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Theoretical modeling of the solid‐state photocatalysis is one of the important issues as various useful photocatalysts have been developed to date. In this work, we investigated the mechanism of the alcohol photooxidation on niobium oxide (Nb2O5) which was experimentally developed, using the density functional theory (DFT)/time‐dependent (TD)DFT calculations based on the cluster model. The alcohol adsorption and the first hydrogen transfer from hydroxy group to surface occur in the ground state, while the second hydrogen transfer from CH proceeds in the excited states during the photoirradiation of UV or visible light. The spin crossing was identified and the low‐lying triplet states were solved for the reaction pathway. The photoabsorption in the visible light region was characterized as the charge transfer transition from O 2p of alcohol to Nb 4d of the Nb2O5 surface. The spin density and the natural population analysis indicated the generation of spin density in the moiety of carbonyl compound and its dissipation to the interface of the surface, which partly explains the electron paramagnetic resonance measurement. It was confirmed that the rate determining step is the desorption of carbonyl compound and water molecule in agreement with the experimental rate equation analysis. The present findings with the theoretical modeling will provide useful information for the further studies of the solid‐state photocatalysis. [ABSTRACT FROM AUTHOR]

The regioselective radical CH trifluoromethylation of aromatic compounds have been shown to proceed in good yield and high regioselectivity when cyclodextrin (CD) is present. Yet, the reaction mechanism and the role of CD during the reaction have remained obscure. To this end, here we performed density functional theory (DFT) calculations to the conformations obtained by semiempirical quantum mechanical molecular dynamics calculations to reveal the reaction mechanism and the role of CD in controlling regioselectivity. The results show that metal salt increases the yield but do not affect the regioselectivity, which we further confirmed by an experiment. In contrast, multiple CD‐substrate complex conformations and reaction pathways were obtained, and CD was shown to contribute to improving the regioselectivity by stabilizing the intermediate state via encapsulation. The present study indicates that CDs can increase the regioselectivity by stabilizing the intermediate and product states while only marginally affecting the transition state. [ABSTRACT FROM AUTHOR]

Density functional theory (DFT) calculations explore the stability of a single platinum atom on various flat, stepped, and defective ceria surfaces, in the context of single‐atom catalysts (SACs) for the water–gas shift (WGS) reaction. The adsorption properties and diffusion kinetics of the metal strongly depend on the support termination with large stability on metastable and stepped CeO2(100) and (210) surfaces where the diffusion of the platinum atom is hindered. At the opposite, the more stable CeO2(111) and (110) terminations weakly bind the platinum atom and can promote the growth of metallic clusters thanks to fast diffusion kinetics. The adsorption of carbon monoxide on the single platinum atom supported on the various ceria terminations is also sensitive to the surface structure. Carbon monoxide weakly binds to the single platinum atom supported on reduced CeO2(111) and (211) terminations. The desorption of the CO2 formed during the WGS reaction is thus facilitated on the latter terminations. A vibrational analysis underlines the significant changes in the calculated scaled anharmonic CO stretching frequency on these catalysts. [ABSTRACT FROM AUTHOR]

DFT functionals are of paramount importance for an accurate electronic and structural description of transition metal systems. In this work, a systematic analysis using some well‐known and commonly used DFT functionals is performed. A comparison of the structural and energetic parameters calculated with the available experimental data is made in order to find the adequate functional for an accurate description of the TiO2 bulk and surface of both anatase and rutile structures. In the absence of experimental data on the surface energy, the theoretical predictions obtained using the high‐accuracy HSE06 functional were used as a reference to compare against the surface energy values calculated with the other DFT functionals. A clear improvement in the electronic description of both anatase and rutile was observed by introducing the Hubbard U correction term to PBE, PW91, and OptPBE functionals. The OptPBE‐U4 functional was found to offer a good compromise between accurately describing the structural and electronic properties of titania. [ABSTRACT FROM AUTHOR]

A symmetric anion mediated dynamic kinetic asymmetric Knoevenagel reaction was established as a general and efficient method for accessing both N−C and N−N atropisomers. The resulting highly enantio‐pure pyridine‐2,6(1H,3H)‐diones exhibit diverse structures and functional groups. The key to excellent regio‐ and remote enantiocontrol could be owed to the hydrogen bond between the enolate anion and triflamide block of the organocatalyst. This connected the enolate anion and iminium cation by a chiral backbone. The mechanism investigation via control experiments, correlation analysis, and density functional theory calculations further revealed how the stereochemical information was transferred from the catalyst into the axially chiral pyridine‐2,6(1H,3H)‐diones. The synthetic applications also demonstrated the reaction's potential. [ABSTRACT FROM AUTHOR]

Regulating competitive reaction pathways to direct the selectivity of electrochemical CO2 reduction reaction toward a desired product is crucial but remains challenging. Herein, switching product from HCOOH to CO is achieved by incorporating Sb element into the CuS, in which the Cu−S ionic bond is coupled with S−Sb covalent bond through bridging S atoms that elongates the Cu−S bond from 2.24 Å to 2.30 Å. Consequently, CuS with a shorter Cu−S bond exhibited a high selectivity for producing HCOOH, with a maximum Faradaic efficiency (FE) of 72 %. Conversely, Cu3SbS4 characterized by an elongated Cu−S bond exhibited the most pronounced production of CO with a maximum FE of 60 %. In situ spectroscopy combined with density functional theory calculations revealed that the altered Cu−S bond length and local coordination environment make the *HCOO binding energy weaker on Cu3SbS4 compared to that on CuS. Notably, a volcano‐shaped correlation between the Cu−S bond length and adsorption strength of *COOH indicates that Cu−S in Cu3SbS4 as double‐active sites facilitates the adsorption of *COOH, and thus results in the high selectivity of Cu3SbS4 toward CO. [ABSTRACT FROM AUTHOR]

Spillover of adsorbed species from one active site to another is a key step in heterogeneous catalysis. However, the factors controlling this step, particularly the spillover of polyatomic species, have rarely been studied. Herein, we investigate the spillover dynamics of H* and CH3* species on a single‐atom alloy surface (Rh/Cu(111)) upon the dissociative chemisorption of methane (CH4), using molecular dynamics that considers both surface phonons and electron‐hole pairs. These dynamical calculations are made possible by a high‐dimensional potential energy surface machine learned from density functional theory data. Our results provide compelling evidence that the H* and CH3* can spill over on the metal surface at experimental temperatures and reveal novel dynamical features involving an internal motion during diffusion for CH3*. Increasing surface temperature has a minor effect on promoting spillover, as geminate recombinative desorption becomes more prevalent. However, the poisoning of the active site can be mitigated by the frequent gaseous molecular collisions that occur under ambient pressure in real‐world catalysis, which transfer energy to the trapped adsorbates. Interestingly, the bulky CH3* exhibits a significant spillover advantage over the light H* due to its larger size, which facilitates energy acquisition. These insights help to advance our understanding of spillover in heterogeneous catalysis. [ABSTRACT FROM AUTHOR]

Here, we describe a set of coupled experimental and theoretical analyses. The introduction of one and two additional cyano groups in the carboheptahelicene backbone enhance its electron‐accepting properties. New carboheptahelicene derivatives are synthesized, and relevant characterizations of structural features, photophysical and electrochemical properties, and structure‐property relationships are described. This present work concerns the use of the density functional theory (DFT) to highlight the structural and the optoelectronic properties of carboheptahelicene derivatives and comparing the obtained findings with the experimental ones. The experimental and theoretical spectra (UV‐Vis absorption and photoluminescence) provide excellent concurrence. Afterward, molecular structures, structural parameters, molecular electrostatic potential (MEP), highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energies of frontier molecular orbitals (FMOs) are constructed. Some other optoelectronic parameter including electron affinity (EA), ionization potential (IP), and some reactive descriptor such as chemical potential (μ), global hardness (η), electronegativity (χ) and the overall electrophilicity index (ω) are determined and indicating its potential uses as an active layer in optoelectronic efficient devices. The topological methods such as electron localization function (ELF), localization orbital locator (LOL) and the reduced density gradient method (RDG) were also conducted to clarify the strengths and kinds of interactions. [ABSTRACT FROM AUTHOR]

Herein, the full potential linearized augmented plane wave (FP‐LAPW) method based on density functional theory has been used to compute the electro‐optical and magnetic characteristics of Mg1−xNixS (x = 0%, 6.25%, 12.5%, and 25%) alloys. The stability of the Mg1−xNixS alloys is verified by the enthalpy of formation energy. In electronic features, the band structure and density of states (DOS) demonstrate the semiconducting behavior in pristine MgS compound, while Mg1−xNixS alloys show half‐metallic ferromagnetic to metallic behavior based on the doping concentration. DOS exhibit a strong pd‐hybridization between Ni‐d and S‐p orbitals in the conduction band). For 6.25%, 12.5%, and 25% concentrations, the calculated total magnetic moment is 1.45364, 1.93086, and 0.71829 μB, respectively which is primarily owing to transition metal d states. Optical characteristics including refraction, absorption, complex dielectric function, and reflectivity are studied in the range of 0–10 eV at various concentrations. The absorption of light is noted from visible to UV spans which increase their significance for optoelectronic usages. Results of Mg1−xNixS alloys reveal their potential applications in optical and magnetic storage devices. [ABSTRACT FROM AUTHOR]

The study of polaron dynamics in complex materials has garnered significant attention owing to its implications for various technological applications, including catalysis, solid‐state devices, and energy storage. This paper investigates the photo‐excited electron and hole polaron dynamics in cerium dioxide (CeO2) using time‐resolved X‐ray absorption spectroscopy, with an emphasis on the nano‐size effect. Additionally, density functional theory and multiplet calculations have been utilized to reveal the photo‐excited polaron dynamics in CeO2 single crystal (SC) and nanocrystal (NC). The electron polaron is observed to decay into a deep trap site with a short duration of ≈5 ps, while electrons in the traps stay for more than 1400 ps. The most significant observation is the behavior of holes in NC, which tends to stay longer (≈150 ps) compared to SC (<10 ps) suggesting hole existence more at the surface than at bulk. The fast dissociation of the electron polarons the prolonged lifetime of the electrons above the Fermi level and the enhanced hole lifetime at the surface are proposed to be among the various factors that influence the high reactivity of CeO2. [ABSTRACT FROM AUTHOR]

Strain engineering is a powerful technique for controlling the performance of semiconductor ceramic systems. In this article, the effect of strain engineering, specifically biaxial compressive and tensile strains, on the bonding characteristics, structure, electronic, and optical properties of nonplanar phosphorene‐like (NPP) ZnS ceramic nanolayers was investigated using density functional theory. It was observed that this ceramic exhibits greater stability under significant tensile strains. The structural stability of NPP‐ZnS ceramic, both with and without biaxial strain, was confirmed by its negative formation energy. Biaxial strain strongly influences the electronic band structure of NPP‐ZnS ceramic nanolayers, leading to a transformation from a direct band gap to an indirect gap under tensile strain. Additionally, the bandgap decreases under compressive strain, while it slightly increases under tensile strain. Various optical properties, including refractive index, extinction coefficient, absorption, reflectivity, optical conductivity, and optical susceptibility, were calculated. Biaxial compressive and tensile strains alter the optical properties, shifting them to higher or lower frequencies. NPP‐ZnS ceramic nanolayers exhibit high optical absorption in the UV range, which can be further enhanced by biaxial strain. Furthermore, under increasing compressive strain, the absorption edge moves toward higher energies. This improvement in optical absorption expands the potential applications of NPP‐ZnS ceramic nanolayers in optoelectronic devices. [ABSTRACT FROM AUTHOR]

Fluorescent molecular systems are important for various applications such as sensing of analytes, probes for biologically relevant processes and as optoelectronic materials. Achieving high fluorescence quantum yield across the spectrum of solvent polarity and in solid‐state is challenging in molecular materials. Herein, we present a strategy to achieve strongly fluorescent molecular materials based on weak intramolecular charge‐transfer (ICT) in a family of unsymmetrical donor‐thiazolo[5,4‐d]thiazole‐acceptor systems (both neutral and cationic). Detailed photophysical studies reveal that the delicate balance between the donor and acceptor result in high solution‐state fluorescence quantum yield (>80 %) in both polar protic and apolar solvents. Quantum chemical computations uncover a hitherto unappreciated insight that the extent of ICT is aptly represented by the change in Mulliken charges between the ground and excited state for different fragments rather than the classical approach of monitoring the change in dipole moment for the entire molecule. This insight rationalizes the observed photophysical properties and can have implications in the design of tuneable donor‐π‐acceptor systems. [ABSTRACT FROM AUTHOR]

Typically catalysed by transition metals, alkene isomerisation is a powerful methodology for preparation of internal olefins. In contrast, the use of more earth abundant main group reagents is limited to activated substrates, requiring high temperatures and excess stoichiometric amounts. Opening a new avenue for progressing this field, here we report applications of bulky sodium amide NaTMP (TMP=2,2,6,6‐tetramethylpiperidide) when partnered with tridentate Lewis donor PMDETA (N,N,N′,N′′,N"‐pentamethyldiethylenetriamine) in catalytic alkene isomerisation of terminal olefins under mild reaction conditions. An array of distinct olefins could successfully be isomerised, including unactivated olefins, allylamines, and allylethers, showing the high activity of this partnership. In‐depth mechanistic insights provided by X‐ray crystallography, real‐time nuclear magnetic resonance (NMR) monitoring, and density functional theory (DFT) calculations have unveiled the crucial role of in situ‐generated TMP(H) in facilitating efficient isomerisation, and the choice of alkali‐metal. Additionally, theoretical studies shed light on the observed E/Z selectivity, particularly accounting for the selective formation of Z‐vinyl ethers. The versatility of our method is further demonstrated through the isomerisation of unactivated cycloalkenes, which undergo hydrogen isotope exchange to produce deuterated compounds. [ABSTRACT FROM AUTHOR]

The mechanism of an iron‐catalyzed C—H alkenylation of pivalophenone derivatives with unsymmetric internal alkynes is investigated in details by means of density functional theory calculations. It is shown that the reaction begins with two consecutive ligand exchanges, followed by a fast and reversible oxidative addition C—H activation step. Next, an alkyne insertion into the Fe—H bond, two isomerization steps, and a reductive elimination afford the final product. The reductive elimination is the turnover‐limiting step of the process, and also determines the regiochemical outcome of the reaction. The origin of the regioselectivity is proposed to be the steric repulsion between the bulky trimethylsilyl group and the aromatic fragment in the reductive elimination step leading to the not observed regioisomer. [ABSTRACT FROM AUTHOR]

The integrity of the hydrogenated amorphous silicon/crystalline silicon (a‐Si:H/c‐Si) interface is essential for the enhanced performance of a‐Si:H/c‐Si heterojunction‐based devices. However, during annealing processes aimed at passivating silicon dangling bonds, unexpected Si epitaxy and nanotwin formation tend to emerge, even under low‐temperature conditions. Therefore, understanding the influence of such annealing on the a‐Si:H/c‐Si interfacial structure is therefore pivotal for device optimization. In this study, the atomic‐scale structural transformation of the a‐Si:H/c‐Si heterointerface subjected to low‐temperature annealing is delved into. The dynamic evolution of this interface is captured by employing in situ spherical aberration (CS)‐corrected transmission electron microscopy (TEM), molecular dynamics (MD) simulations, and density functional theory (DFT) calculations. The TEM observations indicated that Si epitaxy initiated before Si nanotwin formation, and these nanotwins are inclined to revert to epitaxial structures upon sustained annealing. Through MD and DFT insights, the thermodynamic and kinetic intricacies driving the concerted tri‐layer atomic shift characterizing the Si nanotwin‐to‐epitaxy transition are decoded. The findings shed light on the thermal behavior of a‐Si:H/c‐Si interfaces, offering new perspectives on the thermal management in silicon heterojunction devices. [ABSTRACT FROM AUTHOR]

Owing to kinetic‐sluggish nature of electrocatalytic oxygen transformation processes, it is pivotal to develop durable and efficient bifunctional air electrode catalysts for fabricating high‐performance Zn–air batteries (ZABs). In this work, oxygen vacancy (Ov) induced Mn(III) sites optimization is achieved via nano‐micro structure modulation. Protonated carbon nitride (p‐C3N4) is applied as a structure‐stiffening module to immobilize α‐MnO2 on N/P‐doped active carbon (NPAC) and induce Ov construction. X‐ray adsorption spectra (XAS) disclose the formation of Ov and Mn(III) sites in MCC, the unit coordination structure is well maintained with the aid of a dual‐carbon strategy. Mn(III) sites efficiently catalyze oxygen reduction/evolution reaction (ORR/OER), MCC shows high half‐wave potential (E1/2) of 0.88 V for ORR and low potential at 10 mA cm−2 (Ej = 10) of 1.64 V for OER. According to density functional theory (DFT) simulations analysis, the gorgeous bifunctional activity is owing to that optimized charge distribution facilitates the intermediates transformation. Aqueous ZABs based on MCC manifests high peak power density of 452 mW cm−2 and durable cycling stability of 1640 h. Quasi‐solid‐state ZABs based on MCC also show satisfactory performances (175 mW cm−2, 105 h). This work provides the route to develop efficient and durable electrocatalyst for constructing ZABs with long lifespan and high‐power‐density. [ABSTRACT FROM AUTHOR]

Urea oxidation reaction (UOR) is an ideal alternative to oxygen evolution reaction (OER) for efficient hydrogen production but is immensely plagued by slow kinetics. Herein, a multilayer hole amorphous boron‐nickel catalyst (a‐NiBx) is fabricated through a simple chemical plating method, which displays intriguing catalytic activity toward UOR, demanding a low working potential of 1.4 V to reach 100 mA cm−2. The high performance is credited to the formation of metaborate (BO2−), which can promote the formation of high‐oxidation‐state NiOOH active phase and optimize the adsorption of urea molecules. This can be confirmed by the operando spectroscopy characteristics and density functional theory calculations. Consequently, the assembled electrolyzer utilizing NiBx as bifunctional catalysts exhibited splendid catalytic activity, requiring an evidently lower voltage of 1.66 V to reach a current density of 100 mA cm−2 and 1.57 V when using Pt/C as a cathode catalyst. Moreover, the assembled electrolyzer secured a robust stability of over 200 h, as well as a four times higher hydrogen production rate than traditional water electrolysis. [ABSTRACT FROM AUTHOR]

2D metal–organic frameworks (2D MOFs) offer promising electrocatalytic potential for urea synthesis, yet the underlying reaction mechanisms and structure‐activity relationships remain unclear. Using Cu‐BDC as a model, density functional theory (DFT) calculations to elucidate these aspects are conducted. The results reveal a novel coupling mechanism involving *NO─CO and *NO─*ONCO, emphasizing the impact of linker modifications on Cu spin states and charge distribution. Notably, Cu‐BDC‐NH2 and Cu─BDC─OH emerge as promising catalysts. Additionally, structure‐activity relationships through descriptors like d‐band center, IE ratio, and L(Cu─O), providing insights for rational catalyst design is established. These findings pave the way for optimized catalysts and sustainable urea production, opening avenues for future research and technological advancements. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: Compared to well‐established 1,5‐HAT of N‐centered radicals, the synthetic applications of 1,2‐HAT process were scarce due to the high barrier and constrained three‐membered transition state. Here, we have developed a novel C(sp3)‐H gem‐difluoroallylation via a base assisted formal 1,2‐HAT of amidyl radicals with the reductive quenching cycle of photocatalyst. This transformation enables the efficient formation of α‐aminoalkyl radicals via 1,2‐HAT and showcases good functional group tolerance. Our preliminary mechanistic experiments, along with Density Functional Theory (DFT) calculations demonstrate the feasibility of 1,2‐HAT of amidyl radicals, especially when assisted by a base. Furthermore, our method also succeeds in the Giese addition of electron‐deficient alkenes as well as styrene. [ABSTRACT FROM AUTHOR]

The influence of the composition of the functional used for density functional theory computations on one structural parameter (a dihedral angle) and a spectroscopic parameter (absorption wavelength) is assessed in this study on the basis of two molecules (flavonols). In this kind of molecules, these two parameters should be correlated according to the nature of the electronic transition involved. However, it is shown herein that by varying the proportion of true exchange and correlation while building a functional, it is possible to obtain independently a large range of values for these parameters without any relation with the underlying real values. Therefore, it is concluded that the choice of a functional after a benchmark, especially using user‐defined functionals, should be carried out with great care to avoid such effects. [ABSTRACT FROM AUTHOR]

In this article, we explore the construction of Hamiltonians with long‐range interactions and their corrections using the short‐range behavior of the wave function. A key aspect of our investigation is the examination of the one‐particle potential, kept constant in our previous work, and the effects of its optimization on the adiabatic connection. Our methodology involves the use of a parameter‐dependent potential dependent on a single parameter to facilitate practical computations. We analyze the energy errors and densities in a two‐electron system (harmonium) under various conditions, employing different confinement potentials and interaction parameters. The study reveals that while the mean‐field potential improves the expectation value of the physical Hamiltonian, it does not necessarily improve the energy of the system within the bounds of chemical accuracy. We also delve into the impact of density variations in adiabatic connections, challenging the common assumption that a mean field improves results. Our findings indicate that as long as energy errors remain within chemical accuracy, the mean field does not significantly outperform a bare potential. This observation is attributed to the effectiveness of corrections based on the short‐range behavior of the wave function, a universal characteristic that diminishes the distinction between using a mean field or not. [ABSTRACT FROM AUTHOR]

Chiral carbon dots (CDs) with circularly polarized luminescence (CPL) are one of the most dynamic areas of modern science. However, the design, preparation, and ambiguity mechanism of solid‐state CPL‐active CDs remains a formidable challenge. Herein, for the first time, CDs with customized chiroptical activities in the solid state, especially CPL, are transcribed from chiral metal–organic framework (CMOFs) via a bottle‐around‐ship strategy. Within these CMOFs⊃CDs assemblies, CDs inherited the chirality of the host CMOFs through host–guest interactions, which is revealed by density functional theory (DFT) simulations and experimental results, and amplified the luminescence dissymmetry factor (glum) by effective artificial chiral light‐harvesting systems. Impressively, CMOFs⊃CDs in pairs generated color‐tunable CPL and white CPL with chromaticity coordinates of (0.32, 0.32). Furthermore, benefiting from excellent processability, as luminescent coatings and 3D printing inks, a white circularly polarized light‐emitting diode, and an extended 3D model “light bulb” featuring white CPL are successfully fabricated, respectively. This strategy paves a new avenue for the synthesis and advanced application of solid‐state CPL‐active CDs‐based materials. [ABSTRACT FROM AUTHOR]

Transition metal sulfides are emerging as promising anode materials for sodium‐ion batteries (SIBs) due to their high theoretical capacity and low cost, their practical application yet face critical issues of sluggish kinetics and poor cycling stability. In this study, a reliable approach is introduced to overcome these challenges by fabrication of Se0.75‐Fe1‐xS0.25@SC hollow nanospheres thanks to the enriched robust Fe─S─C, C─S, and C─Se bonding, which greatly benefit for enhancing both reaction kinetics and structural stability. Kinetic study combining with in situ characterization reveals that the incorporation of rich‐Se into FeSx induces the formation of cationic Fe and Se vacancies, leading to abundant sites and optimized path for sodium storage. Density functional theory calculations also demonstrate how Se‐rich engineering weakens carbonaceous polar C─S─Fe bonds and accelerates reaction dynamics. The as‐prepared Se0.75‐Fe1‐xS0.25@SC can deliver a high reversible capacity of 515 mAh g−1 at 2 A g−1 over 1250 cycles and achieve superior rate capability with maintaining capacity of 418 mAh g−1 at 10 A g−1. This work pioneers the concept of vacancy‐rich functionalized nanostructures, offering a new pathway for designing advanced electrode materials for energy storage devices. [ABSTRACT FROM AUTHOR]

A colloidal synthesis protocol is demonstrated for InAs@InP core@shell quantum dots (QDs) with a tunable InP shell thickness (ranging from 3 to 8 monolayers), utilizing tris(diethylamino)‐arsine and ‐phosphine. Structural analysis reveals that the InP shell preferentially grows onto the tetrahedral InAs cores along the <‐1‐1‐1> directions, forming tetrapodal‐shaped InAs@InP QDs. Growth of the InP shell causes a red shift in the absorption spectrum of the QDs. This is explained by considering that electrons are delocalized throughout the whole core@shell QDs, while holes preferentially leak along the <‐1‐1‐1> directions, as indicated by the density functional theory calculations. This means such heterostructures cannot be described as type‐I or quasi type‐II, contrary to earlier assumptions. The overlap of carrier wavefunctions throughout the entire InAs@InP QD structure results in no significant reduction of the Auger recombination rate, which remains as fast as in InAs QDs. However, the InP shell enhances photoluminescence (PL) efficiency (up to ≈13%) by passivating surface trap states of the InAs QDs (mainly located close to the top of the valence band). The overgrowth of a ZnSe shell endows the QDs with a high PL efficiency (≈55%) and good stability upon air exposure (≈80% PL intensity retention after 14 days). [ABSTRACT FROM AUTHOR]

Chloride–ion batteries (CIBs) offer a compelling alternative to conventional battery systems, particularly in applications demanding cost‐effectiveness and resource sustainability. However, the development of tailored electrode materials remains a critical bottleneck for CIB advancement. In this study, an untapped class of perovskite‐based material, potassium hexachlorostannate (K2SnCl6, denoted as KSC) is synthesized via a facile mechanochemical route for the first time. The prepared KSC is subjected to various characterization techniques to confirm its crystal structure and morphology. Herein, KSC exhibits intriguing electrochemical performance in a non‐aqueous CIB configuration, utilizing a lithium metal counter electrode. Furthermore, ex situ X‐ray diffraction (XRD) and X‐ray photoelectron spectroscopy (XPS) analysis, reveal a conversion reaction mechanism involving chloride ion shuttling and provide insights into structural evolution during cycling. Moreover, the density functional theory (DFT) studies support additional degradation products that can potentially limit the performance of these materials as potential battery electrodes in CIBs. [ABSTRACT FROM AUTHOR]

Electrocatalytic nitrate reduction reaction (NO3RR) can convert nitrate contaminants into ammonia with higher added value. However, due to the NO3RR involving complex multi‐electron reactions, there is an urgent need to develop efficient electrocatalysts. Herein, CoCu Janus nanoparticles loaded on Ti3C2Tx MXene (CoCu‐Ti3C2Tx) is synthesized via the combination of molten salt etching and galvanic replacement strategy. The tandem catalysis of CoCu Janus NPs can maintain the balance between nitrogenous intermediates and active hydrogen (Hads). CoCu‐Ti3C2Tx exhibits a high NH3 yield of 8.08 mg h−1 mgcat.−1 and a satisfactory Faradaic efficiency of 93.6% at −0.7 V versus reversible hydrogen electrode (RHE). The Zn‐NO3− battery assembled with CoCu‐Ti3C2Tx shows an excellent power density of 10.33 mW cm−2, an NH3 yield of 1.52 mg h−1 mgcat.−1 and a Faradaic efficiency of 95.3% at 10 mA cm−2, which enables the simultaneous elimination of nitrate pollutants, ammonia production, and energy supply. Moreover, a series of verification experiments and density functional theory calculation are combined to reveal the reaction path and tandem catalytic mechanism. This work not only provides a new inspiration for the design of tandem catalysts but also promotes the development of Zn‐nitrate battery. [ABSTRACT FROM AUTHOR]

In order to address imminent energy and environmental challenges, photocatalytic water splitting emerges as a promising way for harnessing solar radiation to generate clean chemical energy. 2D arsenene (β‐As) has notable catalytic activity in hydrogen production. Based on first principles calculations and non‐adiabatic molecular dynamics (NAMD) simulations, the β‐As/Ti2CO2 heterojunction is predicted to be a promising Z‐scheme photocatalyst for overall solar water splitting. It has a desirable energy band structure with the valence band maximum of Ti2CO2 and the conduction band minimum of β‐As well below and above the redox potentials of H2O. Both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) can proceed spontaneously under light irradiation. NAMD simulations confirm that it is a Z‐scheme photocatalyst with fast electron–hole combination dynamics. Instead of by intrinsic electric field, such a fast electron–hole combination is driven by a large nonadiabatic coupling. The heterojunction exhibits strong optical absorption in the visible and ultraviolet regions. The estimated solar‐to‐hydrogen (STH) efficiency limit of β‐As/Ti2CO2 reaches 32%, which is the highest among all β‐As based junctions reported in the literature. These results suggest that β‐As/Ti2CO2 is a promising photocatalyst for achieving overall water splitting. [ABSTRACT FROM AUTHOR]

Many ligands commonly used to prepare nanoparticle catalysts with precise nanoscale features contain nitrogen (e.g., oleylamine); here, it is found that the use of nitrogen‐containing ligands during the synthesis of metal oxide nanoparticle catalysts substantially impacts product analysis during photocatalytic studies. These experimental results are confirmed via hybrid Density Functional Theory (DFT) computations of the materials’ electronic properties to evaluate their viability as photocatalysts for nitrogen reduction. This nitrogen ligand contamination, and subsequent interference in photocatalytic studies is avoidable through the careful design of synthetic pathways that exclude nitrogen‐containing constituents. This result highlights the urgent need for careful evaluation of catalyst synthesis protocols, as contamination by nitrogen‐containing ligands may go unnoticed since the presence of nitrogen is often not detected or probed. [ABSTRACT FROM AUTHOR]

The rational construction of a hierarchical noble metal–metal‐organic frameworks (MOFs) structure is anticipated to yield enduring and highly efficient performance in alkaline electrocatalytic water splitting. Herein, a sandwich construction strategy is employed to enhance the stability, wherein active RutheniRu (Ru) nanosheets are incorporated onto nickel foam (NF) and subsequently covered with porphyrinic MOFs (PMOFs). In addition, activated PMOF‐NiOOH‐Ru20/NF‐C/A electrodes are obtained by electrochemical self‐reconstruction as cathode and anode, respectively. Density functional theory (DFT) calculations demonstrated that the resulting PMOF‐NiOOH‐Ru heterointerface effectively facilitated electron transfer, enhanced H2O adsorption capacity, and optimized ΔG values for *H and *O to *OOH. Consequently, PMOF‐NiOOH‐Ru20/NF‐C/A exhibited low overpotentials for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), accompanied by minimal Ru leakage. Furthermore, stable overall water splitting can be achieved with a low voltage of 1.456 V@10 mA cm−2 for over 120 h. Even when operated in simulated seawater, the prepared electrodes demonstrated similar activity and stability. This study contributes to a deeper understanding of the regulation mechanism for the performance and stability of active sites in the electrocatalytic self‐reconstruction process. [ABSTRACT FROM AUTHOR]

Vanadate materials are promising for sodium‐ion batteries (SIBs) due to their low cost, high capacity, and high power characteristics enabled by vanadium's multiple oxidation states. However, their development is hindered by poor conductivity, suboptimal high‐rate performance, and limited cycle life. In this work, a layered structure modification strategy involving Ca/F co‐doping in sodium vanadate Na2CaV2O6F (CVF) is proposed to address these issues. Through a combination of experiments and density functional theory calculations, it is demonstrated that Ca/F synergies enhance the Na layer spacing in CVF, resulting in reduced crystal water content and volume shrinkage compared to Na2V2O6 (NVO). Additionally, Ca/F incorporation significantly mitigates the diffusion potential of Na+ within the material framework. The unmodified CVF sample exhibits a high reversible capacity of 220 mAh g−1 at 10 mA g−1 and an excellent rate capacity of 65.78 mAh g−1 at 400 mA g−1. Furthermore, the cathode material maintains a capacity of up to 138 mAh g−1 at 200 mA g−1 and retains 104.88 mAh g−1 after 100 cycles within the voltage range of 1.5−4.0 V. These findings enhance the understanding of the crystal structure of NVO cathode materials and pave the way for the rational design of high‐quality vanadate cathodes for SIBs. [ABSTRACT FROM AUTHOR]

Small molecule organic materials are widely used as anode materials for lithium‐ion batteries (LIBs) due to their high reversible capacity, designable structure, and environmental friendliness. However, they suffer from poor intrinsic electronic conductivity, severe dissolution, and low initial coulombic efficiency. Recently, metal–organic frameworks (MOFs) have demonstrated in metal‐ion batteries, outperforming some small molecule organic materials in terms of both cycling stability and rate capability. Herein, the first rational design and synthesis of a new cobalt‐based MOF (CoBPDCA), are reported employing cobalt(II) nitrate as the metal source and small organic molecules (2,2‐bipyridyl‐4,4‐dicarboxylic acid, BPDCA) as the ligands, which shows exceptional chemical stability and impressive electron conductivity. Most importantly, CoBPDCA electrodes deliver a high reversible capacity of 1112.9 mAh g−1 at 0.05 C (1 C = 1000 mA g−1) and outstanding high‐rate durability (166.3 mAh g−1 after 2500 cycles at 10 C). Employing a series of spectroscopic and morphological characterizations and density functional theory (DFT) calculations, it is revealed that these impressively electrochemical performances are contributed to the dual active redox centers of Co cations and BPDCA ligands (CN and CO groups), and the superb electron conductivity. This work might provide a new strategy and a deeper understanding of the other MOFs' development for LIBs. [ABSTRACT FROM AUTHOR]

Sulfur‐containing functional groups have garnered considerable attention due to their common occurrence in ligands, pharmaceuticals, and insecticides. Nevertheless, enantioselective synthesis of sulfilimines, particularly diaryl sulfilimines remains a challenging and persistent goal. Herein we report a highly enantio‐ and chemoselective cross–coupling of sulfenamides with aryl diazonium salt to construct diverse S(IV) stereocenters by Pd catalysis. Bisphosphine ligands bearing sulfinamide groups play a crucial role in achieving high reactivity and selectivity. This approach provides a general, modular and divergent framework for quickly synthesizing chiral sulfilimines and sulfoximines that are otherwise challenging to access. In addition, the origins of the high chemoselectivity and enantioselectivity were extensively investigated using density functional theory calculations. [ABSTRACT FROM AUTHOR]

The radical Truce–Smiles rearrangement is a straightforward strategy for incorporating aryl groups into organic molecules for which asymmetric processes remains rare. By employing a readily available and non‐expensive chiral auxiliary, we developed a highly efficient asymmetric photocatalytic acyl and alkyl radical Truce–Smiles rearrangement of α‐substituted acrylamides using tetrabutylammonium decatungstate (TBADT) as a hydrogen atom–transfer photocatalyst, along with aldehydes or C−H containing precursors. The rearranged products exhibited excellent diastereoselectivities (7 : 1 to >98 : 2 d.r.) and chiral auxiliary was easily removed. Mechanistic studies allowed understanding the transformation in which density functional theory (DFT) calculations provided insights into the stereochemistry‐determining step. [ABSTRACT FROM AUTHOR]

Electrocatalytic reduction of CO2 powered by renewable electricity provides an elegant route for converting CO2 into valuable chemicals and feedstocks, but normally suffers from a high overpotential and low selectivity. Herein, Ag and Sn heteroatoms were simultaneously introduced into nanoporous Cu (np‐Ag/Sn−Cu) mainly in the form of an asymmetric local electric field for CO2 electroreduction to CO in an aqueous solution. The designed np‐Ag/Sn−Cu catalyst realizes a recorded 90 % energy efficiency and a 100 % CO Faradaic efficiency over ultrawide potential window (ΔE=1.4 V), outperforming state‐of‐the‐art Au and Ag‐based catalysts. Density functional theory calculations combined with in situ spectroscopy studies reveal that Ag and Sn heteroatoms incorporated into Cu matrix could generate strong and asymmetric local electric field, which promotes the activation of CO2 molecules, enhances the stabilization of the *COOH intermediate, and suppresses the hydrogen evolution reaction, thus favoring the production of CO during CO2RR. [ABSTRACT FROM AUTHOR]

The vast number of element combinations and the explosive growth of composition space pose significant challenges to the development of high‐entropy alloys (HEAs). Here, we propose a procedural research method aimed at accelerating the discovery of efficient electrocatalysts for oxygen reduction reaction (ORR) based on Pt‐based quinary HEAs. The method begins with an element library provided by a large language model (LLM), combined with microscale precursor printing and pulse high‐temperature synthesis techniques to prepare multi‐element combination HEA array in one step. Through high‐throughput measurement using scanning electrochemical cell microscopy (SECCM), precise identification of highly active HEA element combinations and exploration of composition space for a specific combination are achieved. Advantageous element combinations are further validated in practical electrocatalytic evaluations. The contributions of individual element sites and the synergistic effects among elements of such HEAs in enhancing reaction activity are elucidated via density functional theory (DFT) calculations. This method integrates high‐throughput experiments, practical catalyst validation, and DFT calculations, providing a new pathway for accelerating the discovery of efficient multi‐element materials in the field of energy catalysis. [ABSTRACT FROM AUTHOR]

The biosynthesis of six recently reported non‐canonical C16 sesquiterpenoids named after ancient Greek philosophers, archimedene, aristotelene, eratosthenene, pythagorene, α‐democritene and anaximandrene, was investigated through density functional theory (DFT) calculations and isotopic labeling experiments. The results revealed for all compounds except archimedene a unique fragmentation‐recombination mechanism as previously demonstrated for sodorifen biosynthesis, in addition to a remarkable "dancing" mechanism for anaximandrene biosynthesis. [ABSTRACT FROM AUTHOR]

Transition metal sulfides as anode materials for sodium‐ion batteries (SIBs) have the advantage of high capacity. However, their cycle‐life and rate performance at ultra‐high current density is still a thorny issue that limit the applicability of these materials. In this paper, the carbon‐embedded heterojunction with sulfur‐vacancies regulated by ultrafine bimetallic sulfides (vacancy‐CoS2/FeS2@C) with robust interfacial C‐S‐Co/Fe chemical bonds is successfully synthesized and explored as an anode material for sodium‐ion battery. By changing the ratio of two metal cations, the concentration of anion sulfur vacancies can be in‐situ adjusted without additional post‐treatment. The as‐prepared vacancy‐CoS2/FeS2@C anode material offers ultrahigh rate performance (285.1 mAh g−1 at 200 A g−1), and excellent long‐cycle stability (389.2 mAh g−1 at 40 A g−1 after 10000 cycles), outperforming all reported transition metal sulfides‐based anode materials for SIBs. Both in‐situ and ex‐situ characterizations provide strong evidence for the evolution mechanism of the phases and stable solid‐electrolyte interface (SEI) on the vacancy‐CoS2/FeS2@C surface. The density functional theory calculations show that constructing heterojunction with reasonable concentration of vacancies can significantly increase the anode electronic conductivity. Notably, the assembled vacancy‐CoS2/FeS2@C//Na3V2(PO4)3/C full‐cell shows a capacity of 226.2 mAh g−1 after 400 cycles at 2.0 A g−1, confirming this material's practicability. [ABSTRACT FROM AUTHOR]

With the rapid development of flexible displays and wearable electronics, there are a substantial demand for colorless transparent polyimide (CPI) films with different properties. Traditional trial‐and‐error experimental methods are time‐consuming and costly, and density functional theory based prediction of HOMO‐LUMO gap energy also takes time and is prone to varying degrees of error. Inspired by machine learning (ML) applications in molecular and materials science, this paper proposed a data‐driven ML strategy to study the correlation between microscopic molecular mechanisms and macroscopic optical properties. Based on varying degrees of impact of various molecular features on the cutoff wavelength (λcutoff), the ML algorithm is first used to quickly and accurately predict the λcutoff of CPI. Several new CPI films are then designed and prepared based on the key molecular features, and the predicted values of their λcutoff are effectively verified within the experimental error range. The interpretability provided by the model allows to establish correlations between the nine key descriptors identified and their physicochemical meanings. The contributions are also analyzed to the transparency of polyimide films, thereby giving insight into the molecular mechanisms underlying transparency modulation for CPIs. [ABSTRACT FROM AUTHOR]

Quantum computers are expected to outperform classical computers for specific problems in quantum chemistry. Such calculations remain expensive, but costs can be lowered through the partition of the molecular system. In the present study, partition was achieved with range‐separated density functional theory (RS‐DFT). The use of RS‐DFT reduces both the basis set size and the active space size dependence of the ground state energy in comparison with the use of wave function theory (WFT) alone. The utilization of pair natural orbitals (PNOs) in place of canonical molecular orbitals (MOs) results in more compact qubit Hamiltonians. To test this strategy, a basis‐set independent framework, known as multiresolution analysis (MRA), was employed to generate PNOs. Tests were conducted with the variational quantum eigensolver for a number of molecules. The results show that the proposed approach reduces the number of qubits needed to reach a target energy accuracy. [ABSTRACT FROM AUTHOR]

Supramolecular complexes of carbon nanohoops with fullerenes play a key role for the design of novel nanomaterials with technological applications. Herein we investigate with density functional theory (DFT) methods the capability of neutral and dioxidized cycloparaphenylenes (CPPs) to encapsulate all‐boron fullerene B40. Our results show that [9]CPP and [10]CPP are feasible host candidates to encapsulate B40 displaying comparable complexation energies with the all‐carbon analog [10]CPP⊃C60. Upon dioxidation the host‐guest interactions are not affected, whereas the positive charge is delocalized on the CPPs leading to global aromatic character of the hosts. Consequently, the dicationic complexes [n]CPP2+⊃B40 and [10]CPP2+⊃C60 display augmented global shielding cones that strongly shield the guests, as manifested by large upfield shifts in 11B‐NMR and 13C‐NMR signals. Hence, CPP complexes with carbon fullerenes can be extended borospherene B40 host‐guest complexes, as well as to doubly oxidized species stabilized by global host aromaticity, expanding our understanding of carbon nanohoop complexes to boron‐based fullerenes. [ABSTRACT FROM AUTHOR]

The magnetite oxidation process involves magnetite surface adsorption and O2 dissociation, and the presence of impurity elements such as silicon inevitably affects the magnetite surface adsorption process. To explore and analyze the surface adsorption and oxidation behaviors of silicon‐doped Fe3O4, thermogravimetric experiments and density functional theory methods are used to investigate the physicochemical properties of this material during magnetite oxidation. The results of experiments show that with the increase of SiO2 content, the peaks of the oxidation reaction gradually migrate to the high‐temperature region, the initial oxidation temperature of the mineral increases, and the average oxidation rate decreases. The results of calculations show that when the surface system is doped with Si atoms, the relaxation time of the adsorption and dissociation of oxygen on the surface is prolonged, and the presence of Si isomerization tends to stabilize the crystal lattice structure, reduce the migration of ions, and decrease the mineral's oxidizing properties. [ABSTRACT FROM AUTHOR]

Pesticides are being used in unregulated and excessive amounts to increase crop yield, causing food and water contamination. Continuous consumption of these pesticides can lead to a variety of health problems, including cancer, respiratory problems, neurological disorders, and reproductive problems. Vibrational spectroscopy uses the unique vibrational modes of these chemicals to identify and quantify their composition with high sensitivity, selectivity, speed, and accuracy. Density functional theory (DFT) can accurately model the vibrational response of these pesticides. Metribuzin, with a triazinone type ring structure, is one such commercial weedicide that is widely used but has not been extensively studied in literature, especially the study of its vibrational modes is lacking. Metribuzin's Raman and infrared (IR) vibrational modes were analyzed in the present article. The calculated bond length, Raman, and IR spectra (using aug‐cc‐pVTZ B3LYP level of theory) were experimentally confirmed. All the major vibrational modes of Metribuzin were assigned. Also, the basis set comparison was performed for DFT/B3LYP method for Raman spectrum calculation of Metribuzin. The errors in wavenumber and intensity of the Raman vibrational modes for each basis set were compared. Hence, the complete study of Metribuzin's structure and vibrational modes was presented. [ABSTRACT FROM AUTHOR]

Cancer remains a severe global health problem, with its incidence constantly increasing.. Among many varieties of cancer, breast cancer persists as a prevalent global health concern, with its occurrence continually ascending. Among women, breast cancer is a significant cause of illness and death globally. This study examined the antioxidant and anticancer effects of two resynthesized benzoxazine derivatives, OBOP‐01 and OBOP‐02, on human breast cancer cells. The chemicals investigated had intense antioxidant action against DPPH, H2O2, and ABTS free radicals. Furthermore, we evaluated cell viability by converting yellow MTT (3‐(4,5‐dimethylthiazol‐2‐yl)‐2,5‐diphenyl tetrazolium bromide) into purple formazan, dependent on mitochondrial function. Both compounds had IC50 values of 1.52±0.02 mM and 1.72±0.02 mM respectively. Moreover, toxicity predictions using the ProTox‐III webserver showed that the benzoxazines studied have lower LD50 values compared to doxorubicin, suggesting greater safety. We also used Density Functional Theory (DFT) to analyze OBOP‐01 and OBOP‐02′s electrical interactions and properties. Gaining insight into these interactions is essential for understanding the compounds′ potential applications and properties. According to theoretical studies using molecular docking, the derivatives may interact with estrogen receptor alpha (ERα) (ID: 7NDO), a key target molecule in the development of breast cancer. Additionally, the complex OBOP‐01 – ERα′s molecular dynamics simulations were conducted for 100 nanoseconds. These simulations revealed essential details regarding the complex's dynamic behavior in a physiological system. [ABSTRACT FROM AUTHOR]

Excess hypochlorite (ClO−) is harmful to living organisms and can cause various oxidative diseases in the human body. Owing to the toxicity of ClO−, the development of efficient fluorescence sensors to track ClO− is necessary. In this work, we report a novel thiourea‐based fluorescent turn‐on sensor 1‐(9‐ethyl‐9H‐carbazol‐3‐yl)‐3‐(naphthalen‐1‐yl)thiourea (ECNT) for recognizing ClO−. ECNT can detect ClO− with high selectivity, relatively low interference with other analytes, and a significantly fast response time (<1 s) through a desulfurization reaction. The detection limit of ECNT for ClO− is calculated as 5.59 μM. Of note, ECNT is a chemosensor that reacts the fastest with ClO− among the reported thiourea‐based fluorescence turn‐on sensors for detecting ClO−. The response mechanism of ECNT to ClO− is demonstrated through 1H NMR titration, ESI mass, and density functional theory calculations. [ABSTRACT FROM AUTHOR]

Garnet solid‐state electrolyte Li6.5La3Zr1.5Ta0.5O12 (LLZTO) holds significant promise. However, the practical utilization has been seriously impeded by the poor contact of Li|garnet and electron leakage. Herein, one new type of garnet‐based solid‐state battery is proposed with high performance through the disparity in interfacial energy, induced by the reaction between trace fluorinated carbon dots (FCDs) and Li. The work of adhesion of Li|garnet is increased by the acquired Li‐FCD composite, which facilitates an intimate Li|garnet interface with the promoted uniform Li+ deposition, revealed by density functional theory (DFT) calculations. It is further validated that a concentrated C−Li2O−LiF component at the Li|garnet interface is spontaneously constructed, due to the significant disparity in interfacial energy between C−Li2O−LiF|LLZTO and C−Li2O−LiF|Li. Furthermore, The electron transport and Li dendrites penetration are effectively hindered by the formed Li2O and LiF. The Li‐FCD|LLZTO|Li‐FCD symmetrical cells demonstrate stable cycling performance for over 3000 hours at 0.3 mA cm−2 and 800 hours at 0.5 mA cm−2. Furthermore, the LFP|garnet|Li‐FCD full cell exhibits remarkable cycling performance (91.6 % capacity retention after 500 cycles at 1 C). Our research has revealed a novel approach to establish a dendrite‐free Li|garnet interface, laying the groundwork for future advancements in garnet‐based solid‐state batteries. [ABSTRACT FROM AUTHOR]

We herein report a fundamental mechanistic investigation into photochemical metal‐nitrenoid generation and inner‐sphere transposition reactivity using organometallic photoprecursors. By designing Cp*Ir(hydroxamate)(Ar) complexes, we induced photo‐initiated ligand activation, allowing us to explore the amidative σ(Ir–aryl) migration reactivity. A combination of experimental mechanistic studies, femtosecond transient absorption spectroscopy, and density functional theory (DFT) calculations revealed that the metal‐to‐ligand charge transfer enables the σ(N−O) cleavage, followed by Ir‐acylnitrenoid generation. The final inner‐sphere σ(Ir–aryl) group migration results in a net amidative group transposition. [ABSTRACT FROM AUTHOR]

Mixed‐dimensional van der Waals heterostructures (vdWHs) have aroused extensive attention owing to distinctive properties by integrating advantages of materials with different types and dimensionalities for high‐performance optoelectronic devices. Herein, 2D Yb‐doped monolayer WS2 (WS2(Yb)) nanosheets and 3D bulk Te microwires are first prepared using chemical and physical vapor deposition (CVD/PVD) techniques, respectively. 12.7 at% of Yb‐doping concentration in WS2(Yb) matrix is achieved. Te microwires are transferred onto WS2(Yb) triangles by microarea fixed‐point dry transfer technique to form 2D WS2(Yb)/3D Te p–p heterostructures with a clean interface. Both p‐type semiconductors are shown for WS2(Yb) monolayer and bulk Te by calculating their band structures based on density functional theory (DFT), which is consistent with the experimental results. The optoelectronic device based on the WS2(Yb)/Te mixed‐dimensional vdWHs is fabricated using Au/Cr as the electrodes. Further, the photodetector demonstrates outstanding optoelectronic performance, including 1.87 A W−1 of responsivity, 366.7% of external quantum efficiency, and 2.53 × 1011 Jones of specific detectivity under illumination of a 635 nm light. Here a remarkable strategy is provided for preparation of mixed‐dimensional optoelectronic devices with high performances. [ABSTRACT FROM AUTHOR]

Given the pronounced dissolution of electrocatalysts in acidic environments, the quest for effective oxygen evolution reaction (OER) electrocatalysts suitable for proton exchange membrane (PEM) water electrolyzers persists as a formidable challenge. In this investigation, catalysts are synthesized by creating oxygen vacancies within various metal oxides (Nb2O5‐x, Ta2O5‐x, ZrO2‐x, TiO2‐x) through plasma‐assisted method, thereby facilitating the immobilization of IrO2 onto these defect‐rich surfaces. The findings unveil that IrO2/Nb2O5‐x manifests reduced overpotentials during acidic OER, achieving an overpotential down to 225 mV@10 mA cm−2, coupled with outstanding durability at multicurrent densities exceeding 200 h, attributed to strong oxide‐support interaction (SOSI) between the IrO2 catalyst and Nb2O5‐x substrate. Density functional theory (DFT) computations uncover intensified binding affinities between IrO2 and Nb2O5‐x, thus modulating the central energy levels of Ir's d orbitals toward favorable OER conditions, consequently bolstering the electrocatalytic activity and stability of the composite catalyst. Furthermore, employing IrO2/Nb2O5‐x as a PEM electrolyzer anode enables consistent operation at 1000 mA cm−2 for 200 h, with an Ir content of only 0.2852 mg cm−2 and an energy consumption of 4.34 kWh Nm−3 H2. This achievement substantially lowers the cost of hydrogen production to US$ 0.96 per kilogram, underscoring its potential for practical applications. [ABSTRACT FROM AUTHOR]

Bimetallic single‐atom‐dimer (SAD) with unique electronic structures and adsorption properties presents exceptional catalytic performance owing to atomic‐level synergistic effects from direct bonding between different metal atoms. However, inherent characteristics of substrate present great challenges in their synthesis and mechanism investigation. Herein, a unique phosphorus modified atomic layer deposition (P‐ALD) strategy is designed to synthesize P‐anchored Pt–W dimers, overcoming substrate limitation (Pt1W1–P/C). Motivated introduction of atomic P site via ALD can effectively anchor one‐to‐one AB bimetallic dimer structure on various substrates, confirmed by X‐ray absorption spectroscopy (XAS). Density functional theory reveals an interatomic synergistic adsorption mechanism, with W as primary hydrogen adsorption site extending to Pt, optimizing hydrogen coverage, leading to 60‐fold increase in mass activity compared to commercial Pt/C in both acidic and alkaline electrolytes. Anion exchange membrane water electrolyzer with ultra‐low loading Pt1W1–P/C (50 µgPt cm−2) catalyst operates durability at 1000 mA cm−2 for 550 h with ultra‐low degradation of 38 µV h−1. Operando XAS confirms hydrogen adsorption pathway between atoms and remarkable self‐healing ability of P–Pt–W–O sites under all‐pH conditions. These findings extend the application domain of SAD to catalytic manufacturing methods and aid in designing advanced materials with multi‐atomic active sites. [ABSTRACT FROM AUTHOR]

The simulation of EXAFS spectra of thin films via ab initio methods is discussed. The procedure for producing the spectra is presented as well as an application to a two‐dimensional material (WSe2) where the effectiveness of this method in reproducing the spectrum and the linear dichroic response is shown. A series of further examples in which the method has been employed for the structural determination of materials are given. [ABSTRACT FROM AUTHOR]