Vacancy Formation Energy Research Articles

Theoretical Study on Pt1/CeO2 Single Atom Catalysts for CO Oxidation

Understanding the influence of structural configurations on catalytic performance is crucial for optimizing atom‐efficient single‐atom catalysts (SACs). In this study, we conducted a density functional theory (DFT) investigation of single Pt atoms positioned at step‐edges and within a solid solution on the CeO2(111) surface. We compared these configurations in terms of thermodynamic stability, electronic properties, and further potential energy surfaces for CO oxidation. Stability studies revealed that the solid solution catalyst exhibits greater stability compared to the step‐edge catalyst. Additionally, the Pt in the solid solution catalyst can effectively activate lattice oxygen atoms, making the catalyst more conducive to the formation of oxygen vacancies. The CO oxidation process was analyzed using the Mars‐van Krevelen mechanism, revealing that the solid solution catalyst possesses a more moderate CO adsorption energy. This, coupled with its lower oxygen vacancy formation energy, leads to reduced energy barriers throughout the CO oxidation cycle. Our findings highlight the strong dependence of catalytic activity on the specific configuration of Pt atoms within the CeO2 matrix, with the solid solution model demonstrating superior catalytic efficiency compared to the step‐edge‐supported Pt catalysts.

The disorder-order transition of FeCuPt nanoparticles with various Cu content

The effect of adding a third-element on disorder-order transition of FePt has been demonstrated using FeCuPt alloy as a model. The introduction of Cu leads to an increase in the ordering degree, and a moderate amount of Cu enhancing the most. Density Functional Theory calculations indicate that the disorder-order transition in FePt is influenced by the ordering temperature and vacancy formation energy. FePtCu alloy with a moderate Cu content exhibits the lowest vacancy formation energy in the L10-phase, which promotes the atom diffusion during annealing and resulting in a higher ordering degree. This study summarizes the annealing temperature, time, and thermodynamic or kinetic conditions required to achieve L10-FePtX alloy with superior ordering degrees. The findings offer valuable insights for selecting suitable third-elements and annealing parameters to produce L10-FePtX alloy with enhanced ordering degrees.

Constructing an Active Sulfur-Vacancy-Rich Surface for Selective *CH3-CH3 Coupling in CO2-to-C2H6 Conversion With 92% Selectivity.

To achieve high selectivity in photocatalytic CO2 reduction to C2+ products, increasing the number of CO2 adsorption sites and lowering the energy barriers for key intermediates are critical. A ZnIn2S4 (ZIS)/MoO3-x (Z-M) photocatalyst is presented, in which plasmonic MoO3-x generates hot electrons, creating a multielectron environment in ZIS that facilitates efficient C─C coupling reactions. Density functional theory (DFT) calculations reveal that MoO3-x reduces the formation energy of sulfur vacancies (SV) in ZIS, thereby enhancing CO2 adsorption and activation. The SV-rich surface lowers the energy barrier for forming HCOO* to -0.33 eV whereas the energy barrier for forming *COOH is 0.77 eV. Successive hydrogenation of HCOO* leads to *CH2, which converts to *CH3 with an energy barrier of -0.63 eV. The energy barrier for *CH3-CH3 coupling is 0.54 eV, which is lower than the 0.73 eV for *CH2-CH2 coupling to form *C2H4. Thus, Z-M preferentially produces C2H6 over C2H4. Under visible light, Z-M achieves a CO2-to-C2H6 conversion rate of 467.3 µmol g-1 h-1 with 92.0% selectivity. This work highlights the dual role of plasmonic photocatalysts in enhancing CO2 adsorption and improving C2+ production in CO2 reduction.

Cation reactivity inhibits perovskite degradation in efficient and stable solar modules.

Perovskite solar modules (PSMs) show outstanding power conversion efficiencies (PCEs), but long-term operational stability remains problematic. We show that incorporating N,N-dimethylmethyleneiminium chloride into the perovskite precursor solution formed dimethylammonium cation and that previously unobserved methyl tetrahydrotriazinium ([MTTZ]+) cation effectively improved perovskite film. The in situ formation of [MTTZ]+ cation increased the formation energy of iodine vacancies and enhanced the migration energy barrier of iodide and cesium ions, which suppressed nonradiative recombination, thermal decomposition, and phase segregation processes. The optimized PSMs achieved a record (certified) PCE of 23.2% with an aperture area of 27.2 cm2, with a stabilized PCE of 23.0%. The encapsulated PSM retained 87.0% of its initial PCE after ~1900 hours of maximum power point tracking at 85°C and 85% relative humidity under 1.0-sun illumination.

Optimized Design of Quinary High-Entropy Transition Metal Carbide Ceramics Based on First Principles

In this paper, we developed models for 21 quinary high-entropy transition metal carbide ceramics (HETMCCs), composed of carbon and the transition metals Ti, Zr, Mo, V, Nb, W, and Ta, employing the Special Quasirandom Structures (SQS) method. We investigated how the transition metal elements influence lattice distortion, mixing enthalpy, Gibbs free energy of mixing, and the electronic structure of the systems through first-principles calculations. The calculations show that 21 systems can form a stable single phase, among which (TiMoVNbTa)C5, (ZrMoNbWTa)C5, and (MoVNbWTa)C5 exhibit superior stability. The formation energy and migration energy of carbon vacancies in systems with strong single-phase stability were calculated to predict their radiation resistance. The formation energy of carbon vacancies is closely related to the types of surrounding transition metal elements, with values ranging between the maximum and minimum formation energies observed in binary transition metal carbides (TMCs). The range of migration energy for carbon vacancies is wider than that observed in TMCs, which can hinder their long-range migration and enhance the radiation resistance of the materials.

Interstitial Oxygen Acts as Electronic Buffer Stabilizing High-Entropy Alloys for Trifunctional Electrocatalysis.

Understanding the effect of elements' oxygen affinity is essential for comprehending high-entropy alloys' (HEAs) complete properties. However, the origin of HEAs' oxygen-containing structure and stability remains poorly understood, primarily due to their diverse components, hindering synthesis and analysis. Herein, the O-doping HEAs (HEA-O) have demonstrated outstanding performance and stability in electrolyzed water and Zinc-air batteries which can be reassembled after being stable for more than 1600h when the zinc consumption is over. The experiment and DFT simulation demonstrate that Cr with strong oxygen affinity can introduce more oxygen into the system of HEAs. Consequently, interstitial oxygens act as electronic buffers making the binding energy of other metal elements move to a higher level. Additionally, O-doping lowers the d-band center promoting electrochemical activity and increasing vacancy formation energies of metal active sites leading to super stability. The study provides significant insights into the design and comprehension of interstitial oxygen-doped HEAs.

The influence of different vacancies on Zr(0001)/SiC close-packed interface performance: A first-principles study

The first-principles were employed to investigate the structure, adhesion, and tensile properties of the Zr(0001)/SiC close-packed interface with different vacancies. From the perspective of vacancy formation energy, SiC coating is beneficial for enhancing the irradiation resistance of Zr cladding. When vacancies are present, except for the Zr2 and Zr3 vacancies, introducing other vacancies reduces the stability of Zr/SiC interfaces. The C-terminated interface is more stable than the Si-terminated interface. Through electronic structure analysis, vacancies at the interface primarily reduce the bonds between Zr and SiC, decreasing the interface stability. Vacancies on the side of SiC indirectly alter the strength or quantity of covalent (bonding or anti-bonding) and ionic bonds at the interface, thus intricately lowering the interface stability. In tensile tests, the cleavage of all interfaces with vacancies still occurs on the side of Zr. Vacancies on the SiC side partly lead to increased electrons between Zr1-Zr2 or Zr2-Zr3, strengthening the metallic bonds and enhancing the interface's ideal strength and ductility. The present study offers a novel perspective from the standpoint of bonding mechanisms, providing good insights into the effects of different vacancies on the performance of Zr/SiC interfaces.

Atomic-scale mechanistic study of oxygen reduction mechanism for B-site doped Pr(Ba,Sr)Co2O5+δ by density functional theory calculations

Pr(Ba,Sr)Co2O5+δ is a promising cathode material for solid oxide fuel cell (SOFC) due to its high oxygen ion transport capability and oxygen reduction activity. Density functional theory (DFT) calculations were performed to elucidate the oxygen reduction mechanism of B-site doped Pr(Ba,Sr)(Co,M)2O5+δ (M = Fe, Ni, Cu, and Zn) materials. First, we investigated the formation of O vacancies. The results indicate that Cu and Zn doping facilitate O vacancy formation, resulting in lower O vacancy formation energies. Furthermore, the interaction between oxygen and the (0 0 1) surfaces of B-site doped Pr(Ba,Sr)(Co,M)2O5+δ has been comprehensively discussed, involving both perfect and defective surfaces. The results demonstrate that the presence of O vacancies enhances the catalytic activity for oxygen reduction, by reducing the energy required for O2 dissociation. Zn-doped Pr(Ba,Sr)(Co,M)2O5+δ exhibits a low O vacancy formation energy, resulting in a stable adsorption configuration upon oxygen dissociation, indicating its potential as a cathode material for SOFC.

A Study on Oxygen Vacancy Resistance Mechanism of V2O5

Introduction: Due to its magnetic and semiconductor properties, V2O5 has shown tremendous potential in resistive switching memory. Method: Therefore, this paper investigates the resistive mechanism of oxygen vacancies in V2O5. The formation energies of different oxygen vacancies are calculated. Results: The results indicate that oxygen vacancies tend to form single-component conductive filaments. In mixed oxygen vacancies clusters, the charge transfer characteristics and density of states of the V2O5-VO 13 vacancies are the most significant, which is consistent with the analysis of formation energy data. Conclusions: Additionally, the charge transfer of cluster oxygen vacancies was calculated, showing that V atoms directly connected to oxygen vacancies tend to lose electrons, while adjacent oxygen atoms are more likely to gain electrons. In V2O5-VO 12 and V2O5-VO 13, the number of electrons obtained by O2 and O16 exceeds the average by 36.4% and 33.2%. Thus, the formation of oxygen vacancies effectively improves the resistance characteristics of the V2O5.

Effect of impurities on hydrogen defect stability and migration barrier in yttrium dihydride crystal

The impurity or alloying atoms in YH2 can alter the local electronic structure and so the hydrogen defect stability, as well as the H migration barrier energy. Thus, DFT calculations were employed to determine the effect of foreign elements from alkali and alkaline earth metals to transition metals and one critical impurity element, O, on H vacancy stability and retention characteristics in YH2. Results revealed that alloying elements act as hydrogen vacancy sinks by reducing the vacancy formation energy at neighboring sites. The implantation of non-magnetic foreign elements (s1, s2, and d10 valence electrons) in hydrogen energy landscape was calculated to be minor; while the hydrogen vacancy formation energy was reduced from 1.37 eV to 1.00 eV, the migration energy barrier of hydrogen was increased from 0.87 eV to 1.15 eV for non-magnetic foreign elements. The migration energy barrier monotonically decreased with increasing d-shell occupancy, reaching as low as 0.4 eV for Cr, Mo(d4), and Fe (d4). Alloying with late transition metals (d8 and d9) moderately impacted the hydrogen vacancy formation. Finally, it was found to be O addition into the YH2- lattice did not alter the energy landscape of hydrogen vacancies. Since alloyed YH2 has not been studied extensively, this study provides an atomistic understanding how alloying elements and impurities trap vacancies and affects hydrogen mobility YH2. Meanwhile, the main findings of this study may serve as guidelines for introducing alloying elements in ZrH2 as well.

Promoting Surface Reconstruction in Spinel Oxides via Tetrahedral-Octahedral Phase Boundary Construction for Efficient Oxygen Evolution.

Understanding the origin of surface reconstruction is crucial for developing highly efficient lattice oxygen oxidation mechanism (LOM) based spinel oxides. Traditionally, the reconstruction has been achieved through electrochemical procedures, such as cyclic voltammetry (CV), linear sweep voltammetry (LSV). In this work, we found that the surface reconstruction in LOM-based CoFe0.25Al1.75O4 catalyst was an irreversible oxygen redox chemical reaction. And a lower oxygen vacancy formation energy (EO-V) could benefit the combination of the activated lattice oxygen atoms with adsorbed water molecular. Motivated by this finding, a strategy of phase boundary construction from Co tetrahedral to octahedral was employed to decrease EO-V in CoFe0.25Al1.75O4. The results showed that as the Co octahedral occupancy ratio rose to 64 %, a 3.5 nm-thick reconstructed layer formed on the catalyst surface with a 158 mV decrease in overpotential. Further experiments indicated that the coexistence of tetrahedral-octahedral (O-T) phase would result in lattice mismatch, promoting non-bonding oxygen states and lowering EO-V. Then more active lattice oxygen combined with H2O molecules to generate hydroxide ions (OH-), followed by soluble cation leaching, which enhanced the reconstruction process. This work provided new insights into the relationship between the intrinsic structure of pre-catalysts and surface reconstruction in LOM-based spinel electrocatalysts.

Electronic Confinement-Restrained Anti-Site Defects in Sodium-Rich Phosphates Toward Multi-Electron Transfer and High Energy Efficiency.

Sodium (Na) super-ionic conductor structured Na3MnTi(PO4)3 (NMTP) cathodes have garnered interest owing to their cost-effectiveness and high operating voltages. However, the voltage hysteresis phenomenon triggered by anti-site defects ( -ASD), namely, the occupation of Mn2+ in the Na2 vacancies in NMTP, leads to sluggish diffusion kinetics and low energy efficiency. This study employs an innovative electronic confinement-restrained strategy to achieve the regulation of -ASD. Partial replacement of titanium (Ti) with electron-rich vanadium (V) favors strong electronic interactions with Mn2+, restraining Mn2+ migration. The results suggest that this strategy can significantly increase the vacancy formation energy and migration energy barrier of manganese (Mn), thus inhibiting -ASD formation. As proof of this concept, an Na-rich Na3.5MnTi0.5V0.5(PO4)3 (NMTVP) material is designed, wherein the electronic interaction enhanced the redox activity and achieved more Na+ storage under high-voltage. The NMTVP cathode delivered a reversible specific capacity of up to 182.7 mAh g-1 and output an excellent specific energy of 513.8Wh kg-1, corresponding to ≈3.2 electron transfer processes, wherein the energy efficiency increased by 35.5% at 30C. Through the confinement effect of electron interactions, this strategy provides novel perspectives for the exploitation and breakthrough of high-energy-density cathode materials in Na-ion batteries.

Experimental and DFT studies of mercury adsorption and oxidation on CuCo2O4(110) surface

Elemental mercury (Hg0) is a typical toxic pollutant in flue gas from coal-fired power plants. The specific role of oxygen transfer on Hg0 oxidation over CuCo2O4 oxygen carrier and the involved reaction mechanisms were systematically studied by experimental and theoretical methods. In this study, the CuCo2O4 oxygen carrier with spinel-structure was prepared with salt-assisted combustion method. To reduce the grain size and increase the specific surface area of the oxygen carrier, the optimal KCl: CuCo2O4 ratio of 1:1 was obtained. Oxygen uncoupling ability of CuCo2O4 oxygen carrier was very strong, and the oxygen-releasing performance was slightly decreased after ten cyclic processes. Simulation based on density functional theory (DFT) shows that CuCo2O4 has relative low oxygen vacancy formation energy and oxygen transport energy barrier, and the oxygen vacancy is the preferred O2 adsorption site. Hg0 removal experiments show that CuCo2O4 has a strong ability to remove Hg0. The proportion of Hg2+ increases with the temperature, and the proportion of HgP decreases accordingly. Simulation shows that the 3-Co site on the surface of the CuCo2O4 oxygen carrier is the optimum Hg0 adsorption site. CuCo2O4 is found as a strong oxygen-releasing oxygen carrier, which can effectively promote the oxidation of Hg0.

In Situ Unraveling Surface Reconstruction of Ni‐CoP Nanowire for Excellent Alkaline Water Electrolysis

The surface reconstruction behavior of transition metal phosphides precursors is considered as an important method to prepare efficient oxygen evolution catalysts, but there are still significant challenges in guiding catalyst design at the atomic scale. Here, the CoP nanowire with excellent water splitting performance and stability is used as a catalytic model to study the reconstruction process. Obvious double redox signals and valence evolution behavior of the Co site are observed, corresponding to Co2+/Co3+ and Co3+/Co4+ caused by auto‐oxidation process. Importantly, the in situ Raman spectrum exhibits the vibration signal of Co–OH in the non‐Faradaic potential interval for oxygen evolution reaction, which is considered the initial step in reconstruction process. Density functional theory and ab initio molecular dynamics are used to elucidate this process at the atomic scale: First, OH− exhibits a lower adsorption energy barrier and proton desorption energy barrier at the configuration surface, which proposes the formation of a single oxygen (–O) group. Under a higher –O group coverage, the Co–P bond is destroyed along with the POx groups. Subsequently, lower P vacancy formation energy confirm that the Ni‐CoP configuration can fast transform into a highly active phase. Based on the optimized reconstruction behavior and rate‐limiting barrier, the Ni‐CoP nanowire exhibit an excellent overpotential of 1.59 V at 10 mA cm−2 for overall water splitting, which demonstrates low degradation (2.62%) during the 100 mA cm−2 for 100 h. This work provide systematic insights into the atomic‐level reconstruction mechanism of transition metal phosphides, which benefit further design of water splitting catalysts.

Phonon spectroscopy and features of low-temperature heat capacity of solid solutions of electrolytes

The kinetic characteristics of thermal frequency phonons in the region of helium temperatures in ceramic samples of the Ce1–xGdxO2–y electrolyte solid solution have been studied. To explain the temperature dependence of the phonon mean free path, we used the previously performed calculations of the energy of vacancy formation in the anion sublattice of a solid solution of zirconium dioxide stabilized by yttrium ZrO2:Y2O3 (YSZ) with a similar crystal structure. It is shown that in the Ce1–xGdxO2–y system under study, the formation of structural defects associated with the presence of vacancies in the anion sublattice with energy Δ = 8.53 K is possible. It has been established that analysis of the temperature dependences of the YSZ heat capacity allows one to trace the degree of disorder (amorphization) of the solid solution depending on its level of stabilization.

Using Post‐Treatment Additives for Crystal Modulation and Interface Passivation Enables the Fabrication of Efficient and Stable Perovskite Solar Cells in Air

AbstractHigh‐performance perovskite solar cells (PSCs) fabricated in ambient air are considered inevitable for low‐cost commercial manufacturing. However, passivating perovskite film defects and controlling the crystallization process are critical for achieving high performance in PSCs. This study proposes using the novel 2D material MBene in green antisolvent to simultaneously modulate the crystallization and passivation defects of perovskites. MBene facilitates the passivation of uncoordinated Pb2+ ions, thereby enhancing the formation energy of vacancies within the perovskite film and adjusting the energy level structure. Moreover, MBene increases nucleation sites for perovskite, significantly extending crystal growth and improving film crystallinity, thereby reducing non‐radiative recombination. Consequently, champion devices treated with MBene achieve a power conversion efficiency (PCE) of 24.22% when fabricated in air, and exhibit superior humidity and long‐term stability. Furthermore, PSCs with added MBene exhibit significant long‐term stability under various environmental conditions, including humidity and heat. The study results lay a foundation for the development of MBene materials in photovoltaics, revealing their mechanism as a new type of 2D material in perovskites, and providing new insights for industrially producing efficient and stable solar cells.

Mild and rapid construction of Ti electrodes for efficient and corrosion-resistant oxidative catalysis at industrial-grade intensity

The development of cost-effective and corrosion-resistant catalytic electrodes for chlorine/oxygen evolution reaction (CER/OER) in large-scale industrial applications is a significant challenge. Herein, the sol–gel method is employed to achieve a uniform coating of ruthenium (Ru) doping copper (Cu) on titanium sheet (Ru + 20 %Cu@Ti), and the highly efficient industrial grade stable Ti dimensional stable anode can be quickly constructed at 723.15 K for 2 h. Cu doping reduces the vacancy formation energy of surface oxygen, promotes additional lattice oxygen vacancy assisted hydrolysis dissociation pathway, improves the selectivity and specific activity of CER at high concentration doping, and reduces the binding energy of OER intermediates (e.g., *OH, *O, and *OOH) at adjacent Ru active sites. The overpotentials require to reach the current density of 10 mA cm−2 for CER and OER were only 365 mV and 232 mV at the conditions of 5.0 M NaCl (pH = 7.0) and 1.0 M KOH + 0.5 M NaCl. More importantly, Ru + 20 %Cu@Ti demonstrates excellent stability, operates continuously for over 340h at industrial current density in neutral and alkaline electrolytes, and its strengthening life reaches 64 h, with ultra-low performance attenuation. Impressively, the designed applied electrode (8.0 cm ✕ 15.0 cm) achieves long-term CER at 0.2–0.3 A cm−2. Further industrial grade evaluation of CER shows that its chlorine extraction polarizability, enhances life and weight loss meet the requirements of industrial applications.

Hydrogen-Induced Topotactic Phase Transformations of Cobaltite Thin Films.

Manipulating physical properties through ion migration in complex oxide thin films is an emerging research direction to achieve tunable materials for advanced applications. While the reduction of complex oxides has been widely reported, few reports exist on the modulation of physical properties through a direct hydrogenation process. Here, we report an unusual mechanism for hydrogen-induced topotactic phase transitions in perovskite La0.7Sr0.3CoO3 thin films. Hydrogenation is performed upon annealing in a pure hydrogen gas environment, offering a direct understanding of the role that hydrogen plays at the atomic scale in these transitions. Topotactic phase transformations from the perovskite (P) to hydrogenated-brownmillerite (H-BM) phase can be induced at temperatures as low as 220 °C, while at higher hydrogenation temperatures (320-400 °C), the progression toward more reduced phases is hindered. Density functional theory calculations suggest that hydroxyl bonds are formed with the introduction of hydrogen ions, which lower the formation energy of oxygen vacancies of the neighboring oxygen, enabling the transition from the P to H-BM phase at low temperatures. Furthermore, the impact on the magnetic and electronic properties of the hydrogenation temperature is investigated. Our research provides a potential pathway for utilizing hydrogen as a basis for low-temperature modulation of complex oxide thin films, with potential applications in neuromorphic computing.

Designing water resistant high entropy oxide materials

The ubiquitous presence of moisture usually shows adverse effects on industrial catalysis. Herein, a concept of engineering entropy to design water-resistant oxide catalysts is proposed. The C3H6 oxidation by spinel ACr2O4 (A=Ni, Mg, Cu, Zn, Co) catalysts is selected as a model. Through DFT calculation, the adsorption energy of C3H6, the dissociation energy of molecular H2O on the oxide surface, and the formation energy of oxygen vacancy all suggest better performance induced by higher configurational entropy. Indeed, (Ni0.2Mg0.2Cu0.2Zn0.2Co0.2)Cr2O4 experimentally show excellent water resistance (>100 h) in C3H6 oxidation, while in sharp contrast binary oxides (e.g., NiCr2O4, CoCr2O4) are deactivated in 20 h. H2O-TPD, in-situ Raman, and in-situ FTIR all confirm the low H2O adsorption energy and strong hydrothermal stability of high entropy oxide, which is attributed to their lower Gibbs free energy. This work may inspire the rational design of water-resistant catalysts.

Defects-Rich Heterostructures Trigger Strong Polarization Coupling in Sulfides/Carbon Composites with Robust Electromagnetic Wave Absorption

Defects-rich heterointerfaces integrated with adjustable crystalline phases and atom vacancies, as well as veiled dielectric-responsive character, are instrumental in electromagnetic dissipation. Conventional methods, however, constrain their delicate constructions. Herein, an innovative alternative is proposed: carrageenan-assistant cations-regulated (CACR) strategy, which induces a series of sulfides nanoparticles rooted in situ on the surface of carbon matrix. This unique configuration originates from strategic vacancy formation energy of sulfides and strong sulfides-carbon support interaction, benefiting the delicate construction of defects-rich heterostructures in MxSy/carbon composites (M-CAs). Impressively, these generated sulfur vacancies are firstly found to strengthen electron accumulation/consumption ability at heterointerfaces and, simultaneously, induct local asymmetry of electronic structure to evoke large dipole moment, ultimately leading to polarization coupling, i.e., defect-type interfacial polarization. Such “Janus effect” (Janus effect means versatility, as in the Greek two-headed Janus) of interfacial sulfur vacancies is intuitively confirmed by both theoretical and experimental investigations for the first time. Consequently, the sulfur vacancies-rich heterostructured Co/Ni-CAs displays broad absorption bandwidth of 6.76 GHz at only 1.8 mm, compared to sulfur vacancies-free CAs without any dielectric response. Harnessing defects-rich heterostructures, this one-pot CACR strategy may steer the design and development of advanced nanomaterials, boosting functionality across diverse application domains beyond electromagnetic response.