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Heterostructure catalysts are highly anticipated in the field of photocatalytic water splitting. AlN/Sc2CF2 and GaN/Sc2CF2 heterostructures are proposed in this work, and the electronic structures were revealed with the first-principles method to explore their photocatalytic properties for water splitting. The results found that the thermodynamically stable AlN/Sc2CF2 and GaN/Sc2CF2 heterostructures are indirect semiconductors with reduced band gaps of 1.75 eV and 1.84 eV, respectively. These two heterostructures have been confirmed to have type-â band alignments, with both VBM and CBM contributed to by the Sc2CF2 layer. AlN/Sc2CF2 and GaN/Sc2CF2 heterostructures exhibit the potential for photocatalytic water splitting as their VBM and CBM stride over the redox potential of water. Gibbs free energy changes in HER occurring on AlN/Sc2CF2 and GaN/Sc2CF2 heterostructures are as low as -0.31 eV and -0.59 eV, respectively. The Gibbs free energy change in HER on the AlN (GaN) layer is much lower than that on the Sc2CF2 surface, owing to the stronger adsorption of H on AlN (GaN). The AlN/Sc2CF2 and GaN/Sc2CF2 heterostructures possess significant improvements in absorption range and intensity compared to monolayered AlN, GaN, and Sc2CF2. In addition, the band gaps, edge positions, and absorption properties of AlN/Sc2CF2 and GaN/Sc2CF2 heterostructures can be effectively tuned with strains. All the results indicate that AlN/Sc2CF2 and GaN/Sc2CF2 heterostructures are suitable catalysts for photocatalytic water splitting.
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The electrocatalytic production of hydrogen peroxide (H2O2) through the two-electron oxygen reduction reaction (2e- ORR) has garnered significant research attention in recent years due to its numerous appealing advantages, such as being eco-friendly and exhibiting high energy conversion efficiency. Metal-free carbon materials with specific catalytic sites have been recognized as potential electrocatalysts for 2e- ORR; however, the design of highly efficient catalysts with well-defined structures and long-term stability for large-scale H2O2 production remains unsatisfactory. In this study, three covalent organic frameworks (COFs) - imine-linked LZU-1, oxazole-linked LZU-190, and thiazole-linked LZU-190(S), are successfully synthesized to explore their catalytic activity in electrocatalytic H2O2 production. Among these, the carbon sites LZU-190(S) are predominantly activated by the introduced adjacent heteroatoms via electronic effects, resulting in much higher H2O2 selectivity compared to the oxazole and imine linkages. This work provides new insights into developing COFs-based electrocatalysts for efficient H2O2 generation.
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The design strategy of designing effective local electronic structures of active sites to improve the oxygen evolution reaction (OER) performance is the key to the success of sustainable alkaline water electrolysis processes. Herein, a series of manganese-doped nickel molybdate porous nanosheets with rich oxygen vacancies on the nickel foam (Mn-NiMoO4/NF PNSs) synthesized by the facile hydrothermal and following annealing routes are used as high-efficiency and robust catalysts towards OER. By virtue of unique nanosheets architectures, more exposed active site, rich oxygen vacancies, tailored electronic structures, and improved electrical conductivity induced by Mn incorporation, as predicted, the optimized Mn0.10-NiMoO4/NF PNSs catalyst exhibits superior the OER performance with a low overpotential of 211 mV at 10 mAâ§cm-2, a small Tafel slope of 41.7 mVâ§dec-1, and an excellent stability for 100 h operated at 100 mAâ§cm-2 in 1.0 M KOH electrolyte. The in-situ Raman measurements reveal the surface dynamic reconstruction. Besides, the results of density functional theory (DFT) calculations unveil the reaction mechanism. This study provides an effective design strategy via Mn incorporation to synergistically engineer electronic structures and oxygen vacancies of metal oxides for efficiently boosting the OER performance.
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Auger recombination is a pivotal process for semiconductor nanocrystals (NCs), significantly affecting charge carrier generation and collection in optoelectronic devices. This process depends mainly on the NCs' electronic structures. In our study, we investigated Auger recombination dynamics in manganese (Mn2+)-doped CsPbI3 NCs using transient absorption (TA) spectroscopy combined with theoretical and experimental structural characterization. Our results show that Mn2+ doping accelerates Auger recombination, reducing the biexciton lifetime from 146 to 74 ps with increasing Mn doping concentration up to 10%. This accelerated Auger recombination in Mn-doped NCs is attributed to increased band edge wave function overlap of excitons and a larger density of final states of Auger recombination due to Mn orbital involvement. Moreover, Mn doping reduces the dielectric screening of the excitons, which also contributes to the accelerated Auger recombination. Our study demonstrates the potential of element doping to regulate Auger recombination rates by modifying the materials' electronic structure.
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CONTEXT: The electronic and magnetic properties of non-metallic (NM) elements doping defective graphene-like ZnO (g-ZnO) monolayer including O vacancy (VO) and Zn vacancy (VZn) are studied. The results show that VO-g-ZnO is a semiconductor and VZn-g-ZnO is a magnetic semiconductor. B, C, N, Si, P, 2S, and 2Si doping VO-g-ZnO systems present half-metal and magnetic semiconductors, and the magnetism mainly originates from the spin polarization of doping atoms. For single or double NM elements doping VZn-g-ZnO, 2P doping system presents a semiconductor, while other systems present ferromagnetic metal, half-metal, and magnetic semiconductor. The magnetism of single NM elements doping VZn-g-ZnO mainly comes from the spin polarization of O atoms near the defect point. For double NM elements doping VZn-g-ZnO, spin splitting occurs mainly in p orbitals of O atoms, dopant atoms, and d orbitals of Zn atoms. NM elements doping defect g-ZnO can effectively regulate the electronic and magnetic properties of the system. METHODS: The software package VASP 5.4.1 (Vienna ab initio Simulation Package) is used for calculations in this paper. The local density approximation (LDA) is adopted as an exchange and correlation function to perform the structural optimization and analysis of electronic structure and magnetic properties.
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Electronic structures and quantum transport properties of the monolayer InSe nanoribbons are studied by adopting the tight-binding model in combination with the lattice Green function method. Besides the normal bulk and edge electronic states, a unique electronic state dubbed as edge-surface is found in the InSe nanoribbon with zigzag edge type. In contrast to the zigzag InSe nanoribbon, a singular electronic state termed as bulk-surface is observed along with the normal bulk and edge electronic states in the armchair InSe nanoribbons. Moreover, the band gap, the transversal electron probability distributions in the two sublayers, and the electronic state of the topmost valence subband can be manipulated by adding a perpendicular electric field to the InSe nanoribbon. Further study shows that the charge conductance of the two-terminal monolayer InSe nanoribbons can be switched on or off by varying the electric field strength. In addition, the transport of the bulk electronic state is delicate to even a weak disorder strength, however, that of the edge and edge-surface electronic states shows a strong robustness against to the disorders. These findings may be helpful to understand the electronic characteristics of the InSe nanostructures and broaden their potential applications in two-dimensional nanoelectronic devices as well.
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Both microvoids and helium (He) impurities are widely present in tungsten (W) plasma-facing materials (PFMs), where the interaction between microvoids and He atoms has led to the intriguing development of microvoids. In this paper, we comprehensively investigated the interaction between He atoms and trivacancy (V3), a fundamental microvoid in W-PFMs, at the level of tight-binding theory. Our study showed that He atoms can catalyze the decomposition of the original V3 or facilitate its transformation into another V3 variant. We propose that a He atom near the V3 defect induces significant changes in the distribution of d-electron charges within the W atoms lining the inner wall of the V3 defect, making the W atom nearest to this He atom cationic and the other W atoms anionic. The attractive interaction between them promotes the decomposition and deformation of V3. As electronic excitation increases, the ionization of W atoms on the V3 wall gradually intensifies, thereby enhancing the cationic characteristics of the W atoms closest to the He atom. This process also prompts other W atoms to shift from anions to cations, leading to a transition in the electrostatic interactions between them from attraction to repulsion. This transformation, driven by electronic excitation, plays a significant inhibitory role in the decomposition and deformation of V3.
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Electrocatalysis is a very attractive way to achieve a sustainable carbon cycle by converting CO2 into organic fuels and feedstocks. Therefore, it is crucial to design advanced electrocatalysts by understanding the reaction mechanism of electrochemical CO2 reduction reaction (eCO2RR) with multiple electron transfers. Among electrocatalysts, dual-atom catalysts (DACs) are promising candidates due to their distinct electronic structures and extremely high atomic utilization efficiency. Herein, the eCO2RR mechanism and the identification of intermediates using advanced characterization techniques, with a particular focus on regulating the critical intermediates are systematically summarized. Further, the insightful understanding of the functionality of DACs originates from the variable metrics of electronic structures including orbital structure, charge distribution, and electron spin state, which influences the active sites and critical intermediates in eCO2RR processes. Based on the intrinsic relationship between variable metrics and critical intermediates, the optimized strategies of DACs are summarized containing the participation of synergistic atoms, engineering of the atomic coordination environment, regulation of the diversity of central metal atoms, and modulation of metal-support interaction. Finally, the challenges and future opportunities of atomically dispersed catalysts for eCO2RR processes are discussed.
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Nanotubes have established a new paradigm in nanoscience because of their atomically thin geometries and intriguing properties. However, because of their typical metastability compared to their 2D and 3D counterparts, it is still fundamentally challenging to synthesize nanotubes with controlled size. New strategies have been suggested for synthesizing nanotubes with a controlled geometry. One of these is considering Janus 2D layers, which can self-roll to form a nanotube. Herein, we study 412 nanotubes (along the armchair and zigzag directions) based on 36 Janus IV-VI compounds using density functional theory (DFT) calculations. By investigating the energy-radius relationship using structural models and Bayesian predictions, the most stable nanotubes show negative strain energies and radii below 20 Å, where curvature effects can play a significant role. The band structures show that the selected nanotubes exhibit sizable band gaps and size-dependent electronic properties. More strikingly, the flexoelectricity along the in-plane directions and radial directions in these nanotubes is significantly larger than that in other nanotubes and their 2D counterparts. This work opens up an avenue of structure-property relationships of Janus IV-VI nanotubes and demonstrates giant flexoelectricity in these nanotubes for future electronic and energy applications.
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CONTEXT: In this study, the electronic structure and diffusion barrier of Ca adsorbed MoTe2 system under different degrees of shear deformation were calculated based on the first-principles method. The results show that both the pure MoTe2 system and Ca-adsorbed MoTe2 system are affected by shear deformation. The pure MoTe2 undergoes a transition from direct to indirect band gap under shear deformation. The adsorption of Ca makes MoTe2 changes from semiconductor to quasi-metal. The results of the density of states show that Ca insertion makes the conduction band part of the adsorption system significantly enhanced. The diffusion barrier of Ca through MoTe2 indicates that the shear deformation promotes the diffusion of Ca on the surface of MoTe2. Shear deformation can effectively modulate the electronic properties of the MoTe2 system, which provides a theoretical basis for the application of MoTe2 materials in the field of ion batteries. METHODS: In this study, Materials Studio 8.0 software was used to construct the MoTe2 model and Ca adsorbed MoTe2 model, and the CASTEP module was used for first-principles calculation.
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The photoelectron spectroscopies of RhOn- (n = 1-2) were obtained via using the photoelectron velocity-map imaging (PE-VMI) approach. The experimental values of the adiabatic detachment energy (ADE) and vertical detachment energy (VDE) for RhO- were reported to be 1.58 ± 0.02 eV. The experimental AED and VDE values of RhO2- were reported to be 2.70 ± 0.02 eV and 2.79 ± 0.02 eV, respectively. The vibrational frequencies of RhO- and RhO2- measured from photoelectron spectra (PES) were 817(76) cm-1 and 932(55) cm-1, respectively. Based on the density functional theory (DFT), the RhOn-1/0 (n = 1-4) clusters were investigated. The optimized configurations of corresponding ground states and low-lying clusters were discovered. Meanwhile, the simulated photoelectron spectroscopy (PES) of RhOn- (n = 1-4) and the theoretical ADE and VDE values of RhOn- (n = 1-4) clusters were unveiled to assist future experimental studies of Rhodium oxide clusters. Moreover, the associated molecular orbitals (MOs), natural population analysis (NPA) and bond order analysis have been utilized to investigate the chemical bonding in these groups.
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The extensive applications of MXenes, a novel type of layered materials known for their favorable characteristics, have sparked significant interest. This research focuses on investigating the influence of surface functionalization on the behavior of Mn2NTx (Tx=O2, F2) MXenes monolayers using the "Density functional theory (DFT) based full-potential linearized augmented-plane-wave (FP-LAPW)" method. We elucidate the differences in the physical properties of Mn2NTx through the influence of F and O surface functional groups. We found that O-termination results in half-metallic behavior, whereas the F-termination evolves metallic characteristics within these MXene systems. Similarly, surface termination has effectively influenced their optical absorption efficiency. For instance, Mn2NO2 and Mn2NF2 effectively absorb UV light ~50.15×104â cm-1 and 37.71×104â cm-1, respectively. Additionally, they demonstrated prominent refraction and reflection characteristics, which are comprehensively discussed in the present work. Our predictions offer valuable perspectives into the optical and electronic characteristics of Mn2NTx-based MXenes, presenting the promising potential for implementing them in diverse optoelectronic devices.
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Covalent organic frameworks (COFs) provide a molecular platform for designing a novel class of functional materials with well-defined structures. A crucial structural parameter is the linkage, which dictates how knot and linker units are connected to form two-dimensional polymers and layer frameworks, shaping ordered π-array and porous architectures. However, the roles of linkage in the development of ordered π electronic structures and functions remain fundamental yet unresolved issues. Here we report the designed synthesis of COFs featuring four representative linkages: hydrazone, imine, azine, and C=C bonds, to elucidate their impacts on the evolution of π electronic structures and functions. Our observations revealed that the hydrazone linkage provides a non-conjugated connection, while imine and azine allow partial π conjugation, and the C=C bond permits full π-conjugation. Importantly, the linkage profoundly influences the control of π electronic structures and functions, unraveling its pivotal role in determining key electronic properties such as band gap, frontier energy levels, light absorption, luminescence, carrier density and mobility, and magnetic permeability. These findings highlight the significance of linkage chemistry in COFs and offer a general and transformative guidance for designing framework materials to achieve electronic functions.
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Heterogeneous structures and doping strategies have been intensively used to manipulate the catalytic conversion of polysulfides to enhance reaction kinetics and suppress the shuttle effect in lithium-sulfur (Li-S) batteries. However, understanding how to select suitable strategies for engineering the electronic structure of polar catalysts is lacking. Here, a comparative investigation between heterogeneous structures and doping strategies is conducted to assess their impact on the modulation of the electronic structures and their effectiveness in catalyzing the conversion of polysulfides. These findings reveal that Co0.125Zn0.875Se, with metal-cation dopants, exhibits superior performance compared to CoSe2/ZnSe heterogeneous structures. The incorporation of low Co2+ dopants induces the subtle lattice strain in Co0.125Zn0.875Se, resulting in the increased exposure of active sites. As a result, Co0.125Zn0.875Se demonstrates enhanced electron accumulation on surface Se sites, improved charge carrier mobility, and optimized both p-band and d-band centers. The Li-S cells employing Co0.125Zn0.875Se catalyst demonstrate significantly improved capacity (1261.3 mAh g-1 at 0.5 C) and cycle stability (0.048% capacity delay rate within 1000 cycles at 2 C). This study provides valuable guidance for the modulation of the electronic structure of typical polar catalysts, serving as a design directive to tailor the catalytic activity of advanced Li-S catalysts.
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Transition metals and related compounds are known to exhibit high catalytic activities in various electrochemical reactions thanks to their intriguing electronic structures. What is lesser known is their unique role in storing and transferring electrons in battery electrodes which undergo additional solid-state conversion reactions and exhibit substantially large extra capacities. Here, a full dynamic picture depicting the generation and evolution of electrochemical interfaces in the presence of metallic nanoparticles is revealed in a model CoCO3/Li battery via an in situ magnetometry technique. Beyond the conventional reduction to a Li2CO3/Co mixture under battery operation, further decomposition of Li2CO3 is realized by releasing interfacially stored electrons from its adjacent Co nanoparticles, whose subtle variation in the electronic structure during this charge transfer process has been monitored in real time. The findings in this work may not only inspire future development of advanced electrode materials for next-generation energy storage devices but also open up opportunities in achieving in situ monitoring of important electrocatalytic processes in many energy conversion and storage systems.
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CONTEXT: Transition metal chalcogenides are excellent anode materials for calcium ion batteries (CIBs). In this study, the structural stability, electronic structure, and diffusion barrier of bulk XTe2 (X = Mo, W) were studied by first-principles calculations within the framework of density functional theory. The density of states analysis shows the metal behavior of XTe2 (X = Mo, W) during calcification. The voltage ranges of CayMoTe2 and CayWTe2 are 1.53-0.45 V and 1.48-0.41 V (y = 0-5), respectively. The diffusion barrier of Ca+ through XTe2 indicates that the compressive strain promotes the diffusion of calcium through XTe2. XTe2 is considered to be a promising electrode material for CIBs. METHODS: In this paper, the transition metal chalcogenides model is constructed by Material Studio 8.0, and the first-principles calculation is carried out by CASTEP module.
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Rational tailoring of the electronic structure at the defined active center of reconstructed metal (oxy)hydroxides (MOOH) during oxygen evolution reaction (OER) remains a challenge. With the guidance of density functional theory (DFT), herein a dual-site regulatory strategy is reported to tailor the d-band center of the Co site in CoOOH via the controlled electronic transfer at the RuâOâCoâOâFe bonding structure. Through the bridged O2- site, electrons are vastly flowed from the t2g-orbital of the Ru site to the low-spin orbital of the Co site in the Ru-O-Co coordination and further transfer from the strong electron-electron repulsion of the Co site to the Fe site by the Co-O-Fe coordination, which balancing the electronic configuration of Co sites to weaken the over-strong adsorption energy barrier of OH* and O*, respectively. Benefiting from the highly active of the Co site, the constructed (Ru2Fe2Co6)OOH provide an extremely low overpotential of 248 mV and a Tafel slope of 32.5 mV dec-1 at 10 mA cm-2 accompanied by long durability in alkaline OER, far superior over the pristine and Co-O-Fe bridged CoOOH catalysts. This work provides guidance for the rational design and in-depth analysis of the optimized role of metal dual-sites.
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The crystal structures, stability, mechanical properties and electronic structures of Nb-free and Nb-doped Ti-Al intermetallic compounds were investigated via first-principles calculations. Seven components and eleven crystal configurations were considered based on the phase diagram. The calculated results demonstrate that hP8-Ti3Al, tP4-TiAl, tP32-Ti3Al5, tI24-TiAl2, tI16-Ti5Al11, tI24-Ti2Al5, and tI32-TiAl3 are the most stable phases. Mechanical properties were estimated with the calculated elastic constants, as well as the bulk modulus, shear modulus, Young's modulus, Poisson's ratio and Pugh's ratio following the Voigt-Reuss-Hill scheme. As the Al content increases, the mechanical strength increases but the ductility decreases in the Ti-Al compounds. This results from the enhanced covalent bond formed by the continuously enhanced Al-sp hybrid orbitals and Ti-3d orbitals. Nb doping (~5 at.% in this study) keeps the thermodynamical and mechanical stability for the Ti-Al compounds, which exhibit slightly higher bulk modulus and better ductility. This is attributed to the fact that the Nb 4d orbitals locate near the Fermi level and interact with the Ti-3d and Al-3p orbitals, improving the metallic bonds based on the electronic structures.
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Deep-blue emitters based on combining two approaches are reported here. In the first approach, the nitrogen content of the cyclometallated ligand is increased using 2,4'-bpy ligands, leading to a low highest occupied molecular orbital energy. In the second approach, 2,2'-bpy is replaced with a lower electron donating ligand, leading to a high lowest unoccupied molecular orbital (LUMO) energy. Thus, three new ionic transition metal complexes of [Ir(2,4'-bpy)2(NN)]PF6 [where NN is 2,2'-bpy (1), o-phenylenediamine (2), and 4-methoxy-o-phenylenediamine (3)] were synthesized, and their electronic and photophysical features were studied. In solution, [Ir(2,4'-bpy)2bpy]PF6 emits blue light centered at 396 nm, which is blue-shifted compared to [Ir(ppy)2bpy]PF6. The low electron donation of the diamine ancillary ligands introduces the contribution of the cyclometallated ligand to the LUMO, changing the nature of the emission and leading to different photophysical features. Density functional theory calculations indicate the long bond distances of Ir-Ns at the diamine ligands, suggesting weak metal-ligand interactions and low quantum yields.1.
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Electron-donating/-withdrawing groups (EDGs/EWGs) substitution is widely used to regulate the catalytic performance of transition-metal phthalocyanine (MPc) toward electrochemical CO2 reduction, but the corresponding structure-activity relationships and regulation mechanisms are still ambiguous. Herein, by investigating a series of substitution-functionalized MPc (MPc-X), this work reveals a double-volcano-like relationship between the electron-donating/-withdrawing abilities of the substituents and the catalytic activities of MPc-X. The weak-EDG/-EWG substitution enhances whereas the strong-EDG/-EWG substitution mostly lowers the CO selectivity of MPc. Experimental and calculation results demonstrate that the electronic properties of the substituents influence the symmetry and energy of the highest occupied molecular orbitals of MPc-X, which in turn determine the CO2 adsorption/activation and lead to diverse CO2 reduction pathways on the EWG or EDG substituted MPc via different CO2 adsorption modes. This work provides mechanism insights that could be guidance for the design and regulation of molecular catalysts.