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Employing crystal facets to regulate the catalytic properties in electrocatalytic carbon dioxide reduction reaction (eCO2RR) has been well demonstrated on electrocatalysts containing single metals but rarely explored for bimetallic systems. Here, we synthesize ZnSn(OH)6 (ZSO) microcrystals (MCs) with distinct facets and investigate the facet effects in eCO2RR. Electrochemical studies and in situ Fourier Transform Infrared Spectroscopy (in situ-FTIR) reveal that ZSO MCs produce mainly C1 products of HCOOH and CO. The {111} facet of the ZSO MCS exhibits higher selectivity and faradaic efficiency (FE) than that of the {100} facet over a wide range of potentials (−0.9 V ∼ −1.3 V versus RHE). Density Functional Theory (DFT) calculations elucidate that the {111} facet is favorable to the adsorption/activation of CO2 molecules, the formation of intermediate in the rate-determining step, and the desorption of C1 products of CO and HCOOH molecules.

Catalytic oxidation is used to control carbon monoxide (CO) emissions from industrial exhaust. In this work, The prepared Pta-Fe(OH)x catalysts (x represents the mass fraction of Pt loading (%), a = 0.5, 1 and 2) by the one-pot reduction method exhibited excellent CO catalytic activity, with the Pt2-Fe(OH)x catalyst, 70% and ∼100% CO conversion was achieved at 30°C and 60°C, respectively. In addition, the Pt2-Fe(OH)x catalyst also showed excellent H2O resistance and hydrothermal stability in comparison to the Pt2/Fe(OH)x catalyst prepared by impregnation method. Characterization results showed that the excellent catalytic performance of the catalysts was mainly attributed to the abundant surface oxygen species and Pt0 the presence of H2O, which promoted the catalytic reaction of CO, and Density functional theory (DFT) calculation showed that this was mainly attributed to the catalytic activity of the hydroxyl (-OH) species on Pt2-Fe(OH)x surface, which could easily oxidize CO to -COOH, which could be further decomposed into CO2 and H atoms. This study provides valuable insights into the design of high-efficiency non-precious metal catalysts for CO catalytic oxidation catalysts with high efficiency.

The large Stokes shifts usually result in open circuit voltage (VOC) reduction, which will affect the photovoltaic performance of the material. Recently, three-dimensional organosulfide-halide perovskites (CYS)PbCl2 and (CYS)PbBr2 [CYS: +NH3(CH2)2S−] have received much attention in the photovoltaic field due to their higher stability and similar photoelectric properties (desirable direct bandgap, band dispersion, and light absorption) than MAPbX3 (X = Cl, Br, and I). Unfortunately, both materials exhibit large Stokes shifts emission. Thus, to be clear about their application prospects in the photovoltaic field, the origin of the large Stoke shift needs to be investigated. Moreover, the bandgaps of (CYS)PbBr2 (2.17 eV) and (CYS)PbCl2 (2.32 eV) are higher than the ideal bandgap value of (0.9–1.6 eV) for photovoltaic materials. Based on density functional theory, this paper explores the cause of large Stokes shifts and further improves the photovoltaic performance of the materials by halogen substitution. The calculation results show that the large Stokes shifts come from defect emission rather than intrinsic self-trapping emission and the I atom substitution can reduce the bandgap [(CYS)PbI2; gap = 1.85 eV] and enhance the optical absorption and carrier migration ability without destroying the direct bandgap. Our research will promote the experimental synthesis of more excellent perovskite photovoltaic materials. [ABSTRACT FROM AUTHOR]

This study aimed to investigate the insertion reaction of the polar monomers mediated by the cationic rare earth metal complex [(C5H5)Sc(NMe2CH2C6H4-o)]+ utilizing a combination of density functional theory (DFT) calculations and multivariate linear regression (MLR) methods. The chain initiation step of the insertion reaction could be described by the poisoning effect and the ease of monomer insertion, which could be represented via the DFT-calculated energy difference between σ- and π-coordination complexes (ΔΔE) and insertion energy barrier (ΔG≠), respectively. The results indicate that ΔΔE and ΔG≠ can be predicted by only several descriptors using multiple linear regression methods, with a root mean squared error (RMSE) of less than 2.5 kcal/mol. Furthermore, the qualitative analysis of the MLR models provided effective information on the key factors governing the insertion reaction chain initiation.

Developing an inexpensive and efficient catalyst for a hydrogen evolution reaction (HER) is an effective measure to alleviate the energy crisis. Single-atom catalysts (SACs) based on Janus materials demonstrated promising prospects for the HER. Herein, density functional theory calculations were conducted to systematically investigate the performance of SACs based on the BiTeBr monolayer. Among the one hundred and forty models that were constructed, fourteen SACs with potential HER activity were selected. Significantly, the SAC, in which a single Ru atom is anchored on a BiTeBr monolayer with a Bi vacancy (RuS2/VBi-BiTeBr), exhibits excellent HER activity with an ultra-low |ΔGH*| value. A further investigation revealed that RuS2/VBi-BiTeBr tends to react through the Volmer–Heyrovsky mechanism. An electronic structure analysis provided deeper insights into this phenomenon. This is because the Tafel pathway requires overcoming steric hindrance and disrupting stable electron filling states, making it challenging to proceed. This study finally employed constant potential calculations, which approximate experimental situations. The results indicated that the ΔGH* value at pH = 0 is 0.056 eV for RuS2/VBi-BiTeBr, validating the rationality of the traditional Computational Hydrogen Electrode (CHE) method for performance evaluation in this system. This work provides a reference for the research of new HER catalysts.

Identifying the oxidation structure of two-dimensional interfaces is crucial to improve surface chemistry and electronic properties. Beyond graphene with only phenyl rings, a novel carbon-nitrogen material, C3N, presents an intrinsic heterogeneous surface morphology where each phenyl ring is encircled by six nitrogen atoms, yet its atomistic oxidation structure remains unclear. Here, combining a series of density functional theory calculations and ab initio molecular dynamics simulations, we demonstrate that thermodynamically favorable oxidation loci are confined to the phenyl ring, and kinetic transformations of oxidation structures are feasible along the phenyl ring, whereas those toward nitrogen atoms are proven to be extremely difficult. These results are attributed to the lower barrier of oxygen atom migration along the phenyl ring, while the significantly high barriers toward nitrogen atoms are due to the heterogeneous potential energy surface for oxygen–C3N interaction. This work highlights the significance of surface morphology on the characteristics of oxidation structure, offering insights into tunable electronic properties via confined interfacial oxidation. [ABSTRACT FROM AUTHOR]

The exceptional photophysical and electronic properties of 2D hybrid perovskites possess potential applications in the field of solar energy harvesting. The present work focuses on the two systems, exhibiting the Dion–Jacobson phase of 2D perovskite consisting of methylammonium (MA) and formamidinium (FA) cations at A‐site and 3‐(aminomethyl)pyridinium (3AMPY) as ring‐shaped organic spacer. Altering A‐site cations creates a distortion of inorganic layers and hydrogen bond interactions. It has been noted that the angles of Pb–I–Pb and I–Pb–I are more symmetric (close to 180°) for (3AMPY)(MA)Pb2I7 compared to (3AMPY)(FA)Pb2I7 and result in increase of bandgap from 1.51 to 1.58 eV. This further leads to a significant difference in Rashba splitting energy under the influence of spin‐orbit coupling effects, where the highest splitting (36 meV) is calculated for conduction band edge of the (3AMPY)(FA)Pb2I7, suggesting the promising applications toward spintronics. The calculated absorption spectra cover the range from 300 to 450 nm, indicating significant optical activity of 2D (3AMPY)(MA)Pb2I7 and (3AMPY)(FA)Pb2I7 in the visible and ultraviolet regions, which bodes well for their application in advanced optoelectronic devices. The bandgap and high absorption coefficients present more than 30% of theoretical power conversion efficiency for both systems, as calculated from the spectroscopic‐limited maximum efficiency.

Sustaining the steady state for highly active non‐stoichiometric iridium (Ir)‐based oxide (IrOx) at low Ir loading remains challenging primarily due to the continuous oxidation and sequent dissolution of Ir active sites during the oxygen evolution reaction (OER). In this context, a new iridium–cerium (Ce) substitution solid solution oxide (SSO) has been developed, featuring uniformly dispersed Ir atoms within Ce dioxide (CeO2) matrix as electron buffer, which delivers remarkable acidic OER catalytic activity and enhanced stability. The electron‐buffering capacity of CeO2 facilitates the charge transfer toward Ir atoms, leading to abundant active low‐valence Ir sites and effectively prevent their oxidation and dissolution. As a result, Ir─Ce SSO demonstrates an overpotential of merely 238 mV@10 mA cm−2. Proton exchange membrane water electrolyzer employing Ir─Ce SSO at a low Ir loading of 396 µgIr cm−2 operates consistently for over 100 h@500 mA cm−2. Density functional theory (DFT) calculations corroborate that the electron‐buffering effect of CeO2 enriches the density of IrIII and substantially increases the dissolution energy barrier of Ir atoms. This study presents a viable approach to addressing the issues of instability and low efficiency in Ir‐based OER electrocatalysts for acidic water electrolysis. [ABSTRACT FROM AUTHOR]

Crystalline poly-para-xylylene (parylene) has the potential for use as a protective membrane to delay the nucleation of explosives by separating the explosives and their decomposition products to decrease the explosive sensitivity. Here, molecular dynamics (MD) and density functional theory (DFT) techniques were used to calculate the dissociative adsorption configurations of 1,1-diamino-2,2-dinitroethylene (FOX-7) on (001)- and (101)-oriented crystalline parylene membranes. Based on the results of the calculations, this work demonstrates that the -NO2–π electrostatic interactions are the dominant passivation mechanism of FOX-7 on these oriented surfaces. FOX-7 can dissociatively adsorb on oriented parylene membranes due to the interactions between the LUMO of the toluene (or methyl) groups on parylene and the HOMO of the -NO2 (or -NH2) groups on FOX-7. The formation of a new intermolecular H-bond with the ONO group leads to FOX-7 decomposition via intramolecular C-NO2 bond fission and nitro-to-nitrite rearrangement. The most likely adsorption configurations are described in terms of the decomposition products, surface active groups of parylene, binding behaviors, and N charge transfer. Importantly, the (001)-oriented parylene AF8 membrane is promising for use as a protective membrane to passivate the high-energy -NO2 bonds during the dissociative adsorption of FOX-7. This study offers a new perspective on the development of protective membranes for explosives.

Abstract The characteristics of frustrated Lewis pairs (FLPs) on albite surfaces were analyzed with density functional theory, and the reaction mechanism for H2 activation by the FLPs was studied. The results show that albite is an ideal substrate material with FLPs, and its (001) and (010) surfaces have the typical characteristics of FLPs. In the case of H2 activation, the interaction between the HOMO of H2 and the SOMO of the Lewis base and the electron acceptance characteristics of the Lewis acid are the key factors. In fact, the activation energy of H2 is the required activation energy from the ground state to the excited state, and once the excited state is produced, the dissociative adsorption of H2 will occur directly. This study provides a new ideas and a reference for research on the construction of novel solid FLPs catalysts using ultramicro channel materials.

Abstract Janus nanosystems enable one to achieve complementary properties in a single entity. In the current study, the fundamental properties like structural, electronic, and dynamical of Janus hexagonal boron nitride (h‐BN) by selectively hydrogenating and fluorinating a h‐BN surface are systematically examined, using density functional theory. Functionalization of h‐BN introduces partial sp3 (buckled) character in the predicted materials as compared to planar sp2 h‐BNs. Fully fluorinated and hydrogenated h‐BN have a direct bandgap of 3.42 and 3.37 eV, respectively. All the investigated configurations are predicted to be dynamically stable. Furthermore, optical properties including dielectric function, absorption spectra, refractive index, and reflectivity are evaluated to realize the optical and photocatalytic behavior of considered systems. The dielectric function ɛ2(ω) shows fundamental absorption edge arising at 3.2, 3.9, 2.8, and 3.4 eV for hydrogen on boron and nitrogen, hydrogen on boron and fluorine on nitrogen, fluorine on boron and hydrogen on nitrogen (FBNH) and fluorine on boron and nitrogen which is comparable to the bandgap of respective monolayers. Solar cell parameters of all considered BN structures are calculated using the Shockley–Queisser (SQ) limit. The highest short‐circuit current density (Jsc ) for FBNH is found to be 2.1 mA cm−2 providing the efficiency of 8.27% making FBNH a potential candidate for absorber layer in solar cells.

The corrosion inhibition behavior of Mg-8Li-3Al alloy in NaCl solution with sodium dodecyl sulfate (SDS) was investigated by hydrogen analysis, scanning electron microscopy (SEM), electrochemical test, scanning Kelvin probe force microscopy (SKPFM) and computational methods. Results showed that the corrosion resistance of Mg-8Li-3Al alloy in NaCl solution was effectively improved with SDS. The SEM and SKPFM results confirmed a dense, 200 nm-thick SDS-adsorbed layer had formed on the alloy surface. The separation energy ∆Egap and adsorption energy Eads of SDS on the Mg surface were calculated by density functional theory and molecular dynamics simulations, respectively. And the corrosion inhibition mechanism was hypothesized and described.

An extension of a first-principle combined Monte Carlo method is proposed in this work to obtain the secondary electron emission characteristics of anisotropic crystal Al2O3. Unlike isotropic crystal Cu, density functional theory calculations reveal that the q-dependent energy loss function of Al2O3 in all directions is different. Therefore, an interpolation algorithm is introduced in the Monte Carlo method to determine the loss of energy and inelastic mean free path of electrons. The simulation results are in good agreement with experimental data. This method can be further used to simulate the secondary emission yield of other anisotropic crystal materials. [ABSTRACT FROM AUTHOR]

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.

Catalytic oxidation is used to control carbon monoxide (CO) emissions from industrial exhaust. In this study, a mesoporous silica material, KCC-1, was synthesized and used as a carrier with a high specific surface area to confine active component FeOx nanoparticles (NPs), and the CO catalytic oxidation performance of x%Fe@KCC-1 catalysts (x represents the mass loading of Fe) was studied. The experimental results showed that due to its large specific surface area and abundant mesopores, the FeOx NPs were highly dispersed on the surface of the KCC-1 carrier. The particle size of FeOx was very small, resulting in strong interactions between FeOx NPs and KCC-1, which enhanced the catalytic oxidation reaction on the catalyst. The FeOx loading improved the CO adsorption capability of the catalyst, which facilitated the catalytic oxidation of CO, with the 7%Fe@KCC-1 catalyst achieving 100% CO conversion at 160 °C. The CO catalytic removal mechanism was investigated by a combination of in-situ DRIFTS and DFT calculations. This study advances scientific understanding of the application potential of nano-catalysts in important oxidation reactions and provides valuable insights into the development of efficient CO oxidation catalysts.

Immersed interface method (IIM) is a promising high-accuracy numerical scheme for the Poisson-Boltzmann model that has been widely used to study electrostatic interactions in biomolecules. However, the IIM suffers from instability and slow convergence for typical applications. In this study, we introduced both analytical interface and surface regulation into IIM to address these issues. The analytical interface setup leads to better accuracy and its convergence closely follows a quadratic manner as predicted by theory. The surface regulation further speeds up the convergence for nontrivial biomolecules. In addition, uncertainties of the numerical energies for tested systems are also reduced by about half. More interestingly, the analytical setup significantly improves the linear solver efficiency and stability by generating more precise and better-conditioned linear systems. Finally, we implemented the bottleneck linear system solver on GPUs to further improve the efficiency of the method, so it can be widely used for practical biomolecular applications. © 2019 Wiley Periodicals, Inc.

We synthesized a low metal-to-sulfur atomic ratio (0.5) FeCoS4, exhibiting high reversible specific capacity. Reduced graphene oxide was covered on the surface to improve the cycling stability and rate performance further. Density functional theory calculations show that composite materials can effectively increase the adsorption energy and enhance the diffusion kinetics. [ABSTRACT FROM AUTHOR]

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.

Intermetallic nanoparticles (NPs) possess significant potentials for catalytic applications, yet their production presents challenges as achieving the disorder-to-order transition during the atom ordering process involves overcoming a kinetic energy barrier. Here, we demonstrate a robust approach utilizing atomic gas-migration for the in-situ synthesis of stable and homogeneous intermetallic alloys for propane dehydrogenation (PDH). This approach relies on the physical mixture of two separately supported metal species in one reactor. The synthesized platinum-zinc intermetallic catalysts demonstrate exceptional stability for 1300 h in continuous propane dehydrogenation under industrially relevant industrial conditions, with extending 95% propylene selectivity and propane conversions approaching thermodynamic equilibrium values at 550–600 oC. In situ characterizations and density functional theory/molecular dynamics simulation reveal Zn atoms adsorb on the particle surface and then diffuse inward, aiding in the formation of ultrasmall and highly ordered intermetallic alloys. This in-situ gas-migration strategy is applicable to a wide range of intermetallic systems. Intermetallic alloys (IMAs) hold significant potential for catalysis. Here, the authors present a robust gas-migration method for synthesizing stable and uniform IMAs, which exhibit exceptional stability over 1300 h in propane dehydrogenation. [ABSTRACT FROM AUTHOR]

Catalysts based on Pt single atom (SA) on metal oxides have shown tremendous potentials for alkaline hydrogen evolution reaction (HER), but they are severely limited by insufficient electron interactions of Pt sites and supports. Herein, a new methodology is developed to precisely locate Pt SAs and Pt clusters into NiCo layered double oxide (LDO) nanosheets, achieved using a dual‐ion etching process with subsequent phase transformation method. Uniquely, the Pt SAs are inserted into LDO layers to form Pt─Co bonds by occupying partial Ni positions, significantly strengthening electron interactions with NiCo LDO and promoting activity of HER. Results from density functional theory calculations indicate that the H* species are preferentially absorbed onto O sites on top of these Pt SAs, which are coupled with their adjacent Pt clusters to accelerate water dissociation in the Volmer step. As‐obtained Pt─NiCo LDO exhibits a low overpotential of 92 mV at 10 mA cm−2 and a Tafel slope of 73 mV dec−1, an excellent stability over 105 hours at 60 mA cm−2, and its mass activity is 6 times higher than commercial 20% Pt/C. This study highlights essential functions of coupling interactions between Pt SAs/clusters and LDOs to boost HER for hydrogen energy production. [ABSTRACT FROM AUTHOR]

The electrospun light rare earth orthochromites RCrO3 (R = La, Pr, Nd, Sm, Eu) nanofibers have perovskite-type orthorhombic structures. Raman spectra proved the typical vibration modes of the rotation, bending, and stretching of the CrO6 octahedra in RCrO3 nanofibers. The rare earth element with large ion radius, low electronegativity, and remarkable affinity for oxygen, and the rich redox reaction of Cr endow RCrO3 a potential energy storage material for supercapacitors. It is highly significant to investigate the electrochemical properties of RCrO3. The electrochemical properties of the RCrO3 nanofibers as supercapacitor electrodes were elucidated. At 0.5 A/g, the LaCrO3, PrCrO3, NdCrO3, SmCrO3, and EuCrO3 nanofibers exhibited the specific capacitance values of 267.8, 132.8, 157.6, 170.5, and 170.4 F/g, respectively. First-principles density functional theory method was used to clarify the electronic structure and total density of states of the RCrO3 nanofibers. This study provides a rational design and fabrication method to pseudocapacitor electrodes. [ABSTRACT FROM AUTHOR]

The initial Coulombic efficiency (ICE) for anode materials is usually one of important parameters for the energy density improvement of batteries. However, due to the lack of effective regulatory methods, the excellent ICE is usually difficult to achieve for SnS2 systems based on alloying/conversion mechanisms in Li‐storage process. Herein, a heterostructure constructed from SnS2 nanoflakes in situ anchored on graphene scroll (SnS2@GS) is engineered and fabricated involving a facile in situ sulfurization strategy. The SnS2@GS anode benefiting from 1D open and organized ion diffusion pathways, along with rapid charge transfer in the heterogeneous interfaces, achieves improved reversibility and kinetics. This material exhibits a remarkable specific capacity coupled with a high ICE (≈88%) while yielding robust rate properties. These exceptional lithium storage properties derive from improved conductivity and reduced energy barriers for Li‐ion migration in the heterostructures, as indicated by the density functional theory calculations. Besides, the full‐cell (LiFePO4//SnS2@GS) and the lithium‐ion capacitor based on SnS2@GS anode are assembled and deliver superior energy densities of 330 and 349 W h kg−1, respectively. This proposed approach is also popularized for the fabrication about other metal sulfide wrapped in graphene scroll to construct the anodes with remarkable properties. [ABSTRACT FROM AUTHOR]

The kinetics and storage‐capacity of NiCoMg‐ternary layered double hydroxide (NiCoMg‐LDH) are successfully boosted by valence engineering. As the cathode for aqueous magnesium‐ion batteries (AMIBs), the assembled NiCoMg‐LDH//active carbon (AC) delivers a high specific discharge capacity (121.0 mAh·g−1 at 0.2 A·g−1), long‐term cycling stability (85% capacity retention after 2000 cycles at 1.0 A·g−1) and an excellent performance at −30 °C. Moreover, NiCoMg‐LDH//perylenediimide (PTCDI) is assembled, achieving a high specific discharge capacity and long‐term cycling stability. X‐ray absorption spectra (XAS)/X‐ray photoelectron spectroscopy (XPS) analyses and Density functional theory (DFT) calculations disclose that the electrons are redistributed due to the 3d orbital overlap of Co/Ni atoms in NiCoMg‐LDH, which obviously reduces the valence states of Co/Ni atoms, enhances Mg─O bond strength and degree of hybridization of Co/Ni 3d and O 2p orbitals. Hence, the electronic conductivity is significantly enhanced and the electrostatic repulsion between Mg2+ and host layers is greatly reduced, giving rise to the improved diffusion kinetics and storage‐capacity of Mg2+. Furthermore, in situ Raman/X‐ray diffraction (XRD) and ex situ XPS reveal corresponding energy‐storage mechanism. This paper not only demonstrates the feasibility of LDHs as cathode for AMIBs, but also offers a new modification method of valence engineering for high‐performance electrode materials. [ABSTRACT FROM AUTHOR]

The practical application of solid polymer electrolyte is hindered by the small transference number of Li+, low ionic conductivity and poor interfacial stability, which are seriously determined by the microenvironment in polymer electrolyte. The introduction of functional fillers is an effective solution to these problems. In this work, based on density functional theory (DFT) calculations, it is demonstrated that the anion vacancy of filler can anchor anions of lithium salt, thereby significantly increasing the transference number of Li+ in the electrolyte. Therefore, flower‐like SnS2‐based filler with abundant sulfur vacancies is prepared under the regulation of functionalized carbon dots (CDs). It is worth mentioning that the CDs dotted on the surface of SnS2 have rich organic functional groups, which can serve as the bridging agent to enhance the compatibility of filler and polymer, leading to superior mechanical performance and fast ion transport pathway. Additionally, the in situ formed Li2S/Li3N at the interface of Li metal and electrolyte facilitate the fast Li+ diffusion and uniform Li deposition, effectively mitigating the growth of lithium dendrites. As a result, the assembled lithium metal batteries exhibit excellent cycling stability, reflecting the superiority of the carbon dots derived vacancy‐rich inorganic filler modification strategy. [ABSTRACT FROM AUTHOR]

Transition metal/p‐block compounds are regarded as the most essential materials for electrochemical energy converting systems involving various electrocatalysis. Understanding the role of p‐block element on the interaction of key intermediates and interfacial water molecule orientation at the polarized catalyst‐electrolyte interface during the electrocatalysis is important for rational designing advanced p‐block modified metal electrocatalysts. Herein, taking a sequence of ruthenium phosphides (including Ru2P, RuP and RuP2) as model catalysts, we establish a volcanic‐relation between P‐proportion and alkaline hydrogen oxidation reaction (HOR) activity. The dominant role of P for regulating hydroxyl binding energy is validated by active sites poisoning experiments, pH‐dependent infection‐point behavior, in situ surface enhanced infrared absorption spectroscopy, and density functional theory calculations, in which P could tailor the d‐band structure of Ru, optimize the hydroxyl adsorption sites across the Ru−P moieties, thereby leading to improved proportion of strongly hydrogen‐bonded water and facilitated proton‐coupled electron transfer process, which are responsible for the enhanced alkaline HOR performance. [ABSTRACT FROM AUTHOR]

In this article, the properties of Cs2Pb2O3 have been investigated using the first‐principles method. It covers the relevant structural, stability, electronic properties, conductivity, and optical properties. The phonon spectra and elastic properties analysis show the stability of Cs2Pb2O3, band structure, density of states, charge density diagram, and bond populations are analyzed to show the electronic structure of the system more clearly. The calculated results indicate that considering spin‐orbit coupling (SOC) will reduce the band gap. The charge density diagram and bond populations indicate that the Cs–O bond is mainly ionic and the Pb–O bond is mainly covalent and partially ionic. The analysis of optical properties indicates good transparency, and the calculated hole mobility is 10.88 cm2 V−1 s−1, suggesting that it is a promising p‐type conductive oxide. [ABSTRACT FROM AUTHOR]

Owing to the abundant reserves and low cost, sodium‐ion batteries (SIBs) have garnered unprecedented attention. However, their widespread adoption is hindered by the scarcity of alternative anodes with fast‐charging capability and high stability. To overcome this challenge, a fast‐charging SIB anode, N‐doped Bi/BiOCl embedded in a carbon framework (Bi/BiOCl@NC) with a fast Na+ transport channel and ultra‐high structural stability, is developed. During cycling in ether electrolyte, Bi/BiOCl@NC undergoes a remarkable transformation into a 3D porous skeleton, which significantly reduces the Na+ transport pathway and accommodates volume changes. By employing density functional theory calculations to simulate the storage behavior of Na+ in the structure, Bi/BiOCl@NC is theoretically characterized to have a low Na+ transport barrier (0.056 eV) and outstanding electronic conductivity. Such unique characteristics induce Bi/BiOCl@NC anode to have an ultra‐high Na+ storage capacity of 410 mAh·g−1 at 20 A·g−1 and exhibit outstanding cycling stability with over 2300 cycles at 10 A·g−1. This study provides a rational scenario for the fast‐charging anode design and will enlighten more advanced research to promote the exploitation of SIBs. [ABSTRACT FROM AUTHOR]

Lithium hexafluorophosphate (LiPF6), the most commonly used lithium battery electrolyte salt, is vulnerable to heat and humidity. Quantitative and qualitative determination the variation of LiPF6 have always relied on advanced equipment. Herein, we develop a fast, convenient, high-selective fluorescence detection method based on metal--organic cages (MOC), whose emission is enhanced by nearly 20 times in the presence of LiPF6 with good stability and photobleaching resistance. The fluorescent probe can also detect moisture in battery electrolyte. We propose and verify that the luminescence enhancement is due to the presence of hydrogen bond-induced enhanced emission effect in cages. Fluorescent excitation-emission matrix spectra and variable-temperature nuclear magnetic resonance spectroscopy are employed to clarify the role of hydrogen bonds in guest-loaded cages. Density functional theory (DFT) calculation is applied to simulate the structure of host-guest complexes and estimate the adsorption energy involved in the system. The precisely matched lock-and-key model paves a new way for designing and fabricating novel host structures, enabling specific recognition of other target compounds. [ABSTRACT FROM AUTHOR]

It is unknown how antibiotics would behave after entering the hyporheic zone (HZ), which is an area where groundwater and surface water alternate continuously. In this study, the hydrolysis process in the HZ was investigated based on the intermediates identified by HPLC-Q-TOF-MS and FTIR, and the active sites of sulfamethoxazole (SMX) were predicted by density functional theory (DFT). The results showed that the hydrolysis rate of SMX during surface water recharged groundwater reached 38.94%, and the contribution rate of hydroxyl radicals reached 48.35%. In neutral and alkaline environments, SMX hydrolysed more quickly. This is due to the fact that ·OH, as the main precursor of OH-, is much higher in quantity under alkaline conditions. Inorganic anions such as NO3-, HCO3- and ${\rm CO}_3^{2-}$ CO 3 2 − may inhibit the hydrolysis of SMX by eliminating the reactive oxygen species generated in the HZ. In the process of groundwater recharging to surface water, the concentration of dissolved oxygen (DO) and the rate of SMX hydrolysis gradually reduced. Nitrification, hydroxylation and polymerisation are the main hydrolysis pathways of SMX. The hydrolysis products of SMX in the HZ are more plentiful and have a higher hydrolysis rate compared to the single oxygen environment. The study on the hydrolysis mechanism of SMX in this paper will provide a theoretical basis for the treatment of antibiotic pollution. The degradation pathways and influencing factors of sulfamethoxazole in the hyporheic zone. [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]

Addressing sustainable energy storage remains crucial for transitioning to renewable sources. While Li‐ion batteries have made significant contributions, enhancing their capacity through alternative materials remains a key challenge. Micro‐sized silicon is a promising anode material due to its tenfold higher theoretical capacity compared to conventional graphite. However, its substantial volumetric expansion during cycling impedes practical application due to mechanical failure and rapid capacity fading. A novel approach is proposed to mitigate this issue by incorporating trace amounts of aluminum into the micro‐sized silicon electrode using ball milling. Density functional theory (DFT) is employed to establish a theoretical framework elucidating how grain boundary sliding, a key mechanism involved in preventing mechanical failure is facilitated by the presence of trace aluminum at grain boundaries. This, in turn, reduces stress accumulation within the material, reducing the likelihood of failure. To validate the theoretical predictions, capacity retention experiments are conducted on undoped and Al‐doped micro‐sized silicon samples. The results demonstrate significantly reduced capacity fading in the doped sample, corroborating the theoretical framework and showcasing the potential of aluminum doping for improved Li‐ion battery performance. [ABSTRACT FROM AUTHOR]

Monotypic catalytic site for bifunctional hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) at low overpotential is a grand challenge in alkaline water splitting. Herein, a new strategy of dual‐type atomic site‐support interaction is reported, in which ruthenium heteroatoms are in situ implanted into both the N‐C nanosheet matrix (Ru1‐N‐C) and supported Co2P nanoparticle lattice (Ru2‐P‐Co) for boosting alkaline water splitting. It is found that the Ru1‐N‐C and Ru2‐P‐Co can give rise to a synergistic effect for boosting HER and OER catalysis. Density functional theory calculations disclose that for HER, the Ru‐functionalized Co sites in Co2P assume the task of expediting H2O adsorption‐dissociation, and the adjacent coordination unsaturated Ru1‐N‐C sites can facilitate the following H2 desorption kinetic. The study found that the hydrogen spillover mechanism contributes to an ultralow HER polarization of 69 mV at 10 mA cm−2. While for OER, due to electronegativity discrepancies, the doped Ru within Co2P triggers electronic coupling, thereby efficiently tuning Ru d‐band center. This grants its electronic characteristic preferred for modulating rate‐determining step of OER to reduce the corresponding energy barrier, leading to superior OER catalytic activity. This work offers new understandings into catalyzing different reactions with multiple intermediate adsorptions by different atomic site‐support interplays. [ABSTRACT FROM AUTHOR]

In monolayer transition metal dichalcogenides, defects, such as chalcogen vacancies, play an important role in determining their properties. Herein, monolayer MoSe2 with varying Se vacancy concentrations is successfully prepared by adjusting the amount of the precursors during the chemical vapor deposition synthesis. The Raman and low‐temperature photoluminescence spectra are systematically studied at varying defect concentrations. Furthermore, it is found that Se vacancies introduce in‐gap electronic states, leading to distinct localized exciton emissions, which can be engineered by controlling the concentration of Se vacancies. Density functional theory calculations indicate that the observed variations in localized exciton emission are attributed to the change of defect level with increasing defect concentration. The results provide insights into the influence of varying Se vacancy concentrations on defect‐induced Raman and PL spectroscopy in MoSe2. [ABSTRACT FROM AUTHOR]

Near‐infrared (NIR) phosphors have been widely used in biomedical applications based on their deep tissue penetration. However, the lack of blue‐pumped NIR phosphors with emission ranges beyond 1000 nm has greatly limited the development of NIR phosphor‐converted light‐emitting diodes (pc‐LEDs). Herein, a facile way to boost the luminescence efficiency and thermal stability by introducing the promoters of Ce3+ and Na+ into Nd3+‐doped SrS NIR phosphor is demonstrated, thus achieving light emitting at 850–1500 nm with a peak wavelength of ≈1070 nm. Through sensitization by the allowed 4f → 5d transition of Ce3+, the SrS: Nd3+ phosphors are excitable by using a commercial blue LED, attributing to the effective energy transfer between Nd3+ and Ce3+. Besides, the structural analysis and density functional theory calculations reveal the lattice distortion mechanism and geometry of doping ions contributed to the weakened thermal quenching effect and the increasing of internal quantum efficiency. The optimized NIR phosphor luminescence intensity remains at 91.8% of the initial intensity at 393 K, and the internal quantum efficiency increases to 42.8% from 31.7% of the sample without Na+ doping. The present exploration of Nd3+‐doped NIR phosphors will provide a reference for designing NIR pc‐LEDs with enhanced properties. [ABSTRACT FROM AUTHOR]

In monolayer transition metal dichalcogenides, defects, such as chalcogen vacancies, play an important role in determining their properties. Herein, monolayer MoSe2 with varying Se vacancy concentrations is successfully prepared by adjusting the amount of the precursors during the chemical vapor deposition synthesis. The Raman and low‐temperature photoluminescence spectra are systematically studied at varying defect concentrations. Furthermore, it is found that Se vacancies introduce in‐gap electronic states, leading to distinct localized exciton emissions, which can be engineered by controlling the concentration of Se vacancies. Density functional theory calculations indicate that the observed variations in localized exciton emission are attributed to the change of defect level with increasing defect concentration. The results provide insights into the influence of varying Se vacancy concentrations on defect‐induced Raman and PL spectroscopy in MoSe2. [ABSTRACT FROM AUTHOR]

For lithium‐sulfur batteries (Li‐S batteries), a high‐content electrolyte typically can exacerbate the shuttle effect, while a lean electrolyte may lead to decreased Li‐ion conductivity and reduced catalytic conversion efficiency, so achieving an appropriate electrolyte‐to‐sulfur ratio (E/S ratio) is essential for improving the battery cycling efficiency. A quasi‐solid electrolyte (COF‐SH@PVDF‐HFP) with strong adsorption and high catalytic conversion was constructed for in situ covalent organic framework (COF) growth on highly polarized polyvinylidene fluoride‐hexafluoropropylene (PVDF‐HFP) fibers. COF‐SH@PVDF‐HFP enables efficient Li‐ion conductivity with low‐content liquid electrolyte and effectively suppresses the shuttle effect. The results based on in situ Fourier‐transform infrared, in situ Raman, UV–Vis, X‐ray photoelectron, and density functional theory calculations confirmed the high catalytic conversion of COF‐SH layer containing sulfhydryl and imine groups for the lithium polysulfides. Lithium plating/stripping tests based on Li/COF‐SH@PVDF‐HFP/Li show excellent lithium compatibility (5 mAh cm−2 for 1400 h). The assembled Li‐S battery exhibits excellent rate (2 C 688.7 mAh g−1) and cycle performance (at 2 C of 568.8 mAh g−1 with a capacity retention of 77.3% after 800 cycles). This is the first report to improve the cycling stability of quasi‐solid‐state Li‐S batteries by reducing both the E/S ratio and the designing strategy of sulfhydryl‐functionalized COF for quasi‐solid electrolytes. This process opens up the possibility of the high performance of solid‐state Li‐S batteries. [ABSTRACT FROM AUTHOR]