in WSiP 3 H and WSiAs 3 H with Rashba constant α R up to 770.91 meV Å. Additionally, our first-principles study indicates that Janus WSi Z 3 H monolayers are piezoelectric semiconductors with high out-of-plane piezoelectric coefficient | d 31 | , up to 0.15 pm/V, due to the broken mirror symmetry. Besides, with high electron mobilities and also possessing direct band gaps, WSiP 3 H and WSiAs 3 H monolayers are favorable for applications in optoelectronics. [ABSTRACT FROM AUTHOR]

Diffusion of electrons over distances on the order of 100 μm has been observed in crystals of a small tetraheme cytochrome (STC) from Shewanella oneidensis [J. Huang et al. J. Am. Chem. Soc. 142, 10459–10467 (2020)]. Electron transfer between hemes in adjacent subunits of the crystal is slower and more strongly dependent on temperature than had been expected based on semiclassical electron-transfer theory. We here explore explanations for these findings by molecular-dynamics simulations of crystalline and monomeric STC. New procedures are developed for including time-dependent quantum mechanical energy differences in the gap between the energies of the reactant and product states and for evaluating fluctuations of the electronic-interaction matrix element that couples the two hemes. Rate constants for electron transfer are calculated from the time- and temperature-dependent energy gaps, coupling factors, and Franck–Condon-weighted densities of states using an expression with no freely adjustable parameters. Back reactions are considered, as are the effects of various protonation states of the carboxyl groups on the heme side chains. Interactions with water are found to dominate the fluctuations of the energy gap between the reactant and product states. The calculated rate constant for electron transfer from heme IV to heme Ib in a neighboring subunit at 300 K agrees well with the measured value. However, the calculated activation energy of the reaction in the crystal is considerably smaller than observed. We suggest two possible explanations for this discrepancy. The calculated rate constant for transfer from heme I to II within the same subunit of the crystal is about one-third that for monomeric STC in solution. [ABSTRACT FROM AUTHOR]

Transient absorption (TA) spectroscopy of semiconductor nanocrystals (NCs) is often used for excited state population analysis, but recent results suggest that TA bleach signals associated with multiexcitons in NCs do not scale linearly with exciton multiplicity. In this manuscript, we probe the factors that determine the intensities and spectral positions of exciton and biexciton components in the TA spectra of CdSe quantum dots (QDs) of five diameters. We find that, in all cases, the peak intensity of the biexciton TA spectrum is less than 1.5 times that of the single exciton TA spectrum, in stark contrast to a commonly made assumption that this ratio is 2. The relative intensities of the biexciton and exciton TA signals at each wavelength are determined by at least two factors: the TA spectral intensity and the spectral offset between the two signals. We do not observe correlations between either of these factors and the particle diameter, but we find that both are strongly impacted by replacing the native organic surface-capping ligands with a hole-trapping ligand. These results suggest that surface trapping plays an important role in determining the absolute intensities of TA features for CdSe QDs and not just their decay kinetics. Our work highlights the role of spectral offsets and the importance of surface trapping in governing absolute TA intensities. It also conclusively demonstrates that the biexciton TA spectra of CdSe QDs at the band gap energy are less than twice as intense as those of the exciton. [ABSTRACT FROM AUTHOR]

While dark transitions made bright by molecular motions determine the optoelectronic properties of many materials, simulating such non-Condon effects in condensed phase spectroscopy remains a fundamental challenge. We derive a Gaussian theory to predict and analyze condensed phase optical spectra beyond the Condon limit. Our theory introduces novel quantities that encode how nuclear motions modulate the energy gap and transition dipole of electronic transitions in the form of spectral densities. By formulating the theory through a statistical framework of thermal averages and fluctuations, we circumvent the limitations of widely used microscopically harmonic theories, allowing us to tackle systems with generally anharmonic atomistic interactions and non-Condon fluctuations of arbitrary strength. We show how to calculate these spectral densities using first-principles simulations, capturing realistic molecular interactions and incorporating finite-temperature, disorder, and dynamical effects. Our theory accurately predicts the spectra of systems known to exhibit strong non-Condon effects (phenolate in various solvents) and reveals distinct mechanisms for electronic peak splitting: timescale separation of modes that tune non-Condon effects and spectral interference from correlated energy gap and transition dipole fluctuations. We further introduce analysis tools to identify how intramolecular vibrations, solute–solvent interactions, and environmental polarization effects impact dark transitions. Moreover, we prove an upper bound on the strength of cross correlated energy gap and transition dipole fluctuations, thereby elucidating a simple condition that a system must follow for our theory to accurately predict its spectrum. [ABSTRACT FROM AUTHOR]

We systematically applied excited-state normal mode analysis to investigate and compare the relaxation and internal conversion dynamics of a free-base porphyrin (BP) with those of a novel functional porphyrin (FP) derivative. We discuss the strengths and limitations of this method and employ it to predict very different dynamical behaviors of the two compounds and to clarify the role of high reorganization energy modes in driving the system toward critical regions of the potential energy landscape. We identify the modes of vibrations along which the energy gap between two excited-state potential energy surfaces within the Q band manifold may vanish and find that the excess energy to reach this "touching" region is significantly reduced in the case of FP (0.16 eV) as compared to the one calculated for BP (0.92 eV). Our findings establish a link between the chemical functionalization and the electronic and vibrational structure that can be exploited to control the internal conversion pathways in a systematic way. [ABSTRACT FROM AUTHOR]

The effects of the electrical parameters, including storage capacitance, additional inductance, charging voltage, and electrode gap, on the shock wave induced by spark discharge in gas were experimentally investigated. The results showed that the shock waves induced by spark discharge conform to the attenuation law for weak spherical shock waves outside the spark core. The shock wave amplitude is approximately proportional to the electrode gap and storage energy and decreases with increasing inductance. The effect of the charging voltage on the shock wave amplitude can be almost ignored if the storage energy is the same. The average power in the first quarter cycle of spark discharge was found to be closely related to the shock wave amplitude. An empirical equation was given between the shock wave amplitude and the average discharge power, which provides convenient access to set appropriate electrical parameters to generate shock waves of specified amplitude induced by spark discharge. [ABSTRACT FROM AUTHOR]

In this work, we study the electronic and transport properties of phosphorene nanorings in two perpendicular directions (zigzag and armchair directions) in the presence of a zigzag metallic source and drain leads. Our results are based on the non-equilibrium Green's function method and a five-parameter tight-binding approach. We investigate how system parameters affect the electronic transport. These parameters include the radius of the rings, the width of the leads, and the external potential. Our results show that for all configurations studied, a transport energy gap exists whose size can be tuned by the width of the leads and the radius of the nanoring. The transmission function of wider leads shows more sensitivity to the variation of the inner radius due to higher electronic states that can respond to smaller changes in the scattering region. In addition, the transport along the armchair direction is more susceptible to tuning than the transport along the zigzag direction. The effects of external potentials on the conductance are more pronounced than the geometrical parameters. In particular, the circular potential of the amplitude of 0.1 eV can widen the transport gap by about ∼0.35 eV. [ABSTRACT FROM AUTHOR]

Intramolecular electron transfer between two biphenyl groups linked by an androstane spacer and excitation of the pyridinium-N-phenolate betaine dye B30 to the first excited singlet state are studied by quantum/classical molecular-dynamics simulations at temperatures between 150 and 300 K in solvents with a range of polarities. Temperature dependences of the solvent reorganization energies, free energies, entropies, and the inhomogeneous broadening of B30's absorption band are examined. The variances of fluctuations of the energy gap between the reactant and product states do not have the direct proportionality to temperature that often is assumed to hold. An explanation for the observations is suggested. [ABSTRACT FROM AUTHOR]

We investigate the finite size effects of a three-dimensional second-order topological insulator with fourfold rotational symmetry and time-reversal symmetry. Starting from the effective Hamiltonian of the three-dimensional second-order topological insulator, we derive the effective Hamiltonian of four two-dimensional gapped surface states by perturbative methods. Then, the sign alternation of the mass term of the effective Hamiltonian on the adjacent surface leads to the hinge state. In addition, we obtain the effective Hamiltonian and its wave function of one-dimensional gapless hinge states with semi-infinite boundary conditions based on the effective Hamiltonian of two-dimensional surface states. In particular, we find that the hinge states on the two sides of the same surface can couple to produce a finite energy gap. [ABSTRACT FROM AUTHOR]

Proton transport in aqueous systems occurs by making and breaking covalent bonds, a process that classical force fields cannot reproduce. Various attempts have been made to remedy this deficiency, by valence bond theory or instantaneous proton transfers, but the ability of such methods to provide a realistic picture of this fundamental process has not been fully evaluated. Here we compare an ab initio molecular dynamics (AIMD) simulation of an excess proton in water to a simulation of a classical H3O+ in TIP3P water. The energy gap upon instantaneous proton transfer from H3O+ to an acceptor water molecule is much higher in the classical simulation than in the AIMD configurations evaluated with the same classical potential. The origins of this discrepancy are identified by comparing the solvent structures around the excess proton in the two systems. One major structural difference is in the tilt angle of the water molecules that accept an hydrogen bond from H3O+. The lack of lone pairs in TIP3P produces a tilt angle that is too large and generates an unfavorable geometry after instantaneous proton transfer. This problem can be alleviated by the use of TIP5P, which gives a tilt angle much closer to the AIMD result. Another important factor that raises the energy gap is the different optimal distance in water-water vs H3O+-water H-bonds. In AIMD the acceptor is gradually polarized and takes a hydronium-like configuration even before proton transfer actually happens. Ways to remedy some of these problems in classical simulations are discussed. [ABSTRACT FROM AUTHOR]

A collection of sets displays a proximity gap with respect to some property if for every set in the collection, either (i) all members are δ-close to the property in relative Hamming distance or (ii) only a tiny fraction of members are δ-close to the property. In particular, no set in the collection has roughly half of its members δ-close to the property and the others δ-far from it. We show that the collection of affine spaces displays a proximity gap with respect to Reed--Solomon (RS) codes, even over small fields, of size polynomial in the dimension of the code, and the gap applies to any δ smaller than the Johnson/Guruswami--Sudan list-decoding bound of the RS code.We also show near-optimal gap results, over fields of (at least) linear size in the RS code dimension, for δ smaller than the unique decoding radius. Concretely, if δ is smaller than half the minimal distance of an RS code V ⊂ Fnq, then every affine space is either entirely δ-close to the code or, alternatively, at most an (n/q)-fraction of it is δ-close to the code. Finally, we discuss several applications of our proximity gap results to distributed storage, multi-party cryptographic protocols, and concretely efficient proof systems. We prove the proximity gap results by analyzing the execution of classical algebraic decoding algorithms for Reed--Solomon codes (due to Berlekamp--Welch and Guruswami--Sudan) on a formal element of an affine space. This involves working with Reed--Solomon codes whose base field is an (infinite) rational function field. Our proofs are obtained by developing an extension (to function fields) of a strategy of Arora and Sudan for analyzing low-degree tests. [ABSTRACT FROM AUTHOR]

Generally, the second-harmonic generation and slow light of multi-band topological edge states (TESs) have been studied separately. Therefore, the influence of simultaneous slow light and topology protection on second-harmonic generation (SHG) is deficient. Here, we propose a high-efficiency SHG using dual-frequency TESs in topological photonic crystals (TPCs) with slow-light conditions. The wave vector matching condition and energy conservation condition (frequency doubling) can be achieved by adequately adjusting the overall structural parameters of TPCs. The double-resonant nonlinear interaction between two TESs is enabled using a square lattice TPC. Due to the topological localization of the TES and the long interaction time of slow-light effect, the energy densities of the fundamental wave and SHG are significantly increased. Consequently, the high intrinsic efficiency of SHG can be obtained in the order of 7.40 × 10−4. Our work opens new avenues for using topological protected and slow light enhanced nonlinear frequency conversion in a TPC system. [ABSTRACT FROM AUTHOR]

Atrazine, a human-made herbicide, is infamous for its endocrine-disrupting properties, with adverse consequences on the immune, reproductive, and nervous systems. Consequently, effective recognition of atrazine in various environments, such as water, is critically important. This work presents a precise and efficient method for detecting atrazine across various environments, utilizing a well-established electrochemical technique. A metal organic framework (MOF) ZIF-67 has been synthesized and employed as a catalyst for the electrochemical detection of the triazine herbicide atrazine. Structural, morphological, and chemical analyses were conducted to evaluate the sensing material and to elucidate the interactions between the sensor and the analyte. The ZIF-67 was then integrated on the surface of the working electrode (carbon paste electrode (CPE)) to form a ZIF-67 modified-CPE (ZIF-67/MCPE). The ZIF-67/MCPE was utilized to detect atrazine by electrochemical techniques including differential pulse voltammetry (DPV) and cyclic voltammetry (CV). The sensor demonstrated excellent sensitivity and was effective in detecting atrazine. The modified sensor demonstrated a lower limit of detection (LLOD) of 3.7 μM within a linear concentration range of 4–44 μM and exhibited a strong linear correlation efficiency of 0.97. Computational results corroborated the experimental findings, revealing that the combination of ZIF-67 with atrazine forms minor triangular structures and exhibits enhanced dynamics compared to the pristine MOF. This improvement in the crystallinity of the ZIF-67 MOF with atrazine is attributed to the negative binding energy and reduced energy gap at the interface between the MOF and atrazine. Additionally, the sensor's practical application was evaluated by testing it on sewage water and fresh liquid milk. The sensor demonstrated an exceptional ability to detect atrazine, with a recovery rate ranging from 96% to 99%. This approach holds promise for developing electrochemical or solid-state devices for real-time atrazine monitoring. [ABSTRACT FROM AUTHOR]

A series of heterobimetallic (Au⋯Ag interlocking and Au⋯Cu interlocking) [2]catenanes were studied using DFT and TD-DFT methods to explore the relationship between their structures and properties. In order to fully investigate the influence of metal type in these [2]catenanes and compare the similarities and differences between these heterobimetallic and homometallic catenanes, the results were also compared with our previously studied homometallic Au⋯Au interlocking [2]catenane molecules. The results display that the steric hindrance increases with the increase of the number of monomers, and thus the distances between the center and the edge of the rings become longer, demonstrating a trend of outward expansion. As the size of the ring becomes larger, the total weak interaction increases and shows increasingly dispersed distribution. The value of the dispersion interaction energy increases with the overgrowth of the size of molecular systems and correspondingly the energy level of the frontier orbital decreases and the energy gap becomes bigger when two hexamers interlock. Compared with the Au⋯Ag interlocking [2]catenanes, the Au⋯Cu interlocking [2]catenanes present red-shifted absorption spectra, which is consistent with their smaller energy gap. The hole–electron analysis results indicate that the S0 → S1 excitations are almost unidirectional charge transfer excitations due to the significant separation of holes and electrons, while for the high-energy excited states, local excitations occupy a dominant position. Through the study of the specific proportion of charge transfer on each fragment in the main transition process, we found that for heterometallic [2]catenanes, the Cu atom in the Au⋯Cu interlocking [2]catenanes has a greater influence on the electronic structure. As for homometallic [2]catenanes, the effects of Au atoms in the two rings are equivalent on the electronic structure. [ABSTRACT FROM AUTHOR]

Recent works exploiting photonic valley Hall effect show that large-area topological states can be realized by inserting gapless photonic crystal structures into topological interfaces, thus effectively introducing mode width degree of freedom. However, the previously reported works focus on gapless edge states. It is rare to investigate gapped edge states, especially large-area gapped edge states. In this paper, large-area gapped edge states in a valley photonic crystal heterostructure are achieved and experimentally proved. Compared with large-area gapless topological states, the present gapped edge states are more localized, which provides a more effective way to manipulate electromagnetic waves. We implement a topological energy concentrator and topological resonator cavity based on the large-area topological transmission with the gapped edge states. It is expected that our results broaden photonic systems, which can be used in topological lasing, field enhancement, and high-capacity energy transport. [ABSTRACT FROM AUTHOR]

Despite notable advancements in cancer therapy, it remains a formidable global health challenge. The emergence of combinational treatments, particularly the integration of chemotherapy with photodynamic therapy (chemo-PDT), offers a glimmer of hope. This study introduces the development of zinc-coordinated quercetin-based self-assembled nanoparticles (ZnQ NPs) for advanced dual-mode cancer therapy. These cutting-edge ZnQ nanoparticles were synthesized in a rapid 15-minute single-step process, in stark contrast to the conventional hours or days required. Using Density Functional Theory (DFT) calculations, the optimal binding configurations of ZnQ NPs were precisely determined and further supported by band gap calculations between frontier molecular orbitals. Quercetin, a potent anticancer flavonoid, was used for the first time both as an active drug and as an organic ligand, resulting in pH-responsive nanoparticles with exceptional water dispersibility, stability, and biocompatibility. Additionally, these novel nanoparticles (NPs) were able to load chlorin e6 (Ce6), a photosensitizer known for its high singlet oxygen production, due to hydrophobic interactions within the pores. The ZnQ@Ce6 nanocomposite demonstrated remarkable Ce6 loading (19.03%) and significantly enhanced therapeutic effects, achieving a 77% cell inhibition rate under specific light conditions. This dual-functional platform, enhancing the solubility and bioavailability of Ce6 while harnessing the anticancer properties of quercetin, underscores the potential of ZnQ NPs in clinical nanomedicine, promising improved cancer treatment outcomes. [ABSTRACT FROM AUTHOR]

In order to extend the photo-shielding range of ceria from the ultraviolet (UV) region (≤400 nm) to the high-energy short-wave blue light (BL) region (400–450 nm), three groups of ceria-based materials, including ceria nanoparticles (nano-CeO 2), cerium-oxygen-sulfur (Ce-O-S) composites and samarium-cerium-oxygen-sulfur (Sm-Ce-O-S) composites, were prepared from the perspectives of improving the preparation method, non-metal doping and metal/non-metal co-doping. Although the three groups of as-prepared samples have similar phase composition, morphology and pore structure, the Sm-Ce-O-S composites show remarkable double shielding performance for UV light and short-wave BL. Compared with nano-CeO 2 and Ce-O-S composites, Sm-Ce-O-S composites that retains the characteristics of n-type semiconductor exhibits a greater degree of lattice distortion, higher concentrations of Ce3+ (41.17 %) and oxygen vacancy (77.29 %), and narrower band gap (2.71 eV). Through the comparison of the three groups of samples, the order of modification degree from high to low is as follows: metal/non-metal co-doping > non-metal doping > improving the preparation method. This paper provides experimental and theoretical support for breaking through the bottleneck of ceria in the fields of UV shielding agents and catalysts. [ABSTRACT FROM AUTHOR]

The present study aims to evaluate the impact of adding the Ni 50 Mn 37 Sn 10 Cu 3 alloy to a Ni 0.1 Zn 0.9 O ceramic matrix on structural, morphological, magnetic, thermoresistive, and thermoelectric properties. The Ni 0.1 Zn 0.9 O system was obtained through the combustion reaction method. The microcomposite (Ni 0.1 Zn 0.9 O) 1-x (Ni 50 Mn 37 Sn 10 Cu 3) x , where x = 0, 2.5, 5, 10, 20, and 40, was successfully with sintering at 1223K. The microcomposite samples exhibited a good linear relationship between the logarithm of electrical resistivity (lnρ) and the reciprocal of absolute temperature (1000/T) at 300K–360K. The values of the constants A, B, and C are characteristic of NTC behavior, and their curves closely approximate the experimental data. The resistivity ρ 305 , and the coefficients β, α, and SF obtained from the thermistors are approximately 0.12 MΩcm to 7.28 MΩcm, 5026 K–8436 K, 0.017 K-1 to 0.024 K-1, and 1.03 to 1.4, respectively. The magnetic properties of the samples increased as the alloy addition content increased, with values ranging from 51.7 to 63 for H c , 0.03 to 1.34 for M s , and 2∙10−4 to 0.13 for M r. The values of the band gap remained in the range of 2.23–2.77 eV. The magnetic, thermoelectric, and thermoresistive characteristics can be adjusted to the desired value by altering the content of Ni 50 Mn 37 Sn 10 Cu 3 in the Ni 0.1 Zn 0.9 O matrix. The results demonstrate the potential of the studied system for NTC performance materials, with magnetic and thermoelectric properties. There is significant potential for the development of new microcomposite materials, but it also opens up new research perspectives in the field, especially related to microcomposites containing Heusler alloys. [ABSTRACT FROM AUTHOR]

The pure nanostructured anatase titanium dioxide (TiO 2) and subsequent nitrogen–doped derivatives (TiO 2–x N x; where, x = 0.005, 0.01, 0.05) were synthesized by sol–gel auto–combustion technique. XRD analysis confirms the formation of pure anatase phase of TiO 2 up to doping of 1 mol% (x = 0.01) of nitrogen having tetragonal structure with space group of I 4 1 / amd whereas an additional monoclinic phase of TiO 2 –B was observed at 5 mol% of nitrogen doping in TiO 2. This sample has smallest crystallite size of ∼4.7 ± 0.2 nm corresponding to TiO 2 –B phase and ∼12.0 ± 0.1 nm corresponding to anatase phase. XRD also reveals that the crystallite size of all other samples having pure anatase phase ranges between ∼8.7 ± 0.1 nm & 13.9 ± 0.1 nm. The crystalline phase revealed from XRD of all samples was further supported by the Raman analysis. The direct optical band gap of pure TiO 2 (∼3.4 eV) was reduced non–monotonically after nitrogen doping in the ranges from ∼2.8 eV (TiO 1.95 N 0.05) to ∼2.0 eV (TiO 1.99 N 0.01). FTIR spectra confirm the metal oxide bond formation, surface adsorption of water molecules and presence of residual hydroxyl group in all crystalline samples. HRTEM analysis validates the coexistence of secondary phase of TiO 2 –B along with anatase phase of TiO 2 in studied highest doped sample (TiO 1.95 N 0.05) including its broader particle size distribution as compared to pure TiO 2. The electrical studies reveal that the highest values of dielectric constant and ac conductivity can be realized for pure TiO 2 and at 1 mol% (x = 0.01) of nitrogen doping, among all the studied nitrogen doped samples. • Influence of nitrogen doping on the physical properties of anatase TiO 2. • Highest nitrogen doping level in N:TiO 2 possesses structurally dual phase nature. • TEM images also validate the presence of dual phases within the N:TiO 2 lattice. • Nonmonotonic control of optical band gap can be realized via doping of N in TiO 2. [ABSTRACT FROM AUTHOR]

This study introduces an innovative approach for preparing gas sensors involving the formation of metal oxides from metal–organic framework materials via a two-step calcination process. A gas-sensitive material capable of detecting NH 3 at a concentration of 11 ppb at room temperature was developed using a simple and facile experimental method. Compared with materials produced in previous studies by one-step calcination, the C-doped ZnO developed in this study had a dispersed cubic porous morphology with a higher specific surface area and smaller pore size. During two-step calcination, urea acts as a structure-directing agent and increases the gas adsorption capacity of the final material. Additionally, the incorporation of urea slightly reduced the material's band gap. Further examinations confirmed the material's exceptional selectivity and long-term stability in detecting NH 3 , and response tests at 59 %, 75 %, and 85 % relative humidity indicated its tolerance to high-humidity environments. These outstanding characteristics suggest that the proposed fabrication method can produce metal-oxide materials with substantially enhanced gas-sensing performance. [Display omitted] [ABSTRACT FROM AUTHOR]

Creating the porous Zinc-Zeolitic Imidazolate Framework (Zn-ZIF) using a solvothermal technique addresses the need for advanced materials with distinctive properties and cost-effectiveness in modern applications. The PXRD, SEM, UV-DRS, TEM, and TGA/DTG are used to characterize different concentrations of Zn-ZIF. Zn-ZIF's crystalline structure and phase purity have been verified by PXRD. Using diffuse reflectance spectra, the Kubelka-Monk function determined the band gaps of the Zn-ZIF samples, and scanning electron microscopy revealed a more porous structure. At 77 K and 1 bar, the Zn-ZIF solution with a 2:1 ratio had the highest hydrogen storage capacity (1.71 wt%). The electrochemical behavior of several Zn-ZIF electrodes in a 6 M KOH electrolyte was evaluated by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) experiments. The Zn-ZIF electrode with a 2:1 ratio exhibits a low charge transfer resistance and a high proton diffusion coefficient (D) of 1.687 × 10−4 cm2 s−1. The characteristics of the 2:1 synthesized Zn-ZIF electrode as a supercapacitor were investigated. Our analysis of the generated Zn-ZIF material's specific capacitance values after 2000 cycles revealed an impressive retention rate of nearly 89 %, with values of 296.6 Fg-1. In addition, we examined the photocatalytic activities of the as-synthesized material by exposing it to ultraviolet light and seeing how it degraded organic dyes such as Cango-Red (CR) dye. With a photocatalytic efficacy of 95.06 % for CR dye, Zn-ZIF (2:1 ratio) is the most effective. These findings should provide new knowledge for researchers interested in developing novel Zn-ZIF materials for photocatalytic, energy storage, and hydrogen storage applications. [ABSTRACT FROM AUTHOR]

Augmentation of optical and magnetic properties of ZnO system via mono- and co-doping is an efficient approach to achieve enhanced ferromagnetism and photocatalytic activity. In this scenario, we made an endeavor to prepare the nanocrystalline ZnO, ZnO:Eu, and ZnO:(Eu, Er) samples through a co-precipitation technique. Structural analysis ruled out the effectual substitution of Eu and Er in the ZnO lattice without disturbing the original structure. Both ZnO:Eu and ZnO:(Eu, Er) NPs exhibited lower optical band gap values than pure ZnO. In M − H studies at room temperature, ferromagnetic behavior was observed in ZnO, ZnO:Eu, and ZnO:(Eu, Er) NPs. Expectedly, ZnO:(Eu, Er) NPs showed highest H 2 evolution than both ZnO and ZnO:Eu NPs beneath solar spectrum. The possible roots behind the extended H 2 production are discussed in detail. Hence, ZnO:(Eu, Er) NPs may find in applications is photocatalysis and spintronics. [ABSTRACT FROM AUTHOR]

A series of 14R 2 O/MO-5ZnO-3Al 2 O 3 -40TiO 2 -38P 2 O 5 (R=Li, Na, K; M = Mg, Ca, Sr) glasses were synthesized using the traditional melt-quenching method, and controlled crystallization was used to produce glass-ceramics. The results indicate that the glass transition temperature and crystallization temperature increase when the ion radius increases within the same main group. The hardness of titanium phosphate glass shows a non-linear dependence on the cation field strength, and the highest value is obtained in the glass containing Li+ and Sr2+. The major crystalline phase of the glass-ceramics is RTi 2 (PO 4) 3 /M 0.5 Ti 2 (PO 4) 3 with NASICON structure. The crystal size and cell parameters are positively correlated with the radius of cations. The glass-ceramic containing the major crystalline phase Mg 0.5 Ti 2 (PO 4) 3 crystalline phase exhibits the lowest band gap and the best photocatalytic activity, with a dye degradation rate of 68 % at 120 min, and a reaction rate of 9.24 × 10−3 min−1 is about 5 times higher than that of the same series of low-activity samples. [ABSTRACT FROM AUTHOR]

The primary goal of our research is to develop a photocatalyst capable of degrading organic molecules in water, achieved through the rare earth Yb3+ doping of Zn-Mg spinel ferrites. A key element of our approach is the use of the conventional sol-gel auto-combustion process, which has proven to be an effective method for synthesizing a high-performing, visible light-driven Zn 0.9 Mg 0.1 Fe 2- x Yb x O 4 (x = 0.000, 0.015, 0.030, 0.045, 0.060 and 0.075) nano-ferrites. Many analytical techniques were employed to evaluate the material's physicochemical characteristics, including P-XRD, EDX, FE-SEM, HR-TEM, FTIR, UV–vis, BET, VSM, EIS, and photocatalysis was carried out against the RhB. The impact of Yb3+ ion doping on the material's crystallite size and lattice parameter has been evaluated. It was found that all the samples' crystallite sizes increased between 33 and 41 nm. These magnetite nanoparticles have spherical forms and nanometric particle sizes, as revealed through field scanning electron microscopy (FE-SEM). The FTIR spectra bands at ʋ 1 (518–535) and (401–411) ʋ 2 subsequently revealed the spinel structure of the synthesized nano-ferrites. The band gap in zinc manganese ferrite increases from 2.51 eV to 2.92 eV after adding ytterbium. The surface area of the Yb3+-doped Zn-Mg ferries ranges from 23.6 m2/g to 27.8 m2/g, making them an excellent choice for data storage. The investigation of magnetic behavior shows the superparamagnetic behavior of all the samples. The produced sample's determined squareness value indicates the magnetostatic interaction between the particles. Because of the low produced coercive field value, these materials can be used in ferrofluids and hyperthermia therapy applications. Furthermore, with a higher RhB removal of 93.80 %, the Yb3+-doped sample photocatalyst successfully separated carriers generated by sunlight. The Yb3+-doped sample (ZMY-5) photocatalyst showed outstanding stability after one cycle of the stability test, obtaining an outstanding RhB elimination of 93.80 %. Zn 0.9 Mg 0.1 Yb 0.075 Fe 1.925 O 4 photocatalyst has substantial promise for large-scale pollutant treatment due to its simple synthesis method, superior magnetic characteristics, exceptional photocatalytic activity for RhB, and excellent stability. [ABSTRACT FROM AUTHOR]

This study is the first attempt to examine the electrochemical properties of TiO 2 composite with Fe 3 O 4 thin film. In our analysis, X-Ray diffraction (XRD) confirms the formation of Fe 3 O 4 on TiO 2. Fourier Transform Infrared Spectroscopy (FT-IR) and Raman spectroscopy confirmed the functional groups. The UV–Vis spectroscopy analysis shows that the addition of Fe 3 O 4 results in decrease in optical band gap. Our Cyclic Voltammetry (CV) results demonstrate that, under steady state conditions, the behaviors of TiO 2 and Fe 3 O 4 /TiO 2 electrodes regarding ion adsorption and charge transmission vary. Pseudocapacitive effects and charge transfer affects the functionality of the TiO 2 electrode, whereas two-layer capacitance effects primarily control the response of the Fe 3 O 4 /TiO 2 electrode. Numerous factors, including ion diffusion, rate capability, charge transfer, and series resistance, can be directly determined using electrochemical impedance spectroscopy (EIS). The experimental results and analysis presented in this work brings to light the significance of Fe 3 O 4 in the electrochemical response of an electrode-electrolyte interface. [ABSTRACT FROM AUTHOR]

With the rapid development of global economy and industrialization, the management and protection of water resources have become increasingly important. In this paper, a novel three-dimensional Chitosan/Fe 3 O 4 /TiO 2 @MXene photocatalyst with excellent degradation and bacterial inhibition properties was prepared by a simple one-step hydrothermal method using FeCl 3 ·6H 2 O, Chitosan (CS) and MXene (Ti 3 C 2) as main raw materials. TiO 2 was generated in-situ on the surface of Ti 3 C 2 nanosheets and modified by loading Fe 3 O 4 nanoparticles and CS films. The conformations and band gaps of the composites were modified, and then photocatalytic mechanisms, phase compositions, morphological structures, magnetic properties and photoelectrochemical properties of the photocatalysts were systematically analyzed. The degradation efficiency of the CS/Fe 3 O 4 /TiO 2 @Ti 3 C 2 composite photocatalyst can reach 95.9 % when the ration of CS to FeCl 3 ·6H 2 O is 1:3 and the hydrothermal temperature is 180 °C, which showing excellent photocatalytic performance. Meanwhile, the inhibition rate of Staphylococcus aureus (S. aureus) is close to 98.91 % under the light condition. This study further reveals that visible light is a cost-effective way to treat pollution in terms of degradation and bacteriostatic inhibition, and the composite photocatalysts can be efficiently recycled and reused under the action of a magnetic field. [Display omitted] • CS/Fe 3 O 4 /TiO 2 @MXene with excellent degradation and bacteriostatic properties was synthesized by one-step hydrothermal method. • Fe 3 O 4 formed Schottky heterojunction with TiO 2 generated in situ, CS formed a double-layer film regulation system with Ti 3 C 2. • Bacteriostatic system was built: Nanoparticles brought ROS, loaded on sharp sheets, wrapped by CS with positive charges. • The material also has outstanding cyclic degradation performance, can be easily recycled and reused due to its magnetism. [ABSTRACT FROM AUTHOR]

Cotton textiles play a universal role in everyday life, but they are prone to stain and serve as a primary channel for transmitting viruses and bacteria. The photocatalytic/antibacterial coatings are highly effective in addressing bacterial contamination on fabrics, although their efficacy diminishes with continuous use and washing. Here, insights are provided into the attachment of LiNbO 3 on cotton surfaces using eco-friendly chemical activators to promote resistance to washing cycles, self-cleaning, and bactericide textiles. LiNbO 3 nanoparticles were synthesized by low-temperature hydrothermal synthesis and directly applied to cotton fabric using immersion. The synthesized nanoparticles were characterized by X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) N 2 adsorption, diffuse reflectance for band gap determination, and Raman spectroscopy. A simple and effective impregnation method was used, promoting an ester-bond attachment between the cotton surface and the activators. Microscopy analysis (SEM) confirmed the successful deposition of the nanoparticles on cotton fabric. The LiNbO 3 coating consisted of transparent layers and did not change the properties of cotton. Methylene blue stains are generally eliminated under UV light after 2 h using nanoparticles and activators. Antibacterial properties were evaluated under visible light through direct contact with bacterial suspensions and culturing. The coated cotton fabric that was activated with oxalic acid exhibited significant photocatalytic antibacterial activity against both Escherichia coli (gram-negative) and Staphylococcus aureus (gram-positive) bacteria, with bacterial reduction rate above 97 %, even after 10 washing cycles. This performance can be attributed to the effective coupling of LiNbO 3 with oxalic acid in the cotton's surface and its resistance to washing out. This study's novel synthesis and coating method offers an environmentally friendly, cost-effective, and straightforward approach for producing LiNbO 3 self-cleaning and antibacterial surface-activated cotton. [ABSTRACT FROM AUTHOR]

Based on the hexagonal honeycomb structure and the tri-ligament chiral honeycomb structure, this paper proposes a hybrid material structure with low-frequency elastic wave suppression below 100 Hz. Based on the finite element method and Bloch's theorem, the energy band structure was calculated, and the formation of the band gap and the wave-propagation properties of the structure were carefully studied, the wave attenuation performance of the composite structure was simulated, and the influence of material properties and geometric parameters on the width and position of the band-gap distribution was discussed. The results show that the structure can generate a good band gap in the low-frequency range of 100 Hz, and the wave propagation is suppressed obviously. Demonstrating its potential in practical applications, the research in this paper provides a theoretical basis for the manufacture of low-frequency vibration damping equipment and instruments, and provides a scheme for the design of metamaterials with low-frequency band gaps. [ABSTRACT FROM AUTHOR]

Directional electron flow in the photocatalyst enables efficient charge separation, which is essential for efficient photocatalysis of H2 production. Here, we report a novel class of tetracationic cyclophanes (7) incorporating bipyridine Pt(II) and selenoviologen. X‐ray single‐crystal structures reveal that 7 not only fixes the distances and spatial positions between its individual units but also exhibits a box‐like rigid electron‐deficient cavity. Moreover, host–guest recognition phenomena are observed between 7 and ferrocene, forming host–guest complexes with a 1 : 1 stoichiometry. 7 exhibits good redox properties, narrow energy gaps, and strong absorption in the visible range (370–500 nm) due to containing two selenoviologen (SeV2+) units. Meanwhile, the femtosecond transient absorption (fs‐TA) reveals that 7 has stabilized dicationic biradical, efficient charge separation, and facilitates directional electron flow to achieve efficient electron transfer due to the formation of rigid cyclophane and electronic architecture. Then, 7 is applied to visible‐light‐driven hydrogen evolution with high hydrogen production (132 μmol), generation rate (11 μmol/h), turnover number (221), and apparent quantum yield (1.7 %), which provides a simplified and efficient photocatalytic strategy for solar energy conversion. [ABSTRACT FROM AUTHOR]

Although the electronic state of catalysts is strongly corrected with their oxygen evolution reaction (OER) performances, understanding the role of spin state in dynamic electronic structure evolution during OER process is still challenging. Herein, we developed a spin state regulation strategy to boost the OER performance of CoOOH through elemental doping (CoMOOH, M=V, Cr, Mn, Co and Cu). Experimental results including magnetic characterization, in situ X‐ray absorption spectroscopy, in situ Raman and density functional theory calculations unveil that Mn doping could successfully increase the Co sites from low spin state to intermediate spin state, leading to the largest lattice distortion and smallest energy gap between dxy and dz2 orbitals among the obtained CoMOOH electrocatalysts. Benefiting from the promoted electron transfer from dxy to dz2 orbital, facilitated formation of active high‐valent *O−Co(IV) species at applied potential, and reduced energy barrier of rate‐determining step, the CoMnOOH exhibits the highest OER performance. Our work provides significant insight into the correction between dynamic electronic structure evolution and OER performance by understanding the role of spin state regulation in metal oxyhydroxides, paving a new avenue for rational design of high‐activity electrocatalysts. [ABSTRACT FROM AUTHOR]

Vanadium oxide (VO x) has demonstrated significant potential in various applications, including sensors (included but not limited to photodetection), smart windows, and energy storage devices, attributed to its pronounced semiconductor-to-metal transition near 340 K, coupled with a structural transition. However, the requirement for high-temperature synthesis to achieve the desired phases for these applications has limited its broader utilization, particularly in contexts where high temperatures are impractical. Here, we examined the effect of thermal annealing on the structural, electronic, and photodetection properties of VO x / p- Si heterojunctions fabricated via dip coating. VO x films were categorized into three types: pristine (VO x-1), annealed at 300 °C (VO x-2), and 500 °C (VO x-3). X-ray diffraction analysis confirmed hydrated V 2 O 5 in VO 1-x and VO x-2 , while VO x-3 was pure and crystalline V 2 O 5. Significantly, the band gap narrowed from 2.75 eV in VO x-1 to 2.46 eV in VO x-3 , a result attributed to grain growth and the consequential attenuation of quantum confinement effects. The DFT calculations implemented through the VASP code supported these findings, revealing an annealing-induced increase in the work function, revealing enhanced surface electronic properties favourable to photodetection. The electrical properties of the PN heterojunction Ag/ n- VO x / p- Si/Ag with Ag/ n- VO x terminal grounded showed a transition from ohmic-like in VO x-1 to rectifying behaviour for VO x-2 and VO x-3 with dark condition reverse bias current larger than the forward bias current, showing typical Schottky junction type contact between p- Si and n- VO x. This behaviour highlights the role of annealing in modulating the interface properties between p- Si and n- VO x. Notably, the heterojunctions demonstrated superior photodetection across IR, red, green, blue, and UV spectra, with performance metrics like responsivity and sensitivity markedly improved post-annealing, attributed to increased crystallinity and reduced interface traps and work function tuning. Additionally, the devices exhibited rapid transient responses under periodic LED illumination, highlighting their potential for advanced photodetection applications. The study explores the enhancement of photodetector efficiency through thermal annealing of vanadium oxide on p- Si substrates. Annealing at 300 °C and 500 °C leads to significant improvements in crystal structure and electronic properties, confirmed by X-ray diffraction and DFT calculations. The annealed VO x films show a narrowed band gap, higher work function, and transition from ohmic to rectifying behaviour in electrical characteristics. Photodetection metrics like responsivity and sensitivity improve markedly post-annealing, with rapid response times under LED illumination, highlighting the potential for advanced photodetector applications across a broad spectral range. [Display omitted] • Thermal annealing tunes electrical, optical, and structural properties of dip-coated V2O5 on p-Si. • X-ray Diffraction and optical absorption confirm dehydration, crystallization, and bandgap narrowing. • DFT calculations reveal an annealing-induced increase in work function. • Work function tuning enhances photoresponsivity and rapid transient photocurrents across UV–Vis–NIR spectra. • Heterojunctions exhibit superior performance metrics under LED illumination. [ABSTRACT FROM AUTHOR]

In this study, composite coatings of TiO 2 /Fe3+ were developed by incorporating Fe(NO 3) 3 into TiO 2 -based coatings, produced via plasma electrolytic oxidation (PEO) on unalloyed titanium. The ability of these coatings to photodegrade methylene blue (MB) under visible light was investigated. The morphology, chemical composition, and optical properties of the PEO coatings were characterized using various techniques, including X-ray diffraction, scanning electron microscopy, photoluminescence spectroscopy, and UV–Vis diffuse reflectance. All coatings exhibited a porous structure, with phase analysis revealing the formation of anatase and rutile phases during the coating process. The coatings were also found to be hydrophobic. Increasing the concentration of Fe(NO 3) 3 in the composite coatings from 0 to 0.1 g/L resulted in a decrease in the optical band gap energy from 3.05 eV to 2.95 eV. The PEO coating with 0.10 g/L of Fe(NO 3) 3 showed the highest photocatalytic activity (PA), achieving 70 %. This improvement in PA is likely due to the formation of a heterojunction, which effectively separates electron/hole pairs. [ABSTRACT FROM AUTHOR]

In this paper, summarise the characterization and synthesis of the pure and Eu:WO 3 nanoparticles and their applications in photocatalytic and antibacterial activity. The monoclinic phase confirmed by the XRD analysis of the prepared specimens. SEM and HR-TEM scrutiny revealed nanoplate morphology scrutiny. EDS and XPS scrutiny confirmed the composition of elements of Eu, O, and W. FTIR analysis likely used for additional confirmation of functional groups. UV–Vis Analysis determined the band gap energy (Eg) of the nanoparticles, which decreased with raising the concentration of Eu doping. Optical properties of the band gap energy decreased with raising the concentration of Eu doping. Photocatalytic activity of the nanoparticles exhibited high photocatalytic activity, with a 95.3 % methylene blue (MB) dye split when exposed to visible light. The Eu:WO 3 (7 wt%) nanoparticles showed the best photocatalytic property within 120 min. The Eu:WO 3 (7 wt%) nanoparticles showed the maximum antibacterial efficiency against Staphylococcus aureus , with a zone of embarrassment of 19 mm. Overall, the study demonstrates the successful synthesis of Eu-doped WO 3 nanoparticles and their potential applications in photo catalysis and antibacterial activity, with promising results particularly at higher Eu doping concentrations. [ABSTRACT FROM AUTHOR]

Origami folding structures are vital in shaping programmable mechanical material properties. Of particular note, tunable dynamical properties of elastic wave propagation in origami structures have been reported. Despite the promising features of origami metamaterials, the influence of the kinematics of tessellated origami structures on elastic wave propagation remain unexplored. This study proposes elastic metamaterials using connected Miura-ori tubes, the kinematics of which are coupled by folding and unfolding motions in a tubular axis; achieved by periodically connecting non-rotated and rotated Miura-ori tubes. The kinematics generate wave modes with localized deformations within the unit cell of the metamaterials, affecting the global elastic deformation of Miura-ori tubes via the coupling of wave modes. Dispersion analysis, using the generalized Bloch wave framework based on bar-and-hinge models, verifies the influence of kinematics in the connected tubes on elastic wave propagation. Furthermore, folding the connected tubes changes the coupling strength of wave modes between the kinematics and global elastic deformation of the tubes by breaking the ideal kinematics. The coupling of wave modescontributes to the formation of the band gaps and their tunability. These findings enable adaptive and in situ tunability of band structures to prohibit elastic waves in the desired frequency ranges. This article is part of the theme issue 'Origami/Kirigami-inspired structures: from fundamentals to applications'. [ABSTRACT FROM AUTHOR]

Photocatalytic technology is considered to be a sustainable strategy to convert H2 O and O2 into H2 O2. However, constructing photocatalytically active and stable organic photocatalyst remain a challenge. In this study, a new class of porous aromatic framework photocatalysts (BF-PAFs) were designed and synthesized, in which 9,9′-bifluorenylidene (99′-BF) and different alkynes are alternately connected. The BF-PAFs were constructed and served as photocatalysts for H2 O2 synthesis. Experimental results show that the introduction of different alkynes can effectively regulate the optical band gap and energy band structure, which may further determine their photocatalytic performance. Upon visible light irradiation, PAF-370 exhibits high efficiency for photosynthesis of H2 O2 with a production rate of 730 μmol g–1 h–1 in the presence of sacrificial reagent from water and oxygen via oxygen reduction reaction (ORR) pathway. Furthermore, up to 61 μmol H2 O2 could be generated from this photocatalytic system after 14 hours. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: Graphene nanoribbons (GNRs), which can be considered as a special type of conjugated polymers, are quasi‐one‐dimensional graphene cutouts with an opened band gap, revealing great potential as functional materials in optoelectronic, spintronic, and energy‐related applications. An effective strategy to modulate the properties of GNRs is doping heteroatoms into the π‐skeleton. Thanks to the bottom‐up synthetic approach, a number of heteroatom‐doped GNRs with precise structures have been reported, exhibiting intriguing properties. Nevertheless, a comprehensive summary of the progress of this field has remained elusive. In this review, we summarize the history and advances in bottom‐up synthesized heteroatom‐doped GNRs, including their synthetic routes, electronic properties, and promising applications. We hope to establish the reliable structure–property relationship, and provide guidance for the molecular design of heteroatom‐doped GNRs in the future. [ABSTRACT FROM AUTHOR]