Oxygen Vacancy Formation Energy Research Articles

Synthesis and carbon monoxide purification performance of ZSM-5 molecular sieve Co-doped Mn/V catalytic material

Trackless, rubber-tired, diesel-powered vehicles are widely used in the mining industry. In recent years, the use of high-performance catalysts to remove carbon monoxide (CO) from diesel vehicle exhaust has attracted much attention. In this paper, a series of manganese-vanadium doped ZSM-5 molecular sieve catalysts were prepared by an impregnation method. The structures of the catalysts were characterized and experiments were conducted to evaluate their performance. The CO catalytic oxidation performance experiments revealed that Mn0.6-V0.4-ZSM-5 had the best performance, with a conversion rate of 97.5 % at 300 °C. The catalyst was also tested for water resistance and stability. Kinetic measurements were performed and the fitted activation energy was 22.68 kJ/mol. Characterization studies revealed that the surface defects formed by Mn and V doping provided a large number of active sites and oxygen vacancies for CO oxidation, increased the number of adsorbed oxygen species on the surface, and enhanced the redox capacity through the interaction of Mn4+ and V5+ to improve the catalytic oxidation performance of the catalyst. The adsorption configurations, adsorption energy (Ebin), and formation energy of oxygen vacancies of CO at different adsorption sites and different active fractions were calculated with density functional theory. The Ebin of CO on Mn2V2O7, the active fraction of Mn0.6-V0.4-ZSM-5, was −1.29 eV, which was the most stable adsorption configuration. This configuration had good oxygen mobility, and was conducive to CO catalysis, confirming the characterization and performance experiments.

Balancing Layered Ordering and Lattice Oxygen Stability for Electrochemically Stable High-Nickel Layered Cathode for Lithium-ion Batteries

Despite the high-capacity nature of high-nickel cathode materials, achieving their practical implementation is challenging due to the susceptibility of atomic arrangement to calcining conditions. Extensive studies have enlightened the correlation between layered ordering and calcining conditions; nevertheless, the alterations in the electronic structure of lattice oxygen remain obscure. In this study, by comparing cathode materials with varying degrees of layered ordering, achieved through adjustments in calcination temperature and lithium equivalent, it is shown that although layered ordering increases, it compromises the electronic structure, creating a labile lattice oxygen environment. Fine structural analysis reveals that a higher local Li/O ratio in highly ordered cathode subsequently alters the band structure by narrowing the band gap between Ni 3d and O 2p, which enhances transition metal–oxygen covalency, and reduces the oxygen vacancy formation energy, adversely affecting cyclability. In highly ordered cathode, the tendency of lattice oxygen to reside within a Li-enriched environment arises from the changes in the favorability of non-paired antisite defects contingent upon the calcination temperature and lithium equivalent. This research underscores the need to balance layered ordering and lattice oxygen stability, offering important insights for the future design of high-nickel cathodes.

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.

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.

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.

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.

Transition-Metal-Doped CeO2 for the Reverse Water-Gas Shift Reaction: An Experimental and Theoretical Study on CO2 Adsorption and Surface Vacancy Effects.

Transition metal-doped ceria (M-CeO2) catalysts (M = Fe, Co, Ni and Cu) with multiple loadings were experimentally investigated for reverse water gas shift (RWGS) reaction. Density functional theory (DFT) calculations were performed to benchmark the properties that impact catalytic activity of CO2 reduction. Temperature-programmed desorption (TPD) was conducted to study the CO2 binding strength on doped CeO2 surfaces; the trend of the energy along increasing metal loading agrees with the DFT calculations. Notably, CO2 dissociative adsorption energy and oxygen vacancy (OV) formation energy are key descriptors obtained from both DFT and experiments, which can be used to evaluate catalytic performance. Results show the effectiveness of transition metal doping in enhancing CO2 adsorption and reducibility of the surfaces, with Fe showing particularly promising results, i.e., CO2 conversion higher than 56% at 600 °C and 100% selectivity to CO. Cu exhibits 100% selectivity to CO but low CO2 conversion, while Co and Ni showed notable ability of methanation, particularly at high loadings. This study finds that an effective CeO2 based RWGS catalyst corresponds to OV sites that have low OV formation energies for surface reduction, and moderate CO2 adsorption energies for strong interaction with the surface to promote C-O bond scission.

Effect of Cu doping on morphology and properties of calcium ferrite and its application as oxygen carrier in chemical looping hydrogen production

Chemical looping hydrogen production with inherent CO2 capture has been widely recognized as a clean and efficient approach to high-purity hydrogen production because of the ultra-pure H2 product without any purification facilities. It is crucial to develop oxygen carriers with better performance to improve fuel conversion and hydrogen production efficiency. The potential of Ca2Fe2O5 in steam converting has been confirmed. However, its lower oxygen transfer capacity, that is, it tends to produce lower fuel conversion in fuel reactors, which will limit its practical application. Here, we report the development of Cu-doped Ca2Fe2O5-based oxygen carriers using sol-gel technology. The effects of B-site substitution of Cu element on the morphological properties and redox properties of Ca2Fe2-xCuxO5 (x = 0, 0.1, 0.25, 0.5, 1) oxygen carriers were evaluated based on experiments and density functional theory calculations. The results show that Cu doping not only elevated the surface oxygen content and enhanced the oxygen activity of the oxygen carriers, but also increased the Fe3+ at the B-site, thus enhanced their binding ability with oxygen molecules. Vacancy formation was a rate-determining step in the chemical looping hydrogen production (CLH), and Cu-doped Ca2Fe2O5 reduced the energy of oxygen vacancy formation. In the CLH process, the doping of Cu significantly improved the hydrogen productivity and fuel conversion rate. The fuel conversion rate was positively correlated with the doping amount of Cu. When x = 1, Ca2Fe2-xCuxO5 had the maximum fuel conversion rate, and its average conversion was 54.2% more than that of undoped Ca2Fe2O5. Ca2Fe2-xCuxO5 with x = 0.25 was the most suitable for CLH with the highest H2 yield, which was 20.3% more than that of Ca2Fe2O5. Moreover, its properties remained stable over multiple redox cycles with high activity and stability for CO-CLH.

Oxygen vacancy modulation for enhanced hydrogen production via chemical looping water-gas shift

Chemical looping water gas shift (CL-WGS)is prospective to generate high-purity hydrogen with integrated CO2 capture. However, this technology is impeded by the lack of active oxygen carriers at mid-temperatures. Here, we synthesized several Ni-doped CoFe2O4-δ to modulate oxygen vacancies and investigate its effect on promoting hydrogen production reaction via chemical looping water gas shift at 650 °C. The findings delineate that doping Ni considerably lowers the energy barriers associated with the oxygen vacancies formation, thereby augmenting their concentration. The underlying mechanism elucidates that within the CL-WGS process, the transfer of lattice oxygen acts as the rate-limiting step. NixCo1-xFe2O4 lowers the formation energy of oxygen vacancies and facilitates the bulk lattice oxygen diffusion through the bulk. Hence, Ni0.5Co0.5Fe2O4 demonstrates the most reduction depth and reversibility via redox reactions, resulting in an elevated hydrogen yield (∼15.5 mmol g−1) at 650 °C, which surpasses the yield from undoped CoFe2O4 by 1.4 times. This performance remains consistently high with only a minimal decline over 100 cycles. The findings introduce a promising approach to promote the reactivity of oxygen carriers, particularly for mid-temperature applications.

Metal-support interaction in supported Pt single-atom catalyst promotes lattice oxygen activation to achieve complete oxidation of acetone at low concentrations

A precious metal catalyst with loaded Pt single atoms was prepared and used for the complete oxidation of C3H6O. Detailed results show that the T100 of the 1.5Pt SA/γ-Al2O3 catalyst in the oxidation process of acetone is 250 °C, the TOF of Pt is 1.09 × 10−2 s−1, and the catalyst exhibits good stability. Characterization reveals that the high dispersion of Pt single atoms and strong interaction with the carrier improve the redox properties of the catalyst, enhancing the adsorption and dissociation capability of gaseous oxygen. DFT calculations show that after the introduction of Pt, the oxygen vacancy formation energy on the catalyst surface is reduced to 1.2 eV, and PDOS calculations prove that electrons on Pt atoms can be quickly transferred to O atoms, increasing the number of electrons on the σp * bond and promoting the escape of lattice oxygen. In addition, in situ DRIFTS and adsorption experiments indicate that the C3H6O oxidation process follows the Mars-van Krevelen reaction mechanism, and CH2 =C(CH3)=O(ads), O* (O2-), formate, acetate, and carbonate are considered as the main intermediate species and/or transients in the reaction process. Particularly, the activation rate of O2 and the cleavage of the -C-C- bond are the main rate-determining steps in the oxidation of C3H6O. This work will further enhance the study of the oxidation mechanism of oxygenated volatile organic pollutants over loaded noble metal catalysts.

BiOBr/FeMoO4 composite achieves oxygen vacancy concentration adjustment to promote persulfate activation degradation of organic pollutants in saline water

The investigation about the mechanism of crystal plane regulation on the generation of oxygen vacancies remains a challenge. In this paper, BiOBr/FeMoO4 composites were synthesized by precise control of crystal plane growth, and it exhibited the enhanced concentration of oxygen vacancies due to lower formation energy of oxygen vacancies. The composite performs higher photo-Fenton-like ability for degrading oxytetracycline hydrochloride (OTC). Structural analyses and theoretical calculations reveal that crystal plane regulation induces significant changes in oxygen vacancy concentration. The BiOBr/FeMoO4/peroxydisulphate (PDS) /light system, which dominated by the non-radical pathway, degraded 96.8 % ± 1.0 % of OTC within 30 min. The activation mechanism of the system and the degradation pathway of OTC were elucidated. The intermediates in the degradation process of OTC were evaluated using liquid chromatograph-mass spectrometer (LC-MS), toxicity evaluation software tool (T.E.S.T) and soybean germination experiments. This work offers novel insights into the pivotal role of crystal plane directional regulation in the quantitative generation of oxygen vacancies.

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

AbstractUnderstanding 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.

Dual-Functional Tungsten-Doped NiO for Highly Sensitive Triethylamine Sensor with ppb Level Detection Limit.

In this study, the W-doped Nickel oxide (NiO) nanoflowers were synthesized using a straightforward hydrothermal method, significantly enhancing the sensing performance toward triethylamine through dual-functional tungsten doping. The optimal doping concentration not only increased the specific surface area of NiO from 25.54 to 189.19 m2 g-1 but also reduced the formation energy of oxygen vacancies. The sensor containing 4 at % W-doped NiO demonstrated exceptional sensitivity to triethylamine, achieving a detection level as high as 229.0 for concentrations of 100 ppm at 237.5 °C. This triethylamine sensor represents a 135-fold enhancement over sensors fabricated from undoped NiO, and offers a rapid response/recovery time of 8 and 30 s, respectively. Furthermore, at a lower triethylamine concentration of 50 ppb, indicating a lower detection limit.

Experimental study and DFT+U calculations on the impact of Rare-Earth ion (La3+, Sm3+, Y3+, Yb3+) doped CeO2 Core-Shell abrasives on polishing performance

A series of carbon spheres coated with Rare-Earth ion-doped (La3+, Sm3+, Y3+, Yb3+) CeO2 (CS@CeO2) were synthesized using eco-friendly hydrothermal and chemical precipitation methods. The structural characteristics of the abrasives were thoroughly analyzed using XRD, SEM, TEM, and FT-IR techniques. A detailed analysis of Ce3+ and Vo concentrations on the CeO2 layer surface was conducted using XPS and Raman spectroscopy. The analysis results indicated that CS@Ce0.9Y0.1O2 abrasives exhibited the highest Ce3+ (46.23 %) and Vo (25.39 %) concentrations. Additionally, the polishing performance of the abrasives was evaluated using atomic force microscopy (AFM). The CS@Ce0.9Y0.1O2 abrasive exhibited superior polishing performance, achieving the lowest surface roughness (Ra = 0.26 nm) compared to commercial abrasives (Ra = 0.77 nm), reducing Ra by 66.23 %. Moreover, density functional theory with the Hubbard U method (DFT+U) was used to systematically investigate the oxygen vacancy formation energy, structural stability, and electronic properties of CeO2 doped with Rare-Earth ions. These findings demonstrate that doping with Rare-Earth ions possessing ionic radii close to that of Ce4+ effectively enhances the concentration of oxygen vacancies and Ce3+ ions, which is crucial for improving polishing performance. This work provides valuable reference data on the doping of Rare-Earth ions in CeO2-based polishing abrasives.

Oxygen vacancy-engineered cerium oxide mediated by copper-platinum exhibit enhanced SOD/CAT-mimicking activities to regulate the microenvironment for osteoarthritis therapy

Cerium oxide (CeO2) nanospheres have limited enzymatic activity that hinders further application in catalytic therapy, but they have an “oxidation switch” to enhance their catalytic activity by increasing oxygen vacancies. In this study, according to the defect-engineering strategy, we developed PtCuOX/CeO2-X nanozymes as highly efficient SOD/CAT mimics by introducing bimetallic copper (Cu) and platinum (Pt) into CeO2 nanospheres to enhance the oxygen vacancies, in an attempt to combine near-infrared (NIR) irradiation to regulate microenvironment for osteoarthritis (OA) therapy. As expected, the Cu and Pt increased the Ce3+/Ce4+ ratio of CeO2 to significantly enhance the oxygen vacancies, and simultaneously CeO2 (111) facilitated the uniform dispersion of Cu and Pt. The strong metal-carrier interaction synergy endowed the PtCuOX/CeO2-X nanozymes with highly efficient SOD/CAT-like activity by the decreased formation energy of oxygen vacancy, promoted electron transfer, the increased adsorption energy of intermediates, and the decreased reaction activation energy. Besides, the nanozymes have excellent photothermal conversion efficiency (55.41%). Further, the PtCuOX/CeO2-X antioxidant system effectively scavenged intracellular ROS and RNS, protected mitochondrial function, and inhibited the inflammatory factors, thus reducing chondrocyte apoptosis. In vivo, experiments demonstrated the biosafety of PtCuOX/CeO2-X and its potent effect on OA suppression. In particular, NIR radiation further enhanced the effects. Mechanistically, PtCuOX/CeO2-X nanozymes reduced ras-related C3 botulinum toxin substrate 1 (Rac-1) and p-p65 protein expression, as well as ROS levels to remodel the inflammatory microenvironment by inhibiting the ROS/Rac-1/nuclear factor kappa-B (NF-κB) signaling pathway. This study introduces new clinical concepts and perspectives that can be applied to inflammatory diseases.Graphical

Constructing oxygen vacancies by selective anion doping in high entropy perovskite oxide for water splitting

High entropy perovskite oxide (HEPO) is a potential electrocatalyst for the oxygen evolution reaction (OER), but insufficient activity remains a problem. Oxygen vacancies can activate the lattice oxygen to induce the lattice oxygen-mediated mechanism (LOM), which can avoid the kinetic limitation present in adsorbate evolution mechanism (AEM), thereby improving the OER activity. Herein, we select the appropriate doping element (S) through analysis of ionic radius, electronegativity, and oxygen vacancy formation energy, and report an effective two-step oxygen vacancy strategy for introducing oxygen vacancies into HEPO through electrospinning and sulfurization treatment. This strategy optimizes the eg orbital filling electron number and significantly increases the active area, oxygen vacancy content and electroconductivity. Furthermore, the apparent pH dependence and the TMA+ inhibition phenomenon suggest the involvement of the LOM. Consequently, the resulting S/LMO-E has a lower overpotential (314 mV at 10 mA cm−2) and faster kinetics, and shows excellent stability. Meanwhile, the water splitting is achieved at 1.59 V to afford 10 mA cm−2 current density for S/LMO-E⎪⎢Pt/C, which is smaller than that of RuO2⎪⎢Pt/C (1.62 V). This work provides an attractive OER electrocatalyst for efficient water splitting to produce renewable hydrogen and opens a new way for the design of effective and stable high entropy material electrocatalysts.

Oxygen vacancy–rich K-Mn3O4@CeO2 catalyst for efficient oxidation degradation of formaldehyde at near room temperature

Synthesis of catalysts with high catalytic degradation activity for formaldehyde (HCHO) at room temperature is highly desirable for indoor air quality control. Herein, a novel K-Mn3O4@CeO2 catalyst with excellent catalytic oxidation activity toward HCHO at near room temperature was reported. In particular, the K addition in K-Mn3O4@CeO2 considerably enhanced the oxidation activity, and importantly, 99.3 % conversion of 10 mL of a 40 mg/L HCHO solution at 30 °C for 14 h was achieved, with simultaneous strong cycling stability. Moreover, the addition of K species considerably influenced the chemical valence state of Mn from +4 (ε-MnO2) to +8/3 (Mn3O4) on the surface of CeO2, which obviously changed the tunnel structure and the number of oxygen vacancies. One part of K species is uniformly dispersed on K-Mn3O4@CeO2, and the other part exists in the tunnel structure of Mn3O4@CeO2, which is mainly used to balance the negative charge of the tunnel and prevent collapse of the structure, providing enough active sites for the catalytic oxidation of HCHO. We observed a phase transition from tunneled KMnO2 to Mn3O4 to tunneled MnO2 with the decreasing K+ content, in which K-Mn3O4@CeO2 exhibited higher HCHO oxidation activity. In addition, K-Mn3O4@CeO2 exhibited lower oxygen vacancy formation and HCHO adsorption energies in aqueous solution based on density functional theory calculations. This is because the K species provide more active oxygen species and richer oxygen vacancies on the surface of K-Mn3O4@CeO2, promote the mobility of lattice oxygen and the room-temperature reduction properties of oxygen species, and enhance the ability of the catalyst to replenish the consumed oxygen species. Finally, a possible HCHO catalytic oxidation pathway on the surface of K-Mn3O4@CeO2 catalyst is proposed.

First-principles studies on the oxygen vacancy formation in α-Na2FePO4F and β-Na2FePO4F

The orthorhombic β-Na2FePO4F has been extensively studied, however, a novel monoclinic α-Na2FePO4F has not been explored sufficiently. Oxygen vacancies (VO) can affect the physical and chemical properties of materials, and oxygen vacancy formation energy reflects the difficulty of VO formation. Using first-principles methods, we have calculated the formation energies of VO and their relevant charge states in both α-Na2FePO4F and β-Na2FePO4F. Our results reveal that charged vacancies (VO+1 or VO+2) are easier to form than neutral vacancies (VO0). The reduction of the Fermi level, the decrease in the oxygen partial pressure, or the increase of the temperature are found to decrease the formation energy of VO. The formation energy of VO in α-Na2FePO4F is slightly lower than that in β-Na2FePO4F. The electronic density of states of α-Na2FePO4F and β-Na2FePO4F suggest that more defect states are introduced into the band gap as the charge states increase. These defect states are mainly the 3d orbitals of the Fe atoms. The introduction of oxygen vacancies distorts the [FeO4F2] octahedra, which affect the charge density distribution and the defect states introduced in the band gap. Significantly, oxygen vacancies have a local impact on the charge density redistribution in both α-Na2FePO4F and β-Na2FePO4F. These findings provide theoretical insights into the formation of oxygen vacancies and the control of oxygen release.

Layered perovskite-derived Ni/La2-2xPr2xO3 catalysts for hydrogen production via auto-thermal reforming of acetic acid

Auto-thermal reforming (ATR) is an effective route to extract hydrogen from acetic acid (HAc) from bio-oil. Nickel-based catalysts were found active for conversion of HAc via the ATR process. However, the main concerns, such as carbon deposition and sintering, led to deactivation of catalysts. Herein, to address these issues, a series of (La,Pr)2NiO4 layered perovskites and the derived catalysts of Ni/La2-2xPrxO3 were prepared, and evaluated by ATR. It was found that with Pr entering the La2O3 lattice, the reduction temperature of Ni oxide was decreased with improved dispersion of Ni0; meanwhile, lattice defects were found within La2-2xPr2xO3, and oxygen vacancies were formed with more reactive oxygen species, promoting gasification of coking precursors. The lower formation energy of oxygen vacancy over Pr-doped La2O3 support was further proved by DFT, confirming the improved oxygen vacancies. Therefore, the Ni0·8La1.35Pr0.73O3.92±δ catalyst exhibited excellent catalytic performance along with a stable HAc conversion near 100% and a hydrogen yield around 2.49 mol-H2/mol-HAc, while no coking was detected.