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Abstract Compositional complex alloys, including high and medium‐entropy alloys (HEAs/MEAs) have displayed significant potential as efficient electrocatalysts for the oxygen evolution reaction (OER), but their structure‐activity relationship remains unclear. In particular, the basic question of which crystal facets are more active, especially considering the surface reconstructions, has yet to be answered. This study demonstrates that the lowest index {100} facets of FeCoNiCr MEAs exhibit the highest activity. The underlying mechanism associated with the {100} facet's low in‐plane density, making it easier to surface reconstruction and form amorphous structures containing the true active species is uncovered. These results are validated by experiments on single crystals and polycrystal MEAs, as well as DFT calculations. The discoveries contribute to a fundamental comprehension of MEAs in electrocatalysis and offer physics‐based strategies for developing electrocatalysts.

Abstract By employing metal oxides as oxygen carriers, chemical looping demonstrates its effectiveness in transferring oxygen between reduction and oxidation environments to partially oxidize fuels into syngas and convert CO2 into CO. Generally, NiFe2O4 oxygen carriers have demonstrated remarkable efficiency in chemical looping CO2 conversion. Nevertheless, the intricate process of atomic migration and evolution within the internal structure of bimetallic oxygen carriers during continuous high‐temperature redox cycling remains unclear. Consequently, the lack of a fundamental understanding of the complex ionic migration and oxygen transfer associated with energy conversion processes hampers the design of high‐performance oxygen carriers. Thus, in this study, we employed in situ characterization techniques and theoretical calculations to investigate the ion migration behavior and structural evolution in the bulk of NiFe2O4 oxygen carriers during H2 reduction and CO2/lab air oxidation cycles. We discovered that during the H2 reduction step, lattice oxygen rapidly migrates to vacancy layers to replenish consumed active oxygen species, while Ni leaches from the material and migrates to the surface. During the CO2 splitting step, Ni migrates toward the core of the bimetallic oxygen carrier, forming Fe–Ni alloys. During the air oxidation step, Fe–Ni migrates outward, creating a hollow structure owing to the Kirkendall effect triggered by the swift transfer of lattice oxygen. The metal atom migration paths depend on the oxygen transfer rates. These discoveries highlight the significance of regulating the release–recovery rate of lattice oxygen to uphold the structures and reactivity of oxygen carriers. This work offers a comprehensive understanding of the oxidation/reduction‐driven atomic interdiffusion behavior of bimetallic oxygen carriers.

Abstract A cost‐effective chemical prelithiation solution, which consists of Li+, polyaromatic hydrocarbon (PAH), and solvent, is developed for a model hard carbon (HC) electrode. Naphthalene and methyl‐substituted naphthalene PAHs, namely 2‐methylnaphthalene and 1‐methylnaphthalene, are first compared. Grafting an electron‐donating methyl group onto the benzene ring can decrease electron affinity and thus reduce the redox potential, which is validated by density functional theory calculations. Ethylene glycol dimethyl ether (G1), diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether solvents are then compared. The G1 solution has the highest conductivity and least steric hindrance, and thus the 1‐methylnaphthalene/G1 solution shows superior prelithiation capability. In addition, the effects of the interaction time between Li+ and 1‐methylnaphthalene in G1 solvent on the electrochemical properties of a prelithiated HC electrode are investigated. Nuclear magnetic resonance data confirm that 10‐h aging is needed to achieve a stable solution coordination state and thus optimal prelithiation efficacy. It is also found that appropriate prelithiation creates a more Li+‐conducing and robust solid‐electrolyte interphase, improving the rate capability and cycling stability of the HC electrode.

Abstract The synthesis of lanthanide‐based organometallic sandwich compounds is very appealing regarding their potential for single‐molecule magnetism. Here, it is exploited by on‐surface synthesis to design unprecedented lanthanide‐directed organometallic sandwich complexes on Au(111). The reported compounds consist of Dy or Er atoms sandwiched between partially deprotonated hexahydroxybenzene molecules, thus introducing a distinct family of homoleptic organometallic sandwiches based on six‐membered ring ligands. Their structural, electronic, and magnetic properties are investigated by scanning tunneling microscopy and spectroscopy, X‐ray absorption spectroscopy, X‐ray linear and circular magnetic dichroism, and X‐ray photoelectron spectroscopy, complemented by density functional theory‐based calculations. Both lanthanide complexes self‐assemble in close‐packed islands featuring a hexagonal lattice. It is unveiled that, despite exhibiting analogous self‐assembly, the erbium‐based species is magnetically isotropic, whereas the dysprosium‐based compound features an in‐plane magnetization.

Abstract Manipulating thermal properties of materials can be interpreted as the control of how vibrations of atoms (known as phonons) scatter in a crystal lattice. Compared to a perfect crystal, crystalline solids with defects are expected to have shorter phonon mean free paths caused by point defect scattering, leading to lower lattice thermal conductivities than those without defects. While this is true in many cases, alloying can increase the phonon mean free path in the Cd‐doped AgSnSbSe3 system to increase the lattice thermal conductivity from 0.65 to 1.05 W m−1 K−1 by replacing 18% of the Sb sites with Cd. It is found that the presence of lone pair electrons leads to the off‐centering of cations from the centrosymmetric position of a cubic lattice. X‐ray pair distribution function analysis reveals that this structural distortion is relieved when the electronic configuration of the dopant element cannot produce lone pair electrons. Furthermore, a decrease in the Grüneisen parameter with doping is experimentally confirmed, establishing a relationship between the stereochemical activity of lone pair electrons and the lattice anharmonicity. The observed “harmonic” behavior with doping suggests that lone pair electrons must be preserved to effectively suppress phonon transport in these systems.

Abstract Single‐atom alloys (SAAs) have gained increasing prominence in the field of selective hydrogenation reactions due to their uniform distribution of active sites and the unique host‐guest metal interactions. Herein, 15 SAAs are constructed to comprehensively elucidate the relationship between host‐guest metal interaction and catalytic performance in the selective hydrogenation of 4‐nitrostyrene (4‐NS) by density functional theory (DFT) calculations. The results demonstrate that the SAAs with strong host‐guest metal interactions exhibit a preference for N─O bond cleavage, and the reaction energy barrier of the hydrogenation process is primarily influenced by the host metal. Among them, Ir1Ni SAA stands out as the prime catalyst candidate, showcasing exceptional activity and selectivity. Furthermore, the Ir1Ni SAA is subsequently prepared through precise synthesis techniques and evaluated in the selective hydrogenation of 4‐NS to 4‐aminostyrene (4‐AS). As anticipated, the Ir1Ni SAA demonstrates extraordinary catalytic performance (yield > 96%). In situ FT‐IR experiments and DFT calculations further confirmed that the unique host‐guest metal interaction at the Ir‐Ni interface site of Ir1Ni SAA endows it with excellent 4‐NS selective hydrogenation ability. This work provides valuable insights into enhancing the performance of SAAs catalysts in selective hydrogenation reactions by modulating the host‐guest metal interactions.

Abstract In this study, Co/Ni‐NC catalyst with hetero‐diatomic Co/Ni active sites dispersed on nitrogen‐doped carbon matrix is synthesized via the controlled pyrolysis of ZIF‐8 containing Co2+ and Ni2+ compounds. Experimental characterizations and theoretical calculations reveal that Co and Ni are atomically and uniformly dispersed in pairs of CoN4‐NiN4 with an intersite distance ≈0.41 nm, and there is long‐range d–d coupling between Co and Ni with more electron delocalization for higher bifunctional activity. Besides, the in situ grown carbon nanotubes at the edges of the catalyst particles allow high electronic conductivity for electrocatalysis process. Electrochemical evaluations demonstrate the superior ORR and OER bifunctionality of Co/Ni‐NC catalyst with a narrow potential gap of only 0.691 V and long‐term durability, significantly prevailing over the single‐atom Co‐NC and Ni‐NC catalysts and the benchmark Pt/C and RuO2 catalysts. Co/Ni‐NC catalyzed Zn–air batteries achieve a high specific capacity of 771 mAh g−1 and a long continuous operation period up to 340 h with a small voltage gap of ≈0.65 V, also much superior to Pt/C‐RuO2.

Abstract Atomically‐dispersed copper sites coordinated with nitrogen‐doped carbon (Cu–N–C) can provide novel possibilities to enable highly selective and active electrochemical CO2 reduction reactions. However, the construction of optimal local electronic structures for nitrogen‐coordinated Cu sites (Cu–N4) on carbon remains challenging. Here, we synthesized the Cu–N–C catalysts with atomically‐dispersed edge‐hosted Cu–N4 sites (Cu–N4C8) located in a micropore between two graphitic sheets via a facile method to control the concentration of metal precursor. Edge‐hosted Cu–N4C8 catalysts outperformed the previously reported M–N–C catalysts for CO2‐to‐CO conversion, achieving a maximum CO Faradaic efficiency (FECO) of 96%, a CO current density of –8.97 mA cm–2 at –0.8 V versus reversible hydrogen electrode (RHE), and over FECO of 90% from –0.6 to –1.0 V versus RHE. Computational studies revealed that the micropore of the graphitic layer in edge‐hosted Cu–N4C8 sites causes the d‐orbital energy level of the Cu atom to shift upward, which in return decreases the occupancy of antibonding states in the *COOH binding. This research suggests new insights into tailoring the locally coordinated structure of the electrocatalyst at the atomic scale to achieve highly selective electrocatalytic reactions.

Abstract Phase engineering is an efficient strategy for enhancing the kinetics of electrocatalytic reactions. Herein, phase engineering was employed to prepare high‐performance phosphorous‐doped biphase (1T/2H) MoS2 (P‐BMS) nanoflakes for hydrogen evolution reaction (HER). The doping of MoS2 with P atoms modifies its electronic structure and optimizes its electrocatalytic reaction kinetics, which significantly enhances its electrical conductivity and structural stability, which are verified by various characterization tools, including X‐ray photoelectron spectroscopy, high‐resolution transmission electron microscopy, X‐ray absorption near‐edge spectroscopy, and extended X‐ray absorption fine structure. Moreover, the hierarchically formed flakes of P‐BMS provide numerous catalytic surface‐active sites, which remarkably enhance its HER activity. The optimized P‐BMS electrocatalysts exhibit low overpotentials (60 and 72 mV at 10 mA cm−2) in H2SO4 (0.5 M) and KOH (1.0 M), respectively. The mechanism of improving the HER activity of the material was systematically studied using density functional theory calculations and various electrochemical characterization techniques. This study has shown that phase engineering is a promising strategy for enhancing the H* adsorption of metal sulfides.

Abstract Understanding the adsorption interactions between carbon materials and sulfur compounds has far‐reaching impacts, in addition to their well‐known important role in energy storage and conversion, such as lithium‐ion batteries. In this paper, properties of intrinsic B or Si single‐atom doped, and B–Si codoped graphene (GR) and graphdiyne (GDY) were investigated by using density functional theory‐based calculations, in which the optimal doping configurations were explored for potential applications in adsorbing sulfur compounds. Results showed that both B or Si single‐atom doping and B–Si codoping could substantially enhance the electron transport properties of GR and GDY, improving their surface activity. Notably, B and Si atoms displayed synergistic effects for the codoped configurations, where B–Si codoped GR/GDY exhibited much better performance in the adsorption of sulfur‐containing chemicals than single‐atom doped systems. In addition, results demonstrated that, after B–Si codoping, the adsorption energy and charge transfer amounts of GDY with sulfur compounds were much larger than those of GR, indicating that B–Si codoped GDY might be a favorable material for more effectively interacting with sulfur reagents.

Abstract Blueberry juice is one of deep‐processed products of blueberries, anthocyanins are main bioactive substance in blueberry juice. However, anthocyanins have poor stability. Thermal, high pressure, electric field, magnetic field and cobalt source irradiation were used to treat blueberry juice, and then the treated blueberry juice composition and antioxidant capacity were determined to explore ways to better protect anthocyanins. Metabolomics was used to qualitatively and quantitatively analyze the anthocyanins in blueberry juice, a total of 54 anthocyanins were identified. Different processing methods of treatment did not significantly change the types of anthocyanins in blueberry juice. Their effects were mainly focused on the changes in content. By determining the antioxidant capacity of blueberry juice, it was found that there is more than a simple linear relationship between the total anthocyanin content of blueberry juice and its antioxidant capacity. Therefore, the structural parameters of the four main anthocyanin monomers of blueberry juice were calculated using density functional theory to predict the antioxidant capacity and the antioxidant capacity of the monomers was determined for validation. The effect of different treatments on the change of antioxidant activity of blueberry juice due to anthocyanin occupancy was explained using equivalent antioxidant. The results showed that the 1 kGy irradiation treatment had a better protective effect on the anthocyanins, whereas the change in the percentage of anthocyanins due to this treatment was the key factor for the change in their antioxidant capacity.

Abstract Vitrimers are an innovative class of polymers that boast a remarkable fusion of mechanical and dynamic features, complemented by the added benefit of end‐of‐life recyclability. This extraordinary blend of properties makes them highly attractive for a variety of applications, such as the automotive sector, soft robotics, and the aerospace industry. At their core, vitrimer materials consist of crosslinked covalent networks that have the ability to dynamically reorganize in response to external factors, including temperature changes, pressure variations, or shifts in pH levels. In this review, the aim is to delve into the latest advancements in the theoretical understanding and computational design of vitrimers. The review begins by offering an overview of the fundamental principles that underlie the behavior of these materials, encompassing their structures, dynamic behavior, and reaction mechanisms. Subsequently, recent progress in the computational design of vitrimers is explored, with a focus on the employment of molecular dynamics (MD)/Monte Carlo (MC) simulations and density functional theory (DFT) calculations. Last, the existing challenges and prospective directions for this field are critically analyzed, emphasizing the necessity for additional theoretical and computational advancements, coupled with experimental validation.

Abstract Raman optical activity (ROA) is commonly measured with green light (532 nm) excitation. At this wavelength, however, Raman scattering of europium complexes is masked by circularly polarized luminescence (CPL). This can be avoided using near‐infrared (near‐IR, 785 nm) laser excitation, as demonstrated here by Raman and ROA spectra of three chiral europium complexes derived from camphor. Since luminescence is strongly suppressed, many vibrational bands can be detected. They carry a wealth of structural information about the ligand and the metal core, and can be interpreted based on density functional theory (DFT) simulations of the spectra. For example, jointly with ROA experimental data, the simulations make it possible to determine absolute configuration of chiral lanthanide compounds in solution.

Abstract Decreasing particle size (like thickness) is a common strategy to enhance the activities of catalysts. In this work, we have synthesized two coppers, which are bismuth‐based metal‐organic framework (CuBi‐MOF) catalysts with different thicknesses (134.8 and 2.0 nm). In contrast to common expectations, large thickness CuBi‐MOF has exhibited superior activities as a comparison to its small‐thickness counterpart in terms of carbon dioxide electroreduction to produce formate, characteristic of high selectivity (Faraday efficiency > 90%), a wide window of potential (−0.6 to −1.6 V vs. reversible hydrogen electrode), and large current densities (up to −380 mA cm−2). The mechanism study has been performed by using density functional theory calculations, which highlight the strong synergic effect between Cu and Bi sites in large‐thickness CuBi‐MOF for activating CO2 molecules. Consequently, large‐thickness CuBi‐MOF could show smaller Gibbs free energies compared to its small counterpart for binding with reaction intermediate (*COOH, 1.1 vs. 1.8 eV). The result of this work could provide new insights into catalyst design toward a number of electrochemical systems.

Abstract The direct conversion of gaseous methane to energy‐dense liquid derivatives such as methanol and ethanol is of profound importance for the more efficient utilization of natural gas. However, the thermo‐catalytic partial oxidation of this simple alkane has been a significant challenge due to the high C−H bond energy. Exploiting electrocatalysis for methane activation via active oxygen species generated on the catalyst surface through electrochemical water oxidation is generally considered as economically viable and environmentally benign compared to energy‐intensive thermo‐catalysis. Despite recent progress in electrochemical methane oxidation to alcohol, the competing oxygen evolution reaction (OER) still impedes achieving high faradaic efficiency and product selectivity. In this review, an overview of current progress in electrochemical methane oxidation, focusing on mechanistic insights on methane activation, catalyst design principles based on descriptors, and the effect of reaction conditions on catalytic performance are provided. Mechanistic requirements for high methanol selectivity, and limitations of using water as the oxidant are discussed, and present the perspective on how to overcome these limitations by employing carbonate ions as the oxidant.

Abstract The dimeric β‐diketiminato calcium hydride, [(DippBDI)CaH]2 (DippBDI = HC{(Me)CN‐2,6‐i‐Pr2C6H3}2), reacts with ortho‐, meta‐ or para‐tolyl mercuric compounds to afford hydridoarylcalcium compounds, [(DippBDI)2Ca2(μ‐H)(μ‐o‐,m‐,p‐tolyl)], in which dimer propagation occurs either via μ2‐η1‐η1 or μ2‐η1‐η6 bridging between the calcium centers. In each case, the orientation and hapticity of the aryl units is dependent upon the position of the methyl substituent. While wholly organometallic meta‐ and para‐tolyl dimers, [(DippBDI)Ca(m‐tolyl)]2 and [(DippBDI)Ca(p‐tolyl)]2, can be prepared and are stable, the ortho‐tolyl isomer is prone to isomerization to a calcium benzyl analog. Computational analysis of this latter process with density functional theory (DFT) highlights an unusual mechanism invoking the generation of an intermediate dicalcium species in which the group 2 centers are bridged by a toluene dianion formed by the formal attachment of the original hydride anion to the initially generated ortho‐tolyl substituent. Use of a more sterically encumbered aryl substituent, {3,5‐t‐Bu2C6H3}, facilitates the selective formation of [(DippBDI)Ca(μ‐H)(μ‐3,5‐t‐Bu2C6H3)Ca(DippBDI)], which can be converted into the unsymmetrically‐substituted σ‐aryl calcium complexes, [(DippBDI)Ca(μ‐Ph)(μ‐3,5‐t‐Bu2C6H3)Ca(DippBDI)] and [(DippBDI)Ca(μ‐p‐tolyl)(μ‐3,5‐t‐Bu2C6H3)Ca(DippBDI)] by reaction with the appropriate mercuric diaryl. Conversion of [(DippBDI)Ca(H)(Ph)Ca(DippBDI)] to afford [{{(DippBDI)Ca}2(μ2‐Cl)}2(C6H5‐C6H5)], comprising a biphenyl dianion, is also reported. Although this latter transformation is serendipitous, AIM analysis highlights that, in a related manner to the ortho‐tolyl to benzyl isomerization, the requisite C–C coupling may be facilitated in an “across dimer” fashion by the experimentally‐observed polyhapto engagement of the aryl substituents with each calcium.

Abstract Finding effective strategies to design efficient photocatalysts and decompose refractory organic compounds in wastewater is a challenging problem. Herein, by coupling element doping and constructing heterostructures, S‐scheme CdS QDs/La‐Bi2WO6 (CS/LBWO) photocatalysts are designed and synthesized by a simple hydrothermal method. As a result, the RhB degradation efficiency of the optimized 5% CS/LBWO reached 99% within 70 min of illumination with excellent stability and recyclability. CS/LBWO shows improvement in the adsorption range of visible light and promotes electron–hole pair generation/migration/separation, attributing the superior degradation performance. The degradation RhB mechanism is proposed by a free radical capture experiment, electron paramagnetic resonance, and high‐performance liquid chromatography‐mass spectrometry results, indicating that h+ and •O2– play a significant role during four degradation processes: de‐ethylation, chromophore cleavage, ring opening, and mineralization. Based on in situ irradiated X‐ray photoelectron spectroscopy, Mulliken electronegativity theory, and the work function results, the S‐scheme heterojunction of CS/LBWO promotes the transfer of photogenerated electron–hole pairs and promotes the generation of reactive radicals. This work not only reports that 5% CS/LBWO is a promising photocatalyst for degradation experiments but also provides an approach to design advanced photocatalysts by coupling element doping and constructing heterostructures.

Abstract The reviving of the “Holy Grail” lithium metal batteries (LMBs) is greatly hindered by severe parasitic reactions between Li anode and electrolytes. Herein, first, we comprehensively summarize the failure mechanisms and protection principles of the Li anode. Wherein, despite being in dispute, the formation of lithium hydride (LiH) is demonstrated to be one of the most critical factors for Li anode pulverization. Secondly, we trace the research history of LiH at electrodes of lithium batteries. In LMBs, LiH formation is suggested to be greatly associated with the generation of H2 from Li/electrolyte intrinsic parasitic reactions, and these intrinsic reactions are still not fully understood. Finally, density functional theory calculations reveal that H2 adsorption ability of representative Li anode protective species (such as LiF, Li3N, BN, Li2O, and graphene) is much higher than that of Li and LiH. Therefore, as an important supplement of well‐known lithiophilicity theory/high interfacial energy theory and three key principles (mechanical stability, uniform ion transport, and chemical passivation), we propose that constructing an artificial solid electrolyte interphase layer enriched of components with much higher H2 adsorption ability than Li will serve as an effective principle for Li anode protection. In summary, suppressing formation of LiH and H2 will be very important for cycle life enhancement of practical LMBs.

Abstract Carbonate melts have been proposed to exist in the lower mantle, but their interaction with other lower mantle melt compositions is poorly understood. To understand miscibility in the carbonate‐silicate‐metal melt system, we simulate endmember, binary, and ternary melt mixtures and study how their Gibbs free energies of mixing evolve with pressure. We find that carbonate‐metal and carbonate‐silicate melts have miscibility gaps that close with increasing pressure, while silicate‐metal melts are immiscible at all lower‐mantle pressures. Extending this analysis to the core‐mantle boundary, we suggest three miscible melt fields near the endmember carbonate, silicate, and iron melt compositions. Analysis of the densities of these miscible melt compositions indicates that some carbonate‐rich and some silicate‐rich melt compositions are gravitationally stable at the core‐mantle boundary and could be candidate compositions to explain ultra‐low velocity zones. Additionally, we evaluate the speciation of an example immiscible melt composition at various pressures throughout the mantle and identify reduced carbon species that would be expected to form in the melt. Our analysis reveals that a majority of Earth's carbon could have been transported to the core during core‐mantle differentiation and that much of Earth's carbon may be stored in the deep interior today.

Abstract A main challenge for the development of two‐dimensional devices based on atomically thin transition‐metal dichalcogenides (TMDs) is the realization of metal–semiconductor junctions (MSJs) with low contact resistance and high charge transport capability. However, traditional metal–TMD junctions usually suffer from strong Fermi‐level pinning (FLP) and chemical disorder at the interfaces, resulting in weak device performance and high energy consumption. By means of high‐throughput first‐principles calculations, we report an attractive solution via the formation of van der Waals (vdW) contacts between metallic and semiconducting TMDs. We apply a phase‐engineering strategy to create a monolayer TMD database for achieving a wide range of work functions and band gaps, hence offering a large degree of freedom to construct TMD vdW MSJs with desired contact types. The Schottky barrier heights and contact types of 728 MSJs have been identified and they exhibit weak FLP (−0.62 to −0.90) as compared with the traditional metal–TMD junctions. We find that the interfacial interactions of the MSJs bring a delicate competition between the FLP strength and carrier tunneling efficiency, which can be utilized to screen high‐performance MSJs. Based on a set of screening criteria, four potential TMD vdW MSJs (e.g., NiTe2/ZrSe2, NiTe2/PdSe2, HfTe2/PdTe2, TaSe2/MoTe2) with Ohmic contact, weak FLP, and high carrier tunneling probability have been predicted. This work not only provides a fundamental understanding of contact properties of TMD vdW MSJs but also renders their huge potential for electronics and optoelectronics.

The application of explainable artificial intelligence in nanomaterial research has emerged in the past few years, which has facilitated the discovery of novel physical findings. However, a fundamental question arises concerning the physical insights presented by deep neural networks; the model interpretation results have not been carefully evaluated. Herein, explainable artificial intelligence and quantum mechanical calculations is bridged to investigate the correlation between light scattering and emission in a WSe2 monolayer. Convolutional neural networks using light scattering and emission data are first trained, while expecting the networks to determine the relationships between them. The trained models are interpreted and the specific phonon contribution during the exciton relaxation process is derived. Finally, the findings are independently evaluated through quantum mechanical calculations, such as the Born–Oppenheimer molecular dynamics simulation and density functional perturbation theory. The study provides reliable fundamental physical insight by evaluating the results of neural networks and suggests a novel methodology that can be applied in materials science.

Abstract Doping of foreign atoms and construction of unique structures are considered as effective approaches to design high‐activity and strong‐durability electrocatalysts. Herein, we report Fe‐doped nickel hydroxide carbonate hierarchical microtubes with Ag nanoparticles (denoted Ag/NiFeHC HMTs) through hydrolysis precipitation process. Experimental tests and density functional theory calculations reveal that Fe doping can tune the electron configuration to enhance the conductivity, markedly improve the electrochemical surface area to expose more active sites, and act as reactive centers to lower the free energy of the rate determination step. In addition, the unique hierarchical structure can also offer active sites and excellent cycling stability. Benefitting from these advantages, the as‐obtained Ag/NiFeHC HMTs show excellent oxygen evolution reaction activity, with an overpotential of 208 mV at 10 mA cm−2 in 1.0 M KOH. Also, it could achieve long‐term stability at a current density of 20 mA cm−2 for 24 h.

Abstract Flexible carbon fiber cloth (CFC) is an important scaffold and/or current collector for active materials in the development of flexible self‐supportive electrode materials (SSEMs), especially in lithium‐ion batteries. However, during the intercalation of Li ions into the matrix of CFC (below 0.5 V vs. Li/Li+), the incompatibility in the capacity of the CFC, when used directly as an anode material or as a current collector for active materials, leads to difficulty in the estimation of its actual contribution. To address this issue, we prepared Ni5P4 nanosheets on CFC (denoted CFC@Ni5P4) and investigated the contribution of CFC in the CFC@Ni5P4 by comparing to the powder Ni5P4 nanosheets traditionally coated on a copper foil (CuF) (denoted P‐Ni5P4). At a current density of 0.4 mA cm−2, the as‐prepared CFC@Ni5P4 showed an areal capacity of 7.38 mAh cm−2, which is significantly higher than that of the P‐Ni5P4 electrode. More importantly, theoretical studies revealed that the CFC has a high Li adsorption energy that contributes to the low Li‐ion diffusion energy barrier of the Ni5P4 due to the strong interaction between the CFC and Ni5P4, leading to the superior Li‐ion storage performance of the CFC@Ni5P4 over the pristine Ni5P4 sample. This present work unveils the underlying mechanism leading to the achievement of high performance in SSEMs.

Abstract The scarcity of high electrocatalysis composite electrode materials has long been suppressing the redox reaction of V(II)/V(III) and V(IV)/V(V) couples in high performance vanadium redox flow batteries (VRFBs). Herein, through ingeniously regulating the growth of Aspergillus Niger, a wrinkle‐like carbon (WLC) material that possesses edge‐rich carbon, abundant heteroatoms, and nature wrinkle‐like structure is obtained, which is subsequently successfully introduced and uniform dispersed on the surface of carbon fiber of graphite felt (GF). This composite electrode presents a lower overpotential and higher charge transfer ability, as the codoped multiheteroatoms increase the electrocatalysis activity and the wrinkled structure affords more abundant reaction area for vanadium ions in the electrolyte when compared with the pristine GF electrode, which is also supported by the density functional theory (DFT) calculations. Hence, the assembled battery using WLC electrodes achieves a high energy efficiency of 74.5% for 300 cycles at a high current density of 200 mA cm−2, as well as the highest current density of 450 mA cm−2. The WLC material not only uncovers huge potential in promoting the application of VRFBs, but also offers referential solution to synthesis microorganism‐based high‐performance electrode in other energy storage systems.

Abstract Plumbene, with a structure similar to graphene, is expected to possess a strong spin–orbit coupling and thus enhances its superconducting critical temperature (Tc). In this work, a buckled plumbene‐Au Kagome superstructure grown by depositing Au on Pb(111) is investigated. The superconducting gap monitored by temperature‐dependent scanning tunneling microscopy/spectroscopy shows that the buckled plumbene‐Au Kagome superstructure not only has an enhanced Tc with respect to that of a monolayer Pb but also possesses a higher value than what owned by a bulk Pb substrate. By combining angle‐resolved photoemission spectroscopy with density functional theory, the monolayer Au‐intercalated low‐buckled plumbene sandwiched between the top Au Kagome layer and the bottom Pb(111) substrate is confirmed and the electron–phonon coupling‐enhanced superconductivity is revealed. This work demonstrates that a buckled plumbene‐Au Kagome superstructure can enhance superconducting Tc and Rashba effect, effectively triggering the novel properties of a plumbene.

Abstract Gallium nitride (GaN) single crystal, as the representative of wide‐band semiconductors, has great prospects for high‐temperature energy storage, of its splendid power output, robust temperature stability, and superior carrier mobility. Nonetheless, it is an essential challenge for GaN‐based devices to improve energy storage. Herein, an innovative strategy is proposed by constructing GaN/Nickel cobalt oxygen (NiCoO2 ）heterostructure for enhanced supercapacitors (SCs). Benefiting from the synergy effect between the porous GaN network as a highly conductive skeleton and the NiCoO2 with massive active sites. The GaN/NiCoO2 heterostructure‐based SCs with ion liquids electrolyte are assembled and delivered an impressive energy density of 15.2 µWh cm−2 and power density, as well as superior service life at 130 °C. The theoretical calculation further explains that the reason for the energy storage enhancement of the GaN/NiCoO2 is due to the presence of the built‐in electric fields. This work offers a novel perspective for meeting the practical application of GaN‐based energy storage devices with exceptional performance capable of operation under high‐temperature environments.

Abstract The rational synergy of chemical composition and spatial nanostructures of electrode materials play important roles in high‐performance energy storage devices. Here, we designed pea‐like MoS2@NiS1.03–carbon hollow nanofibers using a simple electrospinning and thermal treatment method. The hierarchical hollow nanofiber is composed of a nitrogen‐doped carbon‐coated NiS1.03 tube wall, in which pea‐like uniformly discrete MoS2 nanoparticles are enclosed. As a sodium‐ion battery electrode material, the MoS2@NiS1.03–carbon hollow nanofibers have abundant diphasic heterointerfaces, a conductive network, and appropriate volume variation‐buffering spaces, which can facilitate ion diffusion kinetics, shorten the diffusion path of electrons/ion, and buffer volume expansion during Na+ insertion/extraction. It shows outstanding rate capacity and long‐cycle performance in a sodium‐ion battery. This heterogeneous hollow nanoarchitectures designing enlightens an efficacious strategy to boost the capacity and long‐life stability of sodium storage performance of electrode materials.

Abstract Ruthenium has been hailed as a competitive alternative for platinum toward hydrogen evolution reaction (HER), a critical process in electrochemical water splitting. In this study, we successfully prepare metallic Ru nanoparticles supported on carbon paper by utilizing a novel magnetic induction heating (MIH) method. The samples are obtained within seconds, featuring a Cl‐enriched surface that is unattainable via conventional thermal annealing. The best sample within the series shows a remarkable HER activity in both acidic and alkaline media with an overpotential of only ‐23 and ‐12 mV to reach the current density of 10 mA/cm2, highly comparable to that of the Pt/C benchmark. Theoretical studies based on density functional theory show that the excellent electrocatalytic activity is accounted by the surface metal‐Cl species that facilitate charge transfer and downshift the d‐band center. Results from this study highlight the unique advantages of MIH in rapid sample preparation, where residual anion ligands play a critical role in manipulating the electronic properties of the metal surfaces and the eventual electrocatalytic activity.

Abstract A new concentrated ternary salt ether‐based electrolyte enables stable cycling of lithium metal battery (LMB) cells with high‐mass‐loading (13.8 mg cm−2, 2.5 mAh cm−2) NMC622 (LiNi0.6Co0.2Mn0.2O2) cathodes and 50 μm Li anodes. Termed “CETHER‐3,” this electrolyte is based on LiTFSI, LiDFOB, and LiBF4 with 5 vol% fluorinated ethylene carbonate in 1,2‐dimethoxyethane. Commercial carbonate and state‐of‐the‐art binary salt ether electrolytes were also tested as baselines. With CETHER‐3, the electrochemical performance of the full‐cell battery is among the most favorably reported in terms of high‐voltage cycling stability. For example, LiNixMnyCo1–x–yO2 (NMC)‐Li metal cells retain 80% capacity at 430 cycles with a 4.4 V cut‐off and 83% capacity at 100 cycles with a 4.5 V cut‐off (charge at C/5, discharge at C/2). According to simulation by density functional theory and molecular dynamics, this favorable performance is an outcome of enhanced coordination between Li+ and the solvent/salt molecules. Combining advanced microscopy (high‐resolution transmission electron microscopy, scanning electron microscopy) and surface science (X‐ray photoelectron spectroscopy, time‐of‐fight secondary ion mass spectroscopy, Fourier‐transform infrared spectroscopy, Raman spectroscopy), it is demonstrated that a thinner and more stable cathode electrolyte interphase (CEI) and solid electrolyte interphase (SEI) are formed. The CEI is rich in lithium sulfide (Li2SO3), while the SEI is rich in Li3N and LiF. During cycling, the CEI/SEI suppresses both the deleterious transformation of the cathode R‐3m layered near‐surface structure into disordered rock salt and the growth of lithium metal dendrites.

Abstract Transition‐metal dichalcogenides exhibit strong light–matter interactions and unique multifunctional logic behavior. Here, the strong interlayer transition and excellent broadband photodetection of GeSe/MoTe2 van der Waals (vdW) heterojunction are demonstrated. Differential charge density and photoluminescence quenching analyses reveal a strong interlayer transition between GeSe and MoTe2. In addition, density functional theory analysis predicts the formation of staggered band alignment, which contributed to the spatial segregation of photogenerated electron–hole pairs. The diode exhibited excellent optoelectronic characteristics in the visible and near‐infrared region. A high responsivity of ~1.0 × 104 A/W, an excellent detectivity of ~8.4 × 1012 jones, and a fast rise and fall time of 458 and 498 μs, respectively. Finally, a two‐dimensional complementary inverter consisting of p‐channel GeSe and n‐channel MoTe2 is examined to analyze its application for a logic inverter. The findings of this study will play a crucial role in the stimulation and fabrication of multifunctional vdW heterostructure devices.

Abstract The electrochemical CO2 reduction reaction (CO2RR) has been regarded as a promising technique for converting CO2 into high‐value fuels and chemicals. Powered by renewable electricity, the CO2RR provides a viable strategy to mitigate the CO2 concentration in the atmosphere and close the anthropogenic carbon cycle. Recent studies exhibit that copper‐based catalysts are capable of reducing CO2 to C2+ products, such as ethylene and ethanol, which are of higher value compared with C1 products. The reaction process toward C2+ products involves the formation of key intermediate *CO, the C–C bonding, and the post‐C–C bonding to final products. This perspective is focusing on the mechanism leading to C2+ products, examining the evidence from in situ/operando spectroscopy and density functional theory calculations. The effects of Cu facet and electrolyte on catalytic performance are reviewed. An in depth discussion of mechanistic aspects of Cu catalyst is presented, shedding light on the intrinsic features of catalyst and electrode‐electrolyte interface, therefore moving towards an understanding of CO2RR at the atomic level.

Abstract Metal–organic frameworks (MOFs) are recognized as promising electrocatalysts for the oxygen evolution reaction (OER) because of their permanent porosity and rich architectural diversity; however, ionic MOFs enabling fast ions exchange during OER are rarely explored. Here, an ionic MOF (Ni‐btz) constructed with an azolate ligand is selected, and continuous 3D bimetallic MOF (NiFe‐btz) films deriving from high‐degree intergrowth of microsized MOFs particles are fabricated. The as‐prepared NiFe‐btz/NF‐OH electrode exhibits excellent OER performance with a low overpotential of 239 mV at 10 mA cm−2 under alkaline condition. The OER charge transfer process and bimetallic coupling effect in ionic NiFe‐btz are probed by density functional theory calculations and confirmed via X‐ray photoelectron spectroscopy and in situ Raman measurements. The partial density of states of NiFe‐btz indicates that the main contribution for electron density around the Fermi level is from Cl ions clarifying the profitable impact of ionic MOF framework. This work systematically demonstrates the relationship of electronic structure and OER activity in ionic, bimetallic MOFs and expands the scope of 3D MOF films for efficient OER.

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 TiO 2 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., (© 2024 The Authors. Journal of Computational Chemistry published by Wiley Periodicals LLC.)

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 CeO 2 (100) and (210) surfaces where the diffusion of the platinum atom is hindered. At the opposite, the more stable CeO 2 (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 CeO 2 (111) and (211) terminations. The desorption of the CO 2 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., (© 2024 The Authors. Journal of Computational Chemistry published by Wiley Periodicals LLC.)

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., (© 2024 Wiley Periodicals LLC.)

Graphene is the newest form of elemental carbon and it is becoming rapidly a potential candidate in the framework of nano-bio research. Many reports confirm the successful use of graphene-based materials as carriers of anticancer drugs having relatively high loading capacities compared with other nanocarriers. Here, the outcomes of a systematic study of the adsorption behavior of FDA approved Pt II drugs cisplatin, oxaliplatin, and carboplatin on surface models of pristine, holey, and nitrogen-doped holey graphene are reported. DFT investigations in water solvent have been carried out considering several initial orientations of the drugs with respect to the surfaces. Adsorption free energies, calculated including basis set superposition error (BSSE) corrections, result to be significantly negative for many of the drug@carrier adducts indicating that tested layers could be used as potential carriers for the delivery of anticancer Pt II drugs. The reduced density gradient (RDG) analysis allows to show that many kinds of non-covalent interactions, including canonical H-bond, are responsible for the stabilization of the formed adducts., (© 2024 Wiley Periodicals LLC.)

3-Cyanopyridine derivatives are known for exhibiting excellent anticancer activity due to their strong capability to inhibit various biological targets, including Pim-1 kinase, survivin, and tubulin polymerization. On the other hand, N-acylhydrazones (NAH) are known to be a very versatile motif in medicinal chemistry and drug design. Based on these data, we report in this paper, the synthesis of novel 3-cyanopyridines incorporating N-acyl hydrazine scaffold, the evaluation of their cytotoxicity on the breast (MCF-7) and ovarian (A-2780) cancer cell lines and their antioxidant properties. Excluding 4a and 4d, all tested molecules exhibited high cytotoxicity against A-2780, with IC 50 values ranging from 1.14 to 1.76 µM. Conversely, only four molecules 3d, 4b, 4c, and 4d demonstrated cytotoxicity against MCF-7, with IC 50 values ranging from 1.14 to 3.38 µM. On the other hand, all the tested molecules exhibited a moderate antioxidant capacity in both the DPPH and metal chelation assays. Docking and molecular dynamics studies revealed that 2d, 3d, and 4d are potential inhibitors of tubulin and the œstrogen receptor, which may explain their high cytotoxicity. These results are promising to study these newly synthesized 3-cyanopyridine-N-acylhydrazones in depth for use as potential anticancer candidates., (© 2024 Wiley Periodicals LLC.)

A recent work (arXiv:2401.04685) has merged N-centered ensembles of neutral and charged electronic ground states with ensembles of neutral ground and excited states, thus providing a general and in-principle exact (so-called extended N-centered) ensemble density functional theory of neutral and charged electronic excitations. This formalism made it possible to revisit the concept of density-functional derivative discontinuity, in the particular case of single excitations from the highest occupied Kohn-Sham (KS) molecular orbital, without invoking the usual "asymptotic behavior of the density" argument. In this work, we address a broader class of excitations, with a particular focus on double excitations. An exact implementation of the theory is presented for the two-electron Hubbard dimer model. A thorough comparison of the true physical ground- and excited-state electronic structures with that of the fictitious ensemble density-functional KS system is also presented. Depending on the choice of the density-functional ensemble as well as the asymmetry of the dimer and the correlation strength, an inversion of states can be observed. In some other cases, the strong mixture of KS states within the true physical system makes the assignment "single excitation" or "double excitation" irrelevant., (© 2024 The Authors. Journal of Computational Chemistry published by Wiley Periodicals LLC.)

The two-dimensional (2D) monolayer material MoSi 2 N 4 was successfully synthesized in 2020[Hong et al., Science 369, 670, (2020)], exhibiting a plethora of new phenomena and unusual properties, with good stability at room temperature. However, MA 2 Z 4 family monolayer materials involve primarily transition metal substitutions for M atoms. In order to address the research gap on lanthanide and actinide MA 2 Z 4 materials, this work conducts electronic structure calculations on novel 2D MSi 2 N 4 (M = La, Eu) monolayer materials by employing first-principles methods and CASTEP. High carrier mobility is discovered in the indirect bandgap semiconductor 2D LaSi 2 N 4 monolayer (~5400 cm 2  V -1  s -1 ) and in the spin (spin-down channel) carrier mobility of the half-metallic ferromagnetic EuSi 2 N 4 monolayer (~2800 cm 2  V -1  s -1 ). EuSi 2 N 4 monolayer supplements research on spin carrier mobility in half-metallic ferromagnetic monolayer materials at room temperature and possesses a magnetic moment of 5 μ B , which should not be underestimated. Furthermore, due to the unique electronic band structure of EuSi 2 N 4 monolayer (with the spin-up channel exhibiting metallic properties and the spin-down channel exhibiting semiconductor properties), it demonstrates a 100% spin polarization rate, presenting significant potential applications in fields such as magnetic storage, magnetic sensing, and spintronics., (© 2024 Wiley Periodicals LLC.)

The development of novel methods in solid-state quantum chemistry necessitates reliable reference data sets for their assessment. The most fundamental solid-state property of interest is the crystal structure, quantified by the lattice parameters. In the last decade, several studies were conducted to assess theoretical approaches based on the agreement of calculated lattice parameters with respect to experiment as a measure. However, most of these studies used a limited number of reference systems with high symmetry. The present work offers a more comprehensive reference benchmark denoted as Sol337LC, which consists of 337 inorganic compounds with 553 symmetry-inequivalent lattice parameters, representing every element of the periodic table for atomic numbers between 1 and 86, except noble gases, the radioactive elements and lanthanoids. The reference values were taken from earlier benchmarks and from measurements at very low temperature or extrapolation to 0 K. The experimental low-temperature lattice parameters were then corrected for zero-point energy effects via the quasi-harmonic approximation for direct comparison with quantum-chemical optimized structures. A selection of standard density functional approximations was assessed for their deviations from the experimental reference data. The calculations were performed with the crystal orbital program CRYSTAL23, applying optimized atom-centered basis sets of triple-zeta plus polarization quality. The SCAN functional family and the global hybrid functional PW1PW, augmented with the D3 dispersion correction, were found to provide closest agreement with the Sol337LC reference data., (© 2024 The Author(s). Journal of Computational Chemistry published by Wiley Periodicals LLC.)

We developed a method for evaluating the accuracies of the local properties of DFT functionals in detail using a clustering method based on machine learning and structural/electronic descriptors. We generated 36 clusters consistent with human intuition using 30,436 carbon atoms from the QM9 dataset. The results were used to evaluate 13 C NMR chemical shifts calculated using 84 DFT functionals. Carbon atoms were grouped based on their similar environments, reducing errors within these groups. This enables more accurate assessment of the accuracy using a specific DFT functional. Therefore, the present atomic clustering provides more detailed insight into accuracy verification., (© 2024 Wiley Periodicals LLC.)

Machine learning techniques have found their way into computational chemistry as indispensable tools to accelerate atomistic simulations and materials design. In addition, machine learning approaches hold the potential to boost the predictive power of computationally efficient electronic structure methods, such as density functional theory, to chemical accuracy and to correct for fundamental errors in density functional approaches. Here, recent progress in applying machine learning to improve the accuracy of density functional and related approximations is reviewed. Promises and challenges in devising machine learning models transferable between different chemistries and materials classes are discussed with the help of examples applying promising models to systems far outside their training sets., (© 2024 Wiley Periodicals LLC.)

Pidotimod is a chiral drug that possesses two chiral centers, resulting in three isomeric impurities (analytes, A). This study employs electrospray ionization ion trap mass spectrometry (ESI-MS) through collision-induced dissociation (CID) to investigate the chiral recognition of pidotimod and its three isomers to eliminate chromatographic separation. Three approaches were explored: (1) Protonated molecules in CID exhibited discriminative potential for diastereomers, with the ability to distinguish between S,S and R,R configurations, albeit with an R chiral value of ~1.8. However, differentiation between R,S and S,R configurations was not achievable. (2) Alkali adductions (lithium and sodium) only discerned diastereomers. The R chiral values of the diastereomers obtained from alkali adduct ions were significantly lower than those obtained from protonated ions. (3) Therefore, a third approach was used to address the challenge of distinguishing between R,S and S,R configurations, including the introduction of chiral references (ref) and transition metals (M II ) to form metal-bound complexes [M II (A)(ref)-H] + . Additionally, we synthesized a novel ligand, 4-(N-tert-butoxycarbonyl [Boc]-L-prolinamido)phenol (denoted as ligand A), by modifying N-t-Boc-L-Pro with 2-aminophenol, which, in combination with Cu II and Ni II , enabled simultaneous differentiation of all four isomers. Cu II complexes exhibited significant chiral selectivity between R,S and S,R configurations. Density functional theory calculations were performed to further elucidate the stereodynamic behavior and stoichiometry of these ions in the gas phase. These calculations revealed the interaction energy and coordination sites of the precursor ions in the gas phase, correlating well with MS/MS experiment results. Additionally, the logarithm of the Cu II complexes' characteristic fragment ion abundance ratio demonstrated a strong linear relationship with enantiomeric excess (ee). This study presents a novel strategy for chiral drug quality control that eliminates chromatographic separation., (© 2024 Wiley Periodicals LLC.)

In this work, we present simulations of the optical rotation (OR) for five molecular crystals at density functional theory level with periodic boundary conditions (DFT-PBC). Calculations are compared with experimental measurements and show semi-quantitative agreement with experimental data for three of the crystals: tartatic acid, benzil, and pentaerythritol. For the other two crystals, aspartic acid and glutamic acid, the calculated data are in qualitative agreement with, but two orders of magnitude smaller than, the experimental data. We provide some arguments that support the theoretical predictions and suggest that the experiments should be revisited. We also find that the position of H centers provided in experimental X-ray data is not sufficiently reliable for simulating OR, and better results are obtained when H atoms are allowed to relax while keeping heavier elements fixed at the experimental positions. Comparison with molecular cluster calculations with a better functional and a larger basis set indicate that the role of intermolecular interactions (reproduced with the PBC technique) is as or more important than the choice of model chemistry. Despite the current limitations in the level of theory that can be employed, these simulations provide a promising avenue to investigate the effect of intermolecular interactions on this sensitive electronic property of molecules and materials., (© 2024 Wiley Periodicals LLC.)

We present a comprehensive investigation of the electronic properties of fluorinated monolayer violet phosphorus using first-principles calculations. Our results reveal a strong dependence of the electronic properties on the different fluorine coverages of fluorination. As the fluorine coverage increases, monolayer violet phosphorus undergoes a significant transition from a wide direct bandgap semiconductor to a narrow indirect bandgap semiconductor. Moreover, both semi-fluorinated and fully fluorinated monolayer violet phosphorus exhibit advantageous semiconducting characteristics, with a tunable bandgap of 0.50 ~ 1.04 eV under biaxial strain ranging from -6% to 6%. Notably, the fully fluorinated monolayer violet phosphorus demonstrates a higher coefficient of light absorption within the visible range. Therefore, our findings highlight the tunability of monolayer violet phosphorus properties through the absorption of various fluorine coverages, providing valuable insights for the design and development of novel semiconductor devices based on this material., (© 2024 Wiley Periodicals LLC.)

Chlorine is an important chemical which has long been produced in chlor-alkali process using dimensionally stable anodes (DSA). However, some serious drawbacks of DSA inspire the development of alternative anodes for chlorine evolution reaction (CER). In this study, we focused on the graphene- and carbon nanotube-supported platinum tetra-phenyl porphyrins as electrocatalysts for CER, which have been theoretically investigated based on density functional theory. Our results reveal that the supported substrates possess potential CER electrocatalytic activity with very low thermodynamic overpotentials (0.012-0.028 V) via Cl* pathway instead of ClO*. The electronic structures analyses showed that electron transfer from the support to the adsorbed chlorine via the Pt center leads to strong Pt-Cl interactions. Furthermore, the supported electrocatalysts exhibited excellent selectivity toward CER because of high overpotentials and reaction barriers of oxygen evolution process. Therefore, our results may pave the way for designing CER electrocatalyst utilizing emerging carbon nanomaterials., (© 2024 Wiley Periodicals LLC.)

Solvent effects on 31 P-NMR parameters for triphenylphosphine oxide and triphenylphosphine in chloroform have been extensively investigated by testing different solvation models. The solvent is described implicitly, mixed implicitly/explicitly, and using full explicit models. Polarizable continuum model (PCM), molecular dynamic (MD) simulations, and hybrid quantum mechanics/molecular mechanics (QM/MM) calculations are used to disclose the effects of solute/solvent interactions and, more generally, the role of the embedding in NMR simulations. The results show the beneficial effect of carrying out QM/MM optimizations on top of geometries directly extracted from classical MD simulations, used to ensure representative conformational sampling. The nuclear shielding convergence has been tested against a different number of snapshots and with the inclusion of solvent shells into the QM region. An automated MD//QM/MM//GIAO protocol, implemented in the COBRAMM package, is here proposed and tested on trimethyl phosphite showing that our approach boosts the convergence of nuclear shielding satisfactorily. The present work aims to be a stepping-stone to assess proper QM/MM computational strategies in simulating chemical shifts in non-homogeneous systems like supramolecular and biological systems., (© 2024 Wiley Periodicals LLC.)

Investigation of Lewis acid-base interactions has been conducted by ab initio calculations and machine learning (ML) models. This study aims to resolve two critical tasks that have not been quantitatively investigated. First, ML models developed from density functional theory (DFT) calculations predict experimental BF 3 affinity with Pearson correlation coefficients around 0.9 and mean absolute errors around 10 kJ mol -1 . The ML models are trained by DFT-calculated BF 3 affinity of more than 3000 adducts, with input features readily obtained by rdkit. Second, the ML models have the capability of predicting the relative strength of Lewis base binding atoms in Lewis polybases, which is either an extremely challenging task to conduct experimentally or a computationally expensive task for ab initio methods. The study demonstrates and solidifies the potential of combining DFT calculations and ML models to predict experimental properties, especially those that are scarce and impractical to empirically acquire., (© 2024 Wiley Periodicals LLC.)

This paper is the first to look at the structural, electronic, mechanical, optical, and thermodynamic properties of the ANiX (ASc, Ti, Y, Zr, Hf; XBi, Sn) half-Heusler (HH) using DFT based first principles method. The lattice parameters that we have calculated are very similar to those obtained in prior investigations with theoretical and experimental data. The positive phonon dispersion curve confirm the dynamical stability of ANiX (ASc, Ti, Y, Zr, Hf; XBi, Sn). The electronic band structure and DOS confirmed that the studied materials ANiX (ASc, Ti, Y, Zr, Hf; XBi, Sn) are direct band gap semiconductors. The investigation also determined significant constants, including dielectric function, absorption, conductivity, reflectivity, refractive index, and loss function. These optical observations unveiled our compounds potential utilization in various electronic and optoelectronic device applications. The elastic constants were used to fulfill the Born criteria, confirming the mechanical stability and ductility of the solids ANiX (ASc, Ti, Y, Zr, Hf; XBi, Sn). The calculated elastic modulus revealed that our studied compounds are elastically anisotropic. Moreover, ANiX (ASc, Ti, Y, Zr, Hf; XBi, Sn) has a very low minimum thermal conductivity (K min ), and a low Debye temperature (θ D ), which indicating their appropriateness for utilization in thermal barrier coating (TBC) applications. The Helmholtz free energy (F), internal energy (E), entropy (S), and specific heat capacity (Cv) are determined by calculations derived from the phonon density of states., (© 2024 Wiley Periodicals LLC.)