Vacancy Formation Energy Research Articles

Dopant Control of Solution-Processed CuI:S for Highly Conductive p-Type Transparent Electrode.

Copper iodide (CuI) has garnered considerable attention as a promising alternative to p-type transparent conducting oxides owing to its low cation vacancy formation energy, shallow acceptor level, and readily modifiable conductivity via doping. Although sulfur (S) doping through liquid iodination has exhibited high efficacy in enhancing the conductivity with record high figure of merit (FOM) of 630 00MΩ-1, solution-processed S-doped CuI (CuI:S) for low-cost large area fabrication has yet to be explored. Here, a highly conducting CuI:S thin-film for p-type transparent conducting electrode (TCE) is reported using low temperature solution-processing with thiourea derivatives. The optimization of thiourea dopant is determined through a comprehensive acid-base study, considering the effects of steric hindrance. The modification of active groups of thioureas facilitated a varying carrier concentration range of 9×1018-2.52×1020cm-3 and conductivities of 4.4-390.7Scm-1. Consequently, N-ethylthiourea-doped CuI:S exhibited a FOM value of 7 600MΩ-1, which is the highest value among solution-processed p-type TCEs to date. Moreover, the formulation of CuI:S solution for highly conductive p-type TCEs can be extended to CuI:S inks, facilitating high-throughput solution-processes such as inkjet printing and spray coating.

The interplay of surface stability and oxygen vacancy dynamics in RE2Si2O7‐based environmental barrier coatings

AbstractSurface structure and relevant oxygen vacancy play an important role in the application of RE2Si2O7 for environmental barrier coatings, in which the oxygen vacancies in RE2Si2O7 may influence their thermal and optical properties. In this work, the structure and thermodynamics of (0 0 1) and (1 1 0) surfaces of RE2Si2O7 (RE = Yb, Lu) are studied via first‐principles calculations to reveal the underlying mechanism of the surface formation and the associated oxygen vacancy behavior. The (1 1 0) surface is preferred energetically, being in good agreement with the experiential results. It is uncovered that the weak chemical bond broken dominates the decrease of the surface energy, together with the contribution from the polyhedral distortion. Furthermore, the [O3Si–O–SiO3] site is found to be the preferred site for oxygen vacancies on (1 1 0) surface. The formation energies of oxygen vacancies on the (1 1 0) surfaces are lower than those in the bulk, suggesting their segregation on the surfaces. These findings provide essential insights into the surface excitation and oxygen vacancy behaviors of RE2Si2O7, which could shield light on the experimental improvement of the thermal, mechanical, and corrosion properties for RE2Si2O7‐based environmental barrier coating materials.

First‐principle screening of corrosion resistant solutes (Al, Zn, Y, Ce, and Mn) in Mg alloys for Integrated Computational Materials Engineering guided stainless Mg design

AbstractMg alloy suffers from its poor corrosion resistance as a result of anodic dissolution of Mg and hydrogen evolution reaction (HER) in humid environments. In this study, the effects of alloying elements (Al, Zn, Y, Ce, and Mn) on both processes in Mg alloys have been quantitatively predicted. Using first‐principle calculations, we first obtained the substitution energies of alloying elements to compare their segregation preference, and then analyzed the influence of solutes at different layers on the stability and hydrogen adsorption properties of Mg(0001) surface by calculating the formation enthalpy, surface energy, vacancy formation energy, work function, Bader charge, deformation charge density, and adsorption free energy of H atom. It has been found that, on the one hand, the interior Mn solute atoms reduce the dissolution of Mg atoms and the transfer of electrons, consequently slowing down the anodic dissolution process. On another hand, the Mn, Y, and Ce elements on the surface inhibit the cathodic HER process by elevating the absolute value of hydrogen adsorption free energy, as a result of those solutes effectively controlling H adsorption behavior on Mg(0001) surface. In contrast, all five elements dissolved inside the Mg grain do not show significant effects on the H adsorption behavior.

Synergistic effect of Pd single atoms and clusters on the de/re-hydrogenation performance of MgH2

Hydrogen storage plays a pivotal role in the hydrogen industry, yet its current status presents a bottleneck. Diverse strategies have emerged in recent years to address this challenge. MgH2 has stood out as a promising solid-state hydrogen storage material due to its impressive gravimetric and volumetric hydrogen density, but its practical application is hampered by elevated thermal stability and sluggish kinetics. In this study, we introduce a solution by synthesizing Pd metallene through a one-pot solvothermal method, revealing a distinctive highly curved lamellar structure with a thickness of around 1.6 nm. Incorporating this Pd metallene into MgH2 results in a composite system wherein the starting dehydrogenation temperature is significantly lowered to 439 K and complete dehydrogenation occurs at 583 K, releasing 6.14 wt.% hydrogen. The activation energy of dehydrogenation for MgH2 was reduced from 170.4 kJ mol–1 to 79.85 kJ mol–1 after Pd metallene decoration. The enthalpy of dehydrogenation of the MgH2–10 wt.% Pd sample was calculated to be 73 kJ mol–1 H2–1 and decreased by 4.4 kJ mol–1 H2–1 from that of dehydrogenation of pure MgH2 (77.4 kJ mol–1 H2–1). Theoretical calculations show that the average formation energy and average adsorption energy of hydrogen vacancies can be significantly reduced in the presence of both Pd clusters and Pd single atoms on the surface of MgH2/Mg, respectively. It suggests that the synergistic effect of in situ formed Pd single atoms and clusters significantly improves the hydrogenation and dehydrogenation kinetics. The identified active sites in this study hold potential as references for forthcoming multi-sized active site catalysts, underscoring a significant advancement toward resolving hydrogen storage limitations.

The pivotal role of oxygen vacancy and surface hydroxyl in the adsorption and activation of CO2 on ceria-zirconia mixed oxide

Ceria-zirconia mixed metal oxide along with pure ceria and zirconia were prepared by the co-precipitation method and characterized by N2-Physisorption, X-ray diffraction (XRD), H2-temperature programmed reduction (H2-TPR), CO-TPR with mass spectroscopy (CO-TPR/MS), oxygen storage capacity (OSC), CO and CO2-temperature programmed desorption with MS (TPD/MS), Raman spectroscopy, XPS, and diffuse reflectance infrared Fourier transform Spectroscopy (DRIFTS) techniques. Furthermore, Density Functional Theory (DFT) calculations were performed to acquire molecular insights into the role of oxygen vacancies and surface hydroxyl species in CO2 adsorption and subsequent activation. Our experimental and theoretical results corroborated the fact that the incorporation of zirconium ions into the ceria matrix enhanced the overall CO2 adsorption and activation by forming thermally stable surface species, which were eventually detected by DRIFTS. Additionally, DFT calculations revealed the oxygen vacancy mediated change in the electronic structure of ceria-zirconia mixed oxide, which had been argued to improve its catalytic activity. Furthermore, the oxygen vacancy formation energy (OVFE), oxygen storage capacity (OSC) and CO2 adsorption energies were correlated to augment the importance of these properties.

Crystalline phase transformation of Sr-Fe based oxygen carriers modulate the cyclic performance for syngas and CO coproduction in chemical looping ethanol reforming coupled with CO2 splitting

The chemical looping reforming coupled with CO2 splitting (CLR-CS) offers a promising solution for syngas production and simultaneous decomposition of CO2. In this study, the Sr-Fe based oxygen carriers (OCs) were evaluated in CLR-CS using ethanol as fuel. The presence of Sr significantly improved the oxidation performance of iron oxides. The Sr element in fresh Sr-Fe based OCs mainly formed two crystal phases, including SrFe12O19 and Sr4Fe6O13. Increasing the amount of Sr element made it easier to form Sr4Fe6O13 crystal phase. The Sr4Fe6O13 was favorable for syngas production, due to the higher surface oxygen vacancy formation energy with a range of 3.13–3.37 eV. However, the lower oxygen transfer capacity (OTC) of Sr4Fe6O13 resulted in a lower CO yield in the of stage of CO2 decomposition. Compared with Sr4Fe6O13, SrFe12O19 exhibited the higher OTC and the higher reactivity of lattice oxygen, which was preferable to produce more CO2 in the stage of ethanol reforming in fuel reactor. During the cycle tests, the crystalline phase of SrFe12O19 didn’t regenerate under the CO2 atmosphere but transformed into Sr4Fe6O13. It was attributed to the lower energy barrier of CO2 oxidation on the oxygen defect surface of Sr4Fe6O13. The phase transformation of SrFe12O19 accompanied the formation of Fe3O4. The excessive Fe3O4 had poor stability and inactivated easily due to sintering and agglomeration in Sr1Fe4 and Sr1Fe6 samples. The Sr1Fe2, namely the molar ratio of SrO to Fe2O3 of 1:2, exhibited the better performance for syngas (0.291 Nm3/kg OC) and CO (0.141 Nm3/kg OC) coproduction at 800 °C. Additionally, the Sr1Fe2 presented an excellent cyclic stability in 30 cycles due to the suitable proportion of Sr4Fe6O13 and iron oxides formed, which maintained a high syngas yield and avoided sintering of iron oxides. Overall, the Sr1Fe2 is a promising OC candidate in CLR-CS process.

Towards understanding the mechanism of titanium suppressing vacancy clustering/void nucleation in vanadium alloy

The energetics and dynamics of vacancy/vacancyn (Vacn) clusters in presence of Ti in vanadium alloy were systemically investigated by first-principles calculations to elucidate the mechanism of Ti suppressing vacancy clustering/void nucleation. Energetically, Ti can reduce vacancy formation energy and stabilize vacancy/Vacn cluster, and the TimVacn clusters are more stable than alone Vacn over 30 % with m, n = 5, corresponding to the smaller saturated size. Kinetically, mono-/di-vacancy diffusion and vacancy clustering near Ti are predicted by the CI-NEB methods and empirical formula. Vacancy diffusing towards Ti shows a lower barrier of 0.04 eV than 0.39 eV in vanadium and the energy barriers of vacancy migrating towards Ti-Vac complexes decrease gradually and are even close to zero during vacancy clustering. The migration barriers of vacancy dissociating from Ti-Vac complexes are relatively higher, and Ti changes the migration mechanism of di-vacancy from one-step to two-step. Ti significantly reduces vacancy effective diffusivity, and the effective diffusivity decreases with Ti concentration. The present results show that Ti additions provide more nucleation sites of vacancies, forming large numbers of stable small-size complexes and hindering vacancy diffusion, and eventually suppress the formation and growth of large vacancy clusters/voids.

Bandgap engineering and antiferroelectric stability of tantalum doped silver niobate ceramics from first-principles

Extensive research has been conducted on silver niobite (AgNbO3)-based antiferroelectric ceramics for their promising applications in energy storage applications, with various compositional modifications explored to improve their energy storage capabilities. In this theoretical study, we have systematically investigated the electronic, structural, and chemical bonding properties of AgNb1-xTaxO3 (x = 0.00, 0.125, 0.25, 0.375, 0.50, abbreviated as ANT100x) solid solutions based on first-principles calculation. Our results reveal that the bandgap increases from 1.82 eV to 1.89 eV, due to the higher energy level of Ta 5d orbitals compared to Nb 4d orbitals. The enlarged bandgap, accompanied with oxygen vacancy formation energy (ΔEf,vac), contributes to the enhancement of Eb. The Ta substitution of Nb site suppresses the cation displacement, oxygen octahedral distortion, and bond length and angles, indicating an improved stability of antiferroelectric phase. In addition, the electron localization function (ELF) and Bader charge values show weakened covalent bonding of Ta−O bonds compared to Nb−O bonds. These theoretical findings have the potential to aid in the advancement and creation of novel energy storage applications using lead-free AFE perovskites, as well as facilitate the manipulation of their breakdown electric field through bandgap engineering.

Possibility of High Ionic Conductivity and High Fracture Toughness in All-Dislocation-Ceramics.

Based on the results of numerical calculations as well as those of some related experiments which are reviewed in the present paper, it is suggested that solid electrolytes filled with appropriate dislocations, which is called all-dislocation-ceramics, are expected to have considerably higher ionic conductivity and higher fracture toughness than those of normal solid electrolytes. Higher ionic conductivity is due to the huge ionic conductivity along dislocations where the formation energy of vacancies is considerably lower than that in the bulk solid. Furthermore, in all-dislocation- ceramics, dendrite formation could be avoided. Higher fracture toughness is due to enhanced emissions of dislocations from a crack tip by pre-existing dislocations, which causes shielding of a crack tip, energy dissipation due to plastic deformation and heating, and crack-tip blunting. All-dislocation-ceramics may be useful for all-solid-state batteries.

Geometrical Stabilities and Electronic Structures of Rh5 Nanoclusters on Rutile TiO2 (110) for Green Hydrogen Production.

Addressing the urgent need for sustainable energy sources, this study investigates the intricate relationship between rhodium (Rh5) nanoclusters and TiO2 rutile (110) surfaces, aiming to advance photocatalytic water splitting for green hydrogen production. Motivated by the imperative to transition from conventional fossil fuels, this study employs density functional theory (DFT) with DFT-D3 and HSE06 hybrid functionals to analyse the geometrical stabilities and electronic structures of Rh5 nanoclusters on TiO2 rutile (110). TiO2, a prominent photocatalyst, faces challenges such as limited visible light absorption, leading researchers to explore noble metals like Rh as cocatalysts. Our results show that bipyramidal Rh5 nanoclusters exhibit enhanced stability and charge transfer when adsorbed on TiO2 rutile (110) compared to trapezoidal configurations. The most stable adsorption induces the oxidation of the nanocluster, altering the electronic structure of TiO2. Extending the analysis to defective TiO2 surfaces, this study explores the impact of Rh5 nanoclusters on oxygen vacancy formation, revealing the stabilisation of TiO2 and increased oxygen vacancy formation energy. This theoretical exploration contributes insights into the potential of Rh5 nanoclusters as efficient cocatalysts for TiO2-based photocatalytic systems, laying the foundation for experimental validations and the rational design of highly efficient photocatalysts for sustainable hydrogen production. The observed effects on electronic structures and oxygen vacancy formation emphasize the complex interactions between Rh5 nanoclusters and the TiO2 surface, guiding future research in the quest for clean energy alternatives.

Bi‐Ligand Synergy Enables Threshold Low Voltage and Bandgap Stable Pure‐Red Mix‐Halide Perovskite LEDs

AbstractPerovskite light‐emitting diodes (LEDs) emitting in the pure‐red range of 630–640 nm show promise in meeting the requirement of the Rec.2100 standard for high‐resolution displays. However, the high‐performing LEDs (external quantum efficiency, EQE >20%) in the pure‐red range suffer from half‐life time (luminance drop to 50% of the initial luminance) of <1.6 h, resulting from the injection/transportation barrier and surface‐defects–induced charge carrier quenching. Herein, a bi‐ligand synergy strategy is developed to address the T50 issue: the introduction of iodide‐rich ligands with different chain length increases the vacancy formation energy of halogen ions and enhances the exciton binding energy, resulting in a high photoluminescence quantum yield of over 92%. The treated CsPbBrx/I3−x films exhibit 34‐fold improved material stability related to the control at continuous aging at 100 °C. As a result, pure‐red LEDs with CIE coordinates of (0.698, 0.301) approaching the Rec.2100 standard are reported. These pure‐red LEDs exhibit a low turn‐on voltage of 1.8 V, which is the lowest among reported pure‐red perovskite LEDs, and even 0.15 V lower than the optical bandgap energy (1.95 eV); and a maximum EQE of ≈21% with fourfold enhanced T50 relative to the best previous pure‐red perovskite LEDs.

Proton-polaron and thermionic identity of BaCeO3 polymorph for intermediate temperature fuel cell technology: A first principles and molecular dynamics approach

This study employs first principles and classical molecular dynamics approach to investigate distinct proton landscape and scattering events among aristotype and hettotype BaCeO3 polymorph. We systematically sampled different migration pathways to examine the thermionic behaviour and lattice disorder against the activation energy profile as a function of operating temperatures. According to DFT outcomes, the asymmetric landscape among hettotype structures entails a feeble vacancy formation energy (Evac = 0.326 eV and 0.485 eV) with noticeable lattice strain (ε = 0.258 % and 0.167 %) and desirable proton transfer pathway relative to aristotype counterpart. The transport characteristics from molecular dynamics on the other hand reveals an accelerated proton transfer at intermediate temperatures (300–550 °C) due to symmetric hydrogen bonding around the proton neighbourhood with a curtailed translational barrier from the low frequency lattice phonons. However, repellent response at elevated temperatures (>550 °C) illustrates the advent of ambipolar characteristics (H+/O2−), structural phase transitions, defect scattering events and the rise of artificial barrier as localized proton traps via proton polaron and defect (VO..) interactions. The study as a result accentuates the demand of structural and dynamical coherence to extend the commercial utility of BaCeO3 polymorph for the fuel cell technology.

Effect of Ni-doped on switching mechanisms and characteristics of ZnO-based memristor: Experimental and first-principles investigations

In this paper, we explore the impact of Ni doping on the resistive switching (RS) performance of ZnO-based resistive random access memory (RRAM). The Ti/ZnO: Ni/ITO resistive memory exhibits a reduced and less discrete forming voltage (Vforming) and set voltage (Vset), along with a more stable high resistance state (HRS). The doping does not change the conductivity mechanism of the device. The observed outcomes can be attributed to the influence of Ni doping on the generation and breakage of the oxygen vacancy conductive filaments (CF) in the vicinity. Using First-Principles calculations, we calculated the formation energy of oxygen vacancies (Vos), the band structure, the density of states (DOS), charge density, and electronic properties of the doped ZnO cell. The oxygen vacancy formation energy (Efv) is significantly lower in the Ni-doped ZnO cell, which is associated with lower Vforming and Vset. And it allows for less randomness in the generation of CF, which improves the stability of the HRS. The band structure shows that Ni doping can add an additional band at the Fermi energy level of ZnO, corresponding to the defect states in the density of states. The improved storage capacity of Ni-doped ZnO devices has been experimentally demonstrated.

Comprehensive study of the synthetic tychite, Na6Mg2(CO3)4SO4: synthesis, structure and conductive properties.

The structural and conductive properties of the synthetic tychite Na6Mg2(CO3)4SO4 (space group: Fd3̄) were explored. Optimal synthesis parameters were selected by varying the molar ratio of reagents, synthesis temperature and time. For structural descriptions, we carried out scanning electron microscopy, thermal analysis, and Raman and Fourier-transform infrared spectroscopy. We carried out theoretical and experimental studies of conductivity. Theoretical calculations were obtained using geometrical-topological analysis based on Voronoi partitioning (the evaluation of geometrical sizes of voids and channels), the bond valence site energy (BVSE) method (the fast calculation of migration energies, Em), kinetic Monte Carlo simulation (the estimation of ionic conductivity at different temperatures), and density functional theory (the precise assessment of Em and vacancy formation energies). The experimental techniques included electrochemical impedance spectroscopy EIS (total conductivity determination) and direct current DC polarization (electronic conductivity assessment) measurements. Na6Mg2(CO3)4SO4 was found to have a three-periodic Na+-ion migration map with an Em of 0.37 eV and 0.18 eV from BVSE and DFT results, respectively. The theoretical value of cationic conductivity was 2.6 × 10-7 S cm-1 at 100 °C. The experimental total conductivity was equal to 6.0 × 10-7 S cm-1 at 100 °C, which is close to theoretical results. Using additional DC polarization, the electronic contribution to the total conductivity was characterized as insignificant.

EFFECT OF VACANCIES AND VOID DEFECTS ON THE STRUCTURAL AND MECHANICAL BEHAVIOR OF TUNGSTEN UNDER HARSH TEMPERATURE AND PRESSURE CONDITIONS

The body-centered cubic transition metal tungsten is frequently used as a pressure calibration material at high temperatures and pressures due to its outstanding mechanical and thermal properties. In this study, molecular dynamics simulations were performed to investigate the behavior of tungsten under harsh temperature and pressure conditions and the impact of fundamental defects, particularly vacancies, and voids, on its physical, structural, and mechanical properties through their correlation with elastic constants. The study also covers mechanical stability, elastic properties, brittleness and ductility, and hardness. The simulations utilized two different embedded atom methods and one modified embedded atom method interatomic potentials. The results show that the fundamental structural characteristics and properties of pure tungsten crystal, including lattice constant, density, cohesive and vacancy formation energies, elastic constants, and moduli in the ground state for all three potentials, are in good agreement with previous experimental and theoretical calculations and results. The calculated results demonstrate that the elastic constants-related properties for defective structures also have the same trend as the perfect crystal. The presence of defects in the crystal causes a decrease in properties at all temperatures and pressures, directly correlated to the fraction of crystal defects. As the percentage of vacancies increases, a further reduction in the elastic constants is observed. Likewise, these findings reveal that the presence of scattered vacancies in the crystal structure causes a more significant decrease in the substance's properties than a void in the center of the crystal (with the same percentage). The presence of any vacancy weakens the interatomic bonds of the atoms around the vacancy, while the existence of a void in the center has less effect on the interatomic bonds of atoms further away from the center of the crystal.

Impact of vacancy defects on the thermal conductivity of BaAgBi: a comprehensive study using molecular dynamics simulations with neural network potentials.

The presence of vacancy defects significantly impacts thermal properties of materials. In this research, we delve into the effects of vacancy defects on the thermal conductivity of ternary alloy BaAgBi, employing molecular dynamics simulations coupled with a deep neural network potential (NNP). Initially, we validate the precision of our NNP by comparing their predictions for energy, atomic forces, phonon dispersion curves, phonon density of states, and vacancy formation energy with density functional theory calculations, ensuring a high degree of accuracy. Our findings reveal that the reduction in thermal conductivity due to vacancies aligns with the Debye-Callaway model, with variations depending on the type of vacancy. Specifically, Ba vacancies result in the most notable decrement in thermal conductivity, attributable to their low phonon participation ratio and high lattice distortion, both factors that enhance phonon scattering. Besides, we find that the high energy barrier (∼1.66 eV) indicates that Ba vacancies hardly migrate at 300 K. This study helps us understand how vacancies affect thermal conductivity in BaAgBi and how different vacancy types affect it.

A combined AIMD and DFT study of the low-energy radiation responses of GaN.

Although GaN is a promising candidate for semiconductor devices, degradation of GaN-based device performance may occur when the device is bombarded by high-energy charged particles during its application in aerospace, astronomy, and nuclear-related areas. It is thus of great significance to explore the influence of irradiation on the microstructure and electronic properties of GaN and to reveal the internal relationship between the damage mechanisms and physical characteristics. Using a combined density functional theory (DFT) and ab initio molecular dynamics (AIMD) study, we explored the low-energy recoil events in GaN and the effects of point defects on GaN. The threshold displacement energies (Eds) significantly depend on the recoil directions and the primary knock-on atoms. Moreover, the Ed values for nitrogen atoms are smaller than those for gallium atoms, indicating that the displacement of nitrogen dominates under electron irradiation and the created defects are mainly nitrogen vacancies and interstitials. The formation energy of nitrogen vacancies and interstitials is smaller than that for gallium vacancies and interstitials, which is consistent with the AIMD results. Although the created defects improve the elastic compliance of GaN, these radiation damage states deteriorate its ability to resist external compression. Meanwhile, these point defects lead the Debye temperature to decrease and thus increase the thermal expansion coefficients of GaN. As for the electronic properties of defective GaN, the point defects have various effects, i.e., VN (N vacancy), Gaint (Ga interstitial), Nint (N interstitial), and GaN (Ga occupying the N lattice site) defects induce the metallicity, and NGa (N occupying the Ga lattice site) defects decrease the band gap. The presented results provide underlying mechanisms for defect generation in GaN, and advance the fundamental understanding of the radiation resistances of semiconductor materials.

Reactivity of surface oxygen vacancy sites and frustrated Lewis acid-base pairs of In2O3 catalysts in CO2 hydrogenation.

The effects of oxygen vacancy (VO) formation energy and surface frustrated Lewis acid-base pairs (SFLPs) on the CO2 hydrogenation activity of In2O3 catalysts were studied using density functional theory calculations. The VO formation energy of 2.8-3.3 eV was found to favor HCOO formation, whereas the presence of SFLPs is conducive to CO formation.

Computational screening of single-atom doped In2O3 catalysts for the reverse water gas shift reaction.

The reverse water gas shift (RWGS) reaction is an important method for converting carbon dioxide (CO2) into valuable chemicals and fuels by hydrogenation. In this paper, the catalytic activity of single-atom metal-doped (M = Pt, Ir, Pd, Rh, Cu, Ni) indium oxide (c-In2O3) catalysts in the cubic phase for the RWGS reaction was investigated using density functional theory (DFT) calculations. This was achieved by identifying metal sites, screening oxygen vacancies, followed by further calculating the energy barriers for the direct and indirect dissociation pathways of the RWGS reaction. Our results show that the single-atom dopant in the indium oxide lattice promotes the creation of oxygen vacancies on the In2O3 surface, thereby facilitating the adsorption and activation of CO2 by the oxide surface and initiating the subsequent RWGS reaction. Furthermore, we find that the oxygen vacancy (OV) formation energy on the surface of the single-atom metal doped c-In2O3(111) surface can be used as a descriptor for CO2 adsorption, and the higher the OV formation energy, the more stable the CO2 adsorption structure is. The Cu/In2O3 structure has relatively high energy barriers for both direct (1.92 eV) and indirect dissociation (2.09 eV) in the RWGS reaction, indicating its low RWGS reactivity. In contrast, the Ir/In2O3 and Rh/In2O3 structures are more conducive to the direct dissociation of CO2 into CO, which may serve as more efficient RWGS catalysts. Furthermore, microkinetic simulations show that single atom metal doping to In2O3 enhances CO2 conversion, especially under high reaction temperatures, where the formation of oxygen vacancies is the limiting factor for CO2 reactivity on the M/In2O3 (M = Cu, Ir, Rh) models. Among these three single-atom catalysts, the Ir/In2O3 model was predicted to have the best CO2 reactivity at reaction temperatures above 573 K.

Effects of oxygen adsorption on the corrosion behavior of the Ti(0001) surface: a DFT investigation.

The electrochemical corrosion of Ti surfaces is significantly affected by O adsorption, yet the underlying mechanisms remain unexplored. Herein, density functional theory calculations are employed to examine the adsorption energies, structural properties, electronic structures, and thermodynamic stability of atomic O on Ti(0001) surfaces during initial oxidation. Additionally, the impact of O adsorption on Ti dissolution is assessed by introducing a Ti vacancy on the Ti(0001) surface. The passivation of the Ti(0001) surface is predominantly ascribed to the robust adsorption of O atoms. The thermodynamic results reveal that bulk TiO2 easily forms at 300 K, which explains the spontaneous passivation of the Ti(0001) surface. The formation of an O monolayer on the Ti(0001) surface increases the work function (Φ), positively shifting the equilibrium potential and reducing the corrosion rate. The surface vacancy formation energy of Ti on the Ti(0001)/O surface surpasses that on the clean surface. The electrode potential shift for a Ti atom dissolving from the Ti(0001)/O surface is positive, indicating that oxidation impedes the formation of Ti vacancies, rendering Ti atoms less soluble. This study enhances our comprehension of the corrosion mechanism in Ti metal.