Regulating Photocatalytic Selectivity of Anatase TiO2 with {101}, {001}, and {111} Facets

In this work, we demonstrate a novel approach to control the photocatalytic selectivity of TiO₂ though different dominant crystal facets. {101}, {111}, and {001} facets exposed nanoscale anatase TiO₂ were obtained by a simple hydrothermal route with different ratio of NH₄⁺ and F^?, then a calcined progress to clear surface adsorbent atoms. Results reveal that {101} exposed TiO₂ has some remain binding N with a mode of unsaturated N_3c exhibits selectively photocatalytic degradation of methylene orange (MO) in a methylene blue (MB) and methyl orange (MO) mixed solution, whereas TiO₂ with exposed {111} and {001} facets exhibits photocatalytic selectivity for MB. The {111} facets of anatase TiO₂ exhibit a better photocatalytic selective ability than {001} facets. It confirms that the photocatalytic selectivity can be affected by different dominant crystal facets. In a deeper analysis, there are many unsaturated O_2c on the surface of {001} and {111} facets, which enhances adsorbent selectivity and relevant photocatalytic activity of MB, at the same time, the unsaturated O_2c on the surface of {111} facets is much more than that on the surface of {001} facets results in a better photocatalytic selectivity of {111} facets. This research hopes that developing a new strategy for photocatalytic selectivity and providing a deeper understanding of different crystal facets of TiO₂.     

Effect of LiF dosage on morphology of ZrO2 prepared by the molten salt method

Zirconia nanorods and polyhedral particles were prepared using the molten-salt method. The effects of the LiF dosage on the ZrO₂ crystal morphology were studied using XRD combined with Rietveld refinement, FE-SEM combined with EDS, FTIR, Raman spectroscopy, and high-temperature microscopy. The results show that the ZrO₂ obtained with LiF is in the monoclinic phase. ZrO₂ nanorods were synthesized at low LiF dosages. Polyhedral ZrO₂ particles were synthesized, and the ZrO₂ crystal planes (100) and (200) were exposed to a high LiF dosage. LiF promoted the dissolution of ZrO₂ and was adsorbed onto the ZrO₂ crystal surface. This work provides a new strategy for controlling morphology and crystal surface exposure.     

Size driven thermodynamic crossovers in phase stability in zirconia and hafnia

Hafnia (HfO₂) and zirconia (ZrO₂) are of great interest in the quest for replacing silicon oxide in semiconductor field effect transistors because of their high permittivity. Both exhibit extensive polymorphism and understanding the energetics of their transitions is of major fundamental and practical importance. In this study, we present a systematic thermodynamic summary of the influence of particle size on thermodynamic phase stability in hafnia and zirconia using recently measured enthalpy data from the literature. The amorphous phase is found to be the most energetically stable above 165 and 363 m²/g of surface area for HfO₂ and ZrO₂, respectively. Below 16 and 20.3 m²/g of surface area, respectively, the monoclinic phase is the most energetically stable for HfO₂ and ZrO₂. At intermediate sizes there are closely balanced energetics among monoclinic, tetragonal, and cubic phases. The energy crossovers reflect decreasing surface enthalpy in the order monoclinic, tetragonal, cubic and amorphous for both hafnia and zirconia.     

Atomistic thermodynamics study of the adsorption and the effects of water–gas shift reactants on Cu catalysts under reaction conditions

Density-functional theory (DFT) calculations were performed to determine the structure and stability of oxygen, carbon monoxide and sulfur adsorption on Cu(111), (100) and (110) surfaces that are in equilibrium with a water–gas shift (WGS) reactive environment of H₂, H₂S, H₂O and CO. An atomistic thermodynamic framework based on DFT was used for describing the phase behaviors of the adsorbates on different Cu facets. Phase diagrams of each possible adsorbate on each surface were constructed as a function of the corresponding chemical potential which showed sulfur poisoning occurs even at ppm levels of H₂S in the environment at low temperatures. Under reaction conditions relevant to WGS at low temperature, CO and S adsorbed surface structures were found to be more stable then the clean catalyst surfaces. At high temperatures and high hydrogen pressures, a poisoned surface can be regenerated back to a clean surface. The shapes of a Cu nanoparticle in the WGS reaction conditions under various sulfur chemical potentials were determined using the Wulff construction. We found that the crystal shape changes significantly from one dominated by (111) and (100) facets at very low sulfur chemical potentials to a shape dominated by (110) facets at higher sulfur chemical potentials, suggesting that reactive site distributions may change under reaction conditions.     

Two-step method to deposit ZrO2 coating on carbon fiber: Preparation,characterization, and performance in SiC composites

Recently, ceramic matrix composites reinforced by short carbon fibers (CFs) attracted increasing attentions. To further improve mechanical properties and oxidation resistances, CFs were subjected to oxidation and acidification followed by sol-gel dip-coating to deposit ZrO₂ on their surfaces. ZrO₂-C_f/SiC composites were fabricated by joint hot compression molding and sintering, compared to C_f/SiC and SiC prepared by the same method. Microstructural analyses indicated that ZrO₂ coatings were successfully deposited on CF surfaces, formed strong bonding and interfaces between CF and the matrix. Meanwhile, CFs were found uniformly distributed in SiC matrix with random orientations. Flexural curves of ZrO₂-C_f/SiC and C_f/SiC revealed the presence of “false plasticity” regions after sharp drops, which were quite different from brittle flexural behavior of SiC ceramic. Compression strength of the three samples showed step-up growth. ZrO₂-C_f/SiC exhibited the highest value, indicating the introduction of CFs and ZrO₂ coatings do have great influence on mechanical performances. After heat treatment, ZrO₂-C_f/SiC exhibited better oxidation resistance than C_f/SiC, with weight loss ratios estimated to ??3.76% and ??6.43%, respectively. These improved properties indicated that ZrO₂-C_f/SiC would be excellent alternatives to other existence materials under ultra-high temperature environments.     

Unveiling surface stability and oxygen diffusion of rare-earth zirconate pyrochlores by density functional theory

The surface structures, bond variations, and segregation of oxygen vacancies play crucial roles in the structural stability and functionality of nanocrystalline rare-earth zirconate pyrochlores. In this work, the stabilities of (1 0 0), (1 1 0), and (1 1 1) surfaces of pyrochlore A₂Zr₂O₇ (A = La, Ce, Pr, Nd, Pm, Sm, Eu, or Gd) are investigated by first-principles calculations. Surface reconstruction occurs on (1 1 0) surface with a transition of ZrO₆ octahedron to ZrO₄ tetrahedron, leading to their large relaxation energies. In combination with the small amount of broken bonds during the surface formation process, the (1 1 0) surfaces are identified having the lowest surface formation energies than the (1 0 0) and (1 1 1) surfaces. Moreover, the reconstructed (1 1 0) surface has characteristics of the segregation of oxygen vacancies. The surface oxygen vacancies have the low migration barriers (<1.2 eV), which are comparable with those in bulk and ensure the long-distance diffusion of oxygen vacancies in A₂Zr₂O₇. These discoveries provide fundamental insight to the surface structure and related oxygen vacancy behavior, which are expected to guide the optimization of the surface related properties for nanocrystalline rare-earth zirconates.     

Effects of graphene oxide sheets-zirconia spheres nanohybrids on mechanical,thermal and tribological performances of epoxy composites

In this work, graphene oxide sheets-zirconia spheres (ZrO₂-rGO) nanohybrids were fabricated by Schiff base or Michael addition reaction. Their structure was characterized by FT-IR spectroscopy, UV–vis absorption spectra, Raman spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy and atomic force microscope in detail. The reaction process of PDA-capping on rGO and APTES treatment on ZrO₂ nanoparticles were verified and it was proved that the ZrO₂ nanoparticles were successfully adhered onto the wrinkled surface of the graphene oxide. As a new multifunctional nanofillers, the ZrO₂-rGO nanohybrids were introduced into epoxy matrix and the mechanical, thermal properties and tribological performances of the fabricated composites were also detailedly investigated. Compared with the neat EP composites, the tensile strength and elongation at break of 0.1?wt% ZrO₂-rGO/EP are improved by 33% and 40%, respectively. Besides, the propagation of decomposition reactions in the composites could be impeded by anchoring ZrO₂ nanoparticles on the lamellar skeleton of graphene oxide. Furthermore, the lubricating effect and strong interfacial interaction contributed by the ZrO₂-rGO nanohybrids result in efficient load transfer from the matrix to the hybrids, which enables the ZrO₂-rGO/EP composites to have a fairly high wear resistance performance. This novel and effective approach using ZrO₂-rGO nanohybrids as multifunctional nanofillers could be beneficial to promote the development of high performance composites.     

Selective isopentane formation from CH3OH on a new one-atomic layer ZrO2/ZSM-5 hybrid catalyst

A new one-atomic layer ZrO₂/ZSM-5 hybrid catalyst was prepared by using the repeated reactions between Zr(OC₂H₅)₄ and of the OH groups of the external surfaces of ZSM-5, followed by calcination. The one-atomic layer ZrO₂ attached on the ZSM-5 surface was characterized by means of X-ray diffraction, X-ray fluorescence and EXAFS. The ZrO₂ overlayer is suggested to epitaxially grow on the ZSM-5(001) plane in a [111] direction of tetragonal ZrO₂. The one-atomic layer ZrO₂/ZSM-5 is a unique catalyst which produces selectively isopentane from CH₃OH.     

Monolayer dispersion of oxides and salts on surface of ZrO2 and its application in preparation of ZrO2-supported catalysts with high surface areas

The thermostability of ZrO₂ can be improved by dispersing a layer of an active component onto its surface in advance. The research results of seven kinds of catalysts (ZrO₂-supported MoO₃, WO₃, CuO, SO₄ ^2-, NiO, FeSO₄ and Fe₂O₃) show that the surface areas of the samples prepared by impregnating Zr(OH)₄ with the active components and then calcining at high temperature are much larger than those of the samples prepared with an ordinary method, namely, impregnating ZrO₂ calcined at high temperature. The surface areas of the ZrO₂-supported catalysts obtained in this way are several times that of pure ZrO₂ calcined at the same temperature. The characteristic results show: (1) the active components are dispersed on the surface of ZrO₂ as monolayer; (2) there is a good corresponding relationship between the surface coverage and the surface area of the sample; (3) as the loading of an active component comes up to its utmost dispersion capacity, the surface area of the sample will be the largest. The mechanism responsible for these phenomena has been discussed. This revised version was published online in July 2006 with corrections to the Cover Date.     

The role of fluorination during the physicochemical erosion of yttria in fluorine-based etching plasmas

A physicochemical mechanism acting between the reactive plasma and the material surface controls the erosion of polycrystalline ceramics in fluorine containing etching plasmas. In this study, a Y₂O₃/YOF composite was exposed to a fluorine etching plasma. Relocalization enables the direct correlation of crystalline orientation with material response. Our study reveals an orientation dependent surface fluorination of Y₂O₃, which controls the etching resistance and morphology formation. Orientations near the low index planes (001), (010) and (100) exhibit the lowest stability due to a homogeneous surface reaction. The presented results help to extend the mechanistic understanding of the plasma-material interaction of Y₂O₃.     

Trimerization of isobutene over WOx/ZrO2 catalysts

Trimerization of isobutene to produce isobutene trimers has been investigated over WO_x/ZrO₂ catalysts that were obtained by wet-impregnation and successive calcination at high temperatures. Very stable isobutene conversion and high selectivity for trimers are attained over a WO_x/ZrO₂ catalyst obtained by calcination at 700 °C. From the XRD study it can be understood that tetragonal ZrO₂ is beneficial for stable performance; however, monoclinic ZrO₂ is not good for trimerization. Nitrogen adsorption and FTIR experiments suggest that amorphous WO_x/ZrO₂ is inefficient catalyst even though it has high surface area and high concentration of acid sites. The observed performance with the increased selectivity and stable conversion demonstrates that a WO_x/ZrO₂ having tetragonal zirconia, even with decreased porosity and acid sites, is one of the best catalysts to exhibit stable and high conversion, high selectivity for trimers and facile regeneration.     

Mass transfer effects on ZrO2 oxygen concentration cells exposed to non-equilibrium H2-O2 mixtures

We report further studies of ZrO₂ oxygen concentration cells exposed to non-equilibrium gas mixtures. Substantial shifts of cell voltage-(H₂/O₂) composition curves are produced by changes in the gas flow rate past the cell. At high flow rates, there is an abrupt voltage step at about 2.2 times the H₂/O₂ stoichiometric ratio. At low flow rates this voltage step occurs at stoichiometry. These findings are understood on the basis of mass transfer to a heterogeneous catalyst/electrode surface.     

Photoinduced activation of CO2 on TiO2 surfaces: Quantum chemical modeling of CO2 adsorption on oxygen vacancies

Chemical processes that utilize CO₂ emissions from coal-fired power plants will be required as the world progresses towards reducing CO₂ emissions. The conversion of CO₂ using light energy (CO₂ photoreduction) has the potential to produce useful fuels or valuable chemicals while decreasing CO₂ emissions from the use of fossil fuels such as coal. Computational studies on the initial steps of photoinduced CO₂ activation on TiO₂ surfaces, necessary to develop a mechanistic understanding of CO₂ photoreduction are a focus of this article.The results from previous quantum mechanical modeling studies conducted by the authors indicated that stoichiometric TiO₂ surfaces likely do not promote electron transfer to CO₂. Therefore, the role of oxygen vacancies in promoting the light-induced conversion of CO₂ (CO₂ photoreduction) on TiO₂ surfaces was examined in this study. Two different side-on bonded bent-CO₂ (bridging Ti-CO₂^δ•−-Ti species) were formed on the reduced rutile (110) and anatase (010), (001) surfaces, indicating charge transfer from the reduced surface to CO₂. Further steps in the photoexcitation of these bent-CO₂ species were investigated with density functional theory calculations. Consistent with CO₂ adsorption and photodesorption on other n-type metal oxides such as ZrO₂, the results suggest that the bent-CO₂ species do not gain further charge from the TiO₂ surface under illumination and are likely photodesorbed as neutral species. Additionally, although the formation of species such as CO and HCHO is thermodynamically possible, the energy needed to regenerate the oxygen vacancy on TiO₂ surfaces (~ 7 eV) is greater than that available through band-gap illumination (3.2 eV). Therefore, CO₂ reactions with water on irradiated anatase TiO₂ surfaces are likely to be stoichiometric.     

The relationship between the structure and catalytic performance Cu/ZnO/ZrO2 catalysts for hydrogenation of dimethyl 1,4-cyclohexane dicarboxylate

The gas-phase hydrogenation of dimethyl 1,4-cyclohexane dicarboxylate to 1,4-cyclohexane dimethanol (CHDM) was conducted on well-dispersed supported Cu/ZnO/ZrO₂ catalysts. The results indicated that the structure and catalytic performance of resulting copper-based catalysts were profoundly affected by the addition of zirconium. Moreover, the as-synthesized catalyst with 35.0 wt.% ZrO₂ component was found to exhibit superior catalytic performance with a high CHDM yield of 96.8% to other catalysts, which should be mainly attributed to the significant dispersion effect of ZrO₂ on the copper-containing species resulting in a higher metallic copper surface area as well as a larger number of Cu⁺ species.     

Bipolar resistive switching behavior and conduction mechanisms of composite nanostructured TiO2/ZrO2 thin film

In this work, TiO₂/ZrO₂ bilayer thin film was prepared on fluorine doped tin oxide (FTO)/glass substrates by using a simple and low-cost chemical solution deposition method. Reproducible bipolar resistive switching (RS) characteristics in Au/TiO₂/ZrO₂/FTO/glass devices are reported in this work. TiO₂/ZrO₂ bilayer thin films prepared in this work shows reversible bipolar resistive switching and unidirectional conduction performances under applying voltage and these special performances of TiO₂/ZrO₂ bilayer thin films was first reported. Obvious resistive switching performance can be observed after setting a compliance current, the ratio of high/low resistance reached about 100 at a read voltage of +0.1V and −0.1V and the RS properties showed no obvious degradation after 100 successive cycles tests. The resistive switching characteristics of Au/TiO₂/ZrO₂/FTO/glass device can be explained by electron trapping/detrapping related with the vacancy oxygen defects in TiO₂/ZrO₂ bilayer thin film layer. According to slope fitting, the main conduction mechanisms of the sample are Ohmic and Space charge limited current mechanism.     

Properties and in vitro assessment of ZrO2-based coatings obtained by atmospheric plasma jet spraying on biodegradable Mg-Ca and Mg-Ca-Zr alloys

Magnesium (Mg)-based biodegradable alloys have gained a major interest in the biomedical field. The advantages of Mg alloys are depicted by their high biocompatibility, easy biodegradation and satisfactory mechanical properties. However, one major disadvantage of these alloys is represented by their low corrosion resistance in physiological environment. Coatings are considered to be a viable alternative used to improve corrosion, mechanical and cell viability properties of Mg- based metallic alloys. In this paper, two types of ceramic coating materials ZrO₂-Y₂O₃ and ZrO₂-CaO were deposited on Mg-Ca and Mg-Ca-Zr substrates by the atmospheric plasma jet technique. The two types of the deposited coatings exhibit similar Young modulus and a hardness in the range of 0.2–0.4 GPa. Values of the elastic modulus for the layers were measured to be in the range of 11–27 GPa for ZrO₂-Y₂O₃ and of 16–31 GPa for ZrO₂-CaO. The corrosion rate for the ZrO₂-CaO coating has superior values than that for the ZrO₂-Y₂O₃ one. The ZrO₂-CaO coated samples present a better adhesion to the substrate. The MTT colorimetric tests (3-(4,5-dimethyl-thiazol–2-yl)-2,5-diphenyl tetrazolium bromide) did not reveal significant differences in cytocompatibility between the two types of coatings, presenting a moderate cell viability.     

Carbon dioxide reforming of methane over Co-X/ZrO2 catalysts (X = La,Ce, Mn,Mg, K)

Dry reforming of methane has been studied over Co/ZrO₂ catalysts promoted with different metal additives (La, Ce, Mn, Mg, K) aiming to improve the performance of the catalysts and increase their resistance to coking. Scanning electron microscopy studies and different activity levels of the catalysts clearly show that the type of the promoter significantly affected the metal dispersion properties and catalytic performances of Co/ZrO₂ catalysts. La-modified catalyst exhibited high stability, but moderate activity. It showed no severe coke deposition. Ce-doped Co/ZrO₂ displayed the highest activity among all the catalysts prepared and had a very limited activity loss.     

Improved tribological and thermo-mechanical properties of epoxy resin with micro-nano structured ZrO2/Ti3C2 particles

Inherent brittleness and poor wear resistance of epoxy resin severely restricts its practical application in many applications. In this present, a micro-nano structured ZrO₂/Ti₃C₂ particle was employed to improve the tribological and thermo-mechanical properties of epoxy resin. The micro-nano structured ZrO₂/Ti₃C₂ particles are synthesized by hydrothermal growth of nano-ZrO₂ onto the surface of accordion-like Ti₃C₂, and the ZrO₂/Ti₃C₂/epoxy composites are fabricated by solution blending and curing reaction. The surface morphology of ZrO₂/Ti₃C₂ particles and the fracture surface of ZrO₂/Ti₃C₂/epoxy composites were investigated. Test results indicated that the wear rate, storage modulus and glass transition temperature of epoxy resin is effectively improved by incorporation of ZrO₂/Ti₃C₂ particles, maybe ascribing to the strong interfacial interaction between micro-nano structured ZrO₂/Ti₃C₂ and epoxy matrix. In addition, the wear mechanism of ZrO₂/Ti₃C₂/epoxy composites were further revealed by analyzing their worn surfaces and wear debris. This work provides a promising strategy for improving the tribological and thermo-mechanical properties of epoxy.     

Room-temperature UV-ozone assisted solution process for zirconium oxide films with high dielectric properties

A facile, low-cost, and room-temperature UV-ozone (UVO) assisted solution process was employed to prepare zirconium oxide (ZrO_x) films with high dielectric properties. ZrO_x films were deposited by a simple spin-coating of zirconium acetylacetonate (ZrAcAc) precursor in the environment-friendly solvent of ethanol. The smooth and amorphous ZrO_x films by UVO exhibit average visible transmittances over 90% and energy bandgap of 5.7 eV. Low leakage current of 6.0 × 10⁻⁸ A/cm² at 3 MV/cm and high dielectric constant of 13 (100 Hz) were achieved for ZrO_x dielectrics at the nearly room temperature. Moreover, a fully room-temperature solution-processed oxide thin films transistor (TFT) with UVO assisted ZrO_x dielectric films achieved acceptable performances, such as a low operating voltage of 3 V, high carrier mobility of 1.65 cm² V⁻¹ s⁻¹, and on/off current ratio about 10⁴–10⁵. Our work indicates that simple room-temperature UVO is highly potential for low-temperature, solution-processed and high-performance oxide films and devices.     

Electron Paramagnetic Resonance investigation of the nature of active species involved in carbon black oxidation on ZrO2 and Cu/ZrO2 catalysts

To identify the nature of active paramagnetic species involved in the carbon black (CB) oxidation, an Electron Paramagnetic Resonance (EPR) study of (CB–ZrO₂) and (CB–Cu/ZrO₂) loose contact mixtures treated under argon flow has been undertaken. In the presence of pure zirconia catalysts, it was found that ZrO₂ interacts with CB and can be reduced into Zr³⁺ formed in tetragonal phase of this oxide support. In parallel, several EPR signals assigned to carbonaceous radicals were detected: i) carbonaceous radicals on CB surface, ii) radicals located at the CB–ZrO₂ interface and iii) oxygen deficit carbonaceous radicals observed at high treatment temperature. The carbonaceous signals disappeared completely after CB oxidation in agreement with a regeneration of the catalyst treated under air.For copper supported on zirconia catalysts, oxygen surrounding isolated Cu(II) species and oxygen from tetragonal ZrO₂ lattice are involved in carbon black oxidation. The phenomenon is reversible and this catalyst is also regenerated by air. Carbonaceous radical signals were also observed for (CB–Cu/ZrO₂) mixture and their intensity decrease versus temperature appeared in good agreement with the better activity of Cu/ZrO₂ compared to pure ZrO₂.