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Trends in C-O and N-O bond scission on rutile oxides described using oxygen vacancy formation energies.

ABSTRACT: Reactivity trends on transition metals can generally be understood through the d-band model, but no analogous theory exists for transition metal oxides. This limits the generality of analyses in oxide-based catalysis and surface chemistry and has motivated the appearance of numerous descriptors. Here we show that oxygen vacancy formation energy (ΔE _Vac) is an inexpensive yet accurate and general descriptor for trends in transition-state energies, which are usually difficult to assess. For rutile-type oxides (MO₂ with M = 3d metals from Ti to Ni), we show that ΔE _Vac captures the trends in C-O and N-O bond scission of CO₂, CH₃OH, N₂O, and NH₂OH at oxygen vacancies. The proportionality between ΔE _Vac and transition-state energies is rationalized by analyzing the oxygen-metal bonds, which change from ionic to covalent from TiO₂ to NiO₂. ΔE _Vac may be used to design oxide catalysts, in particular those where lattice oxygen and/or oxygen vacancies participate in the catalytic cycles.

SUBMITTER: Su HY

PROVIDER: S-EPMC8152721 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Unraveling the enhanced Oxygen Vacancy Formation in Complex Oxides during Annealing and Growth.

Project description:The reduction of oxides during annealing and growth in low pressure processes is a widely known problem. We hence investigate the influence of mere annealing and of growth in vacuum systems to shed light on the reasons behind the reduction of perovskites. When comparing the existing literature regarding the reduction of the perovskite model material SrTiO3 it is conspicuous that one finds different oxygen pressures required to achieve reduction for vacuum annealing and for chemically controlled reducing atmospheres. The unraveling of this discrepancy is of high interest for low pressure physical vapor depositions of thin films heterostructures to gain further understanding of the reduction of the SrTiO3. For thermal annealing, our results prove the attached measurement devices (mass spectrometer/ cold cathode gauge) to be primarily responsible for the reduction of SrTiO3 in the deposition chamber by shifting the thermodynamic equilibrium to a more reducing atmosphere. We investigated the impact of our findings on the pulsed laser deposition growth at low pressure for LaAlO3/SrTiO3. During deposition the reduction triggered by the presence of the laser plume dominates and the impact of the measurement devices plays a minor role. During post annealing a complete reoxidization of samples is inhibited by an insufficient supply of oxygen.

| S-EPMC5238382 | biostudies-literature

Influence of Mixed Valence on the Formation of Oxygen Vacancy in Cerium Oxides.

Project description:Ceria is one of the most important functional rare-earth oxides with wide industrial applications. Its amazing oxygen storage/release capacity is attributed to cerium's flexible valence conversion between 4+ and 3+. However, there still exists some debate on whether the valence conversion is due to the Ce-4f electron localization-delocalization transition or the character of Ce-O covalent bonds. In this work, a mixed valence model was established and the formation energies of oxygen vacancies and electronic charges were obtained by density functional theory calculations. Our results show that the formation energy of oxygen vacancy is affected by the valence state of its neighboring Ce atom and two oxygen vacancies around a Ce4+ in CeO2 have a similar effect to a Ce3+. The electronic charge difference between Ce3+ and Ce4+ is only about 0.4e. Therefore, we argue that the valence conversion should be understood according to the adjustment of the ratio of covalent bond to ionic bond. We propose that the formation energy of oxygen vacancy be used as a descriptor to determine the valence state of Ce in cerium oxides.

| S-EPMC6947290 | biostudies-literature

Trends in Surface Oxygen Formation Energy in Perovskite Oxides.

Project description:Perovskite oxides comprise an important class of materials, and some of their applications depend on the surface reactivity characteristics. We calculated, using density functional theory, the surface O vacancy formation energy (E Ovac) for perovskite-structure oxides, with a transition metal (Ti-Fe) as the B-site cation, to estimate the catalytic reactivity of perovskite oxides. The E Ovac value correlated well with the band gap and bulk formation energy, which is a trend also found in other oxides. A low E Ovac value, which is expected to result in higher catalytic activity via the Mars-van Krevelen mechanism, was found in metallic perovskites such as CaCoO3, BaFeO3, and SrFeO3. On the other hand, titanates had high E Ovac values, typically exceeding 4 eV/atom, suggesting that these materials are less reactive when O vacancy formation is involved in the reaction mechanism.

| S-EPMC9178614 | biostudies-literature

Guided anisotropic oxygen transport in vacancy ordered oxides.

Project description:Anisotropic and efficient transport of ions under external stimuli governs the operation and failure mechanisms of energy-conversion systems and microelectronics devices. However, fundamental understanding of ion hopping processes is impeded by the lack of atomically precise materials and probes that allow for the monitoring and control at the appropriate time- and length- scales. In this work, using in-situ transmission electron microscopy, we directly show that oxygen ion migration in vacancy ordered, semiconducting SrFeO2.5 epitaxial thin films can be guided to proceed through two distinctly different diffusion pathways, each resulting in different polymorphs of SrFeO2.75 with different ground electronic properties before reaching a fully oxidized, metallic SrFeO3 phase. The diffusion steps and reaction intermediates are revealed by means of ab-initio calculations. The principles of controlling oxygen diffusion pathways and reaction intermediates demonstrated here may advance the rational design of structurally ordered oxides for tailored applications and provide insights for developing devices with multiple states of regulation.

| S-EPMC10539514 | biostudies-literature

Catalytic properties of trivalent rare-earth oxides with intrinsic surface oxygen vacancy.

Project description:Oxygen vacancy (Ov) is an anionic defect widely existed in metal oxide lattice, as exemplified by CeO2, TiO2, and ZnO. As Ov can modify the band structure of solid, it improves the physicochemical properties such as the semiconducting performance and catalytic behaviours. We report here a new type of Ov as an intrinsic part of a perfect crystalline surface. Such non-defect Ov stems from the irregular hexagonal sawtooth-shaped structure in the (111) plane of trivalent rare earth oxides (RE2O3). The materials with such intrinsic Ov structure exhibit excellent performance in ammonia decomposition reaction with surface Ru active sites. Extremely high H2 formation rate has been achieved at ~1 wt% of Ru loading over Sm2O3, Y2O3 and Gd2O3 surface, which is 1.5-20 times higher than reported values in the literature. The discovery of intrinsic Ov suggests great potentials of applying RE oxides in heterogeneous catalysis and surface chemistry.

| S-EPMC11233603 | biostudies-literature

Colossal oxygen vacancy formation at a fluorite-bixbyite interface.

Project description:Oxygen vacancies in complex oxides are indispensable for information and energy technologies. There are several means to create oxygen vacancies in bulk materials. However, the use of ionic interfaces to create oxygen vacancies has not been fully explored. Herein, we report an oxide nanobrush architecture designed to create high-density interfacial oxygen vacancies. An atomically well-defined (111) heterointerface between the fluorite CeO2 and the bixbyite Y2O3 is found to induce a charge modulation between Y3+ and Ce4+ ions enabled by the chemical valence mismatch between the two elements. Local structure and chemical analyses, along with theoretical calculations, suggest that more than 10% of oxygen atoms are spontaneously removed without deteriorating the lattice structure. Our fluorite-bixbyite nanobrush provides an excellent platform for the rational design of interfacial oxide architectures to precisely create, control, and transport oxygen vacancies critical for developing ionotronic and memristive devices for advanced energy and neuromorphic computing technologies.

| S-EPMC7069997 | biostudies-literature

Decoupling free-carriers contributions from oxygen-vacancy and cation-substitution in extrinsic conducting oxides.

Project description:The intrinsic oxygen-vacancies and the extrinsic dopants are two major fundamental free-carrier sources for the extrinsic conducting oxides, such as Sn-doped In(2)O(3). Yet, the individual contributions of the above two free-carrier sources to the total carrier concentrations have never been unraveled. A carrier-concentration separation model is derived in this work, which can define the individual contributions to the total carrier concentration from the intrinsic oxygen-vacancies and the extrinsic dopants, separately. The individual contributions obtained from the present carrier-concentration separation model are verified by the two-state trapping model, photoluminescence, and positron annihilation lifetime (PAL) spectroscopy. In addition, the oxygen-vacancy formation energy of the Sn:In(2)O(3) thin film is determined to be 0.25 eV by PAL spectroscopy.

| S-EPMC3562333 | biostudies-other

Formation of Monofluorinated Radical Cofactor in Galactose Oxidase through Copper-Mediated C-F Bond Scission.

Project description:Galactose oxidase (GAO) contains a Cu(II)-ligand radical cofactor. The cofactor, which is autocatalytically generated through the oxidation of the copper, consists of a cysteine-tyrosine radical (Cys-Tyr•) as a copper ligand. The formation of the cross-linked thioether bond is accompanied by a C-H bond scission on Tyr272 with few details known thus far. Here, we report the genetic incorporation of 3,5-dichlorotyrosine (Cl2-Tyr) and 3,5-difluorotyrosine (F2-Tyr) to replace Tyr272 in the GAOV previously optimized for expression through directed evolution. The proteins with an unnatural tyrosine residue are catalytically competent. We determined the high-resolution crystal structures of the GAOV, Cl2-Tyr272, and F2-Tyr272 incorporated variants at 1.48, 1.23, and 1.80 Å resolution, respectively. The structural data showed only one halogen remained in the cofactor, indicating that an oxidative carbon-chlorine/fluorine bond scission has occurred during the autocatalytic process of cofactor biogenesis. Using hydroxyurea as a radical scavenger, the spin-coupled hidden Cu(II) was observed by EPR spectroscopy. Thus, the structurally defined catalytic center with genetic unnatural tyrosine substitution is in the radical containing form as in the wild-type, i.e., Cu(II)-(Cl-Tyr•-Cys) or Cu(II)-(F-Tyr•-Cys). These findings illustrate a previously unobserved C-F/C-Cl bond cleavage in biology mediated by a mononuclear copper center.

| S-EPMC7737484 | biostudies-literature

High Oxygen Evolution Activity of Tungsten Bronze Oxides Boosted by Anchoring of Co2+ at Nb5+ Sites Accompanied by Substantial Oxygen Vacancy.

Project description:The participation of lattice oxygen in the oxygen evolution reaction (OER) process has been proved to be faster in kinetics than the mechanisms where only metal is involved, although activating the lattice oxygen in the traditional rigid structures remains a big challenge. In this work, efforts are devoted to exploring a new flexible structure that is competent in providing large amounts of oxygen vacancies as well as offering the freedom to manipulate the electronic structure of metal cations. This is demonstrated by anchoring low valence state Co at high valence state Nb sites in the tetragonal tungsten bronze (TTB)-structured Sr0.5Ba0.5Nb2- x Co x O6-? , with different ratios of Co to Nb to optimize the Co substitution proportion. It is found that the occupation of Co in the Nb5+ sites gives rise to the generation of massive surface oxygen vacancies (Ovac), while Co itself is stabilized in Co2+ by adjacent Ovac. The coexistence of Ovac and LS Co2+ enables an oxygen intercalation mechanism in the optimal SBNC45 with specific activity at 1.7 V versus reversible hydrogen electrode that is 20 times higher than for the commercial IrO2. This work illuminates an entirely new avenue to rationally design OER electrocatalysts with ultrafast kinetics.

| S-EPMC7675188 | biostudies-literature

Bond Energies of Enamines.

Project description:Energetics of reactive intermediates underlies their reactivity. The availability of these data provides a rational basis for understanding and predicting a chemical reaction. We reported here a comprehensive computational study on the energetics of enamine intermediates that are fundamental in carbonyl chemistry. Accurate density functional theory (DFT) calculations were performed to determine the bond energies of enamines and their derived radical intermediates. These efforts led to the compilation of a database of enamine energetics including a thermodynamic index such as free-energy stability, bond dissociation energy (BDE), and acid dissociation constant (pK a) as well as a kinetic index such as nucleophilicity and electrophilicity. These data were validated by relating to experimentally determined parameters and their relevance and utility were discussed in the context of modern enamine catalysis. It was found that pK a values of enamine radical cations correlated well with redox potentials of their parent enamines, the former could be used to rationalize the proton-transfer behavior of enamine radical cations. An analysis of the BDE of enamine radical cations indicated that these species underwent facile β-C-H hydrogen transfer, in line with the known oxidative enamine catalysis. The enamine energetics offers the possibility of a systematic evaluation of the reactivities of enamines and related radicals, which would provide useful guidance in exploring new enamine transformations.

| S-EPMC8867489 | biostudies-literature

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