Density functional theory study on the electronic structure of \u3ci\u3en\u3c/i\u3e- and \u3ci\u3ep\u3c/i\u3e-type doped SrTiO\u3csub\u3e3\u3c/sub\u3e at anodic solid oxide fuel cell conditions

The electronic conductivity and thermodynamic stability of mixed n-type and p-type doped SrTiO3 have been investigated at anodic solid oxide fuel cell (SOFC) conditions using density functional theory (DFT) calculations. In particular, constrained ab initio thermodynamic calculations have been performed to evaluate the phase stability and reducibility of various Nb- and Ga-doped SrTiO3 at synthesized and anodic SOFC conditions. The density of states (DOS) of these materials was analyzed to study the effects of n- and p-doping on the electronic conductivity. In agreement with experimental observations, we find that the transformation from 20% Nb-doped Sr-deficient SrTiO3 to a non-Sr-deficient phase occurs at high temperature and low oxygen partial pressure, which leads to a significant improvement in electronic conductivity. A mixed ionic/electronic conductor is obtained when doping 20% Nb-doped SrTiO3 with small amounts of Ga (10%) in a reducing environment and high temperature. Doping with higher concentrations of Ga, e.g., 20%, diminishes the electronic conductivity of the material. These findings suggest that independent of the specific dopant, mixed ionic/electronic conductivity can be obtained in perovskite oxides under reducing conditions and high temperatures by doping the B-site with small amounts of both n-type and p-type dopants

Photocatalytic NOₓ oxidation of BiOCl nanostructure-based films grown using aerosol-assisted chemical vapor deposition

Coating of photocatalytic nanomaterials on various surfaces enables interesting applications. This work demonstrates the ability of the aerosol-assisted chemical vapor deposition (AACVD) approach to prepare high-quality BiOCl nanostructure-based films and also to tune the nanostructure and photocatalytic properties of the films by varying the solvent and carrier gas. Solvents have a dramatic impact on the surface morphologies and crystallite size. X-ray diffraction (XRD) and grazing incidence X-ray diffraction (GIXRD) analyses indicate that BiOCl crystals displayed preferential growth in the (101) plane in most samples, while both the (101) and (102) planes were favored in films deposited using ethyl acetate and methanol. Surface energy and adsorption energy calculation reveal that the preferred growth depends on the interaction between the Bi atom and solvent molecules. X-ray photoelectron spectroscopy (XPS) and energy-dispersive X-ray spectroscopy (EDS) characterizations showed that all films did not contain any impurity elements but did contain some oxygen vacancies. The obtained nanostructured BiOCl films show good photocatalytic properties. The highest photocatalytic NOx removal efficiency is achieved in the film prepared using ethyl acetate and air, which we attribute to the large crystallite size and therefore high mobility of the carriers. Herein, we show that different crystal morphologies and sizes of BiOCl have strong impacts on the photocatalytic activity toward NO oxidation, and both factors can be effectively tuned in the AACVD process. Such knowledge may be useful for future research on coating materials for resolving environmental problems

Ecofriendly alkali metal cations diffusion improves fabrication of mixed-phase titania polymorphs on fixed substrate by chemical vapor deposition (CVD) for photocatalytic degradation of azo dye

Controlling the nanoscale synthesis of semiconductor TiO2 on a fixed substrate has fascinated the curiosity of academics for decades. Synthesis development is required to give an easy-to-control technique and parameters for TiO2 manufacture, leading to advancements in prospective applications such as photocatalysts. This study, mixed-phase TiO2(B)/other titania thin films were synthesized on a fused quartz substrate utilizing a modified Chemical vapor depodition involving alkali-metal ions (Li+, Na+, and K+) solution pre-treatment. It was discovered that different cations promote dramatically varied phases and compositions of thin films. The films had a columnar structure with agglomerated irregular-shaped particles with a mean thickness of 800–2000 nm. Na+ ions can promote TiO2(B) more effectively than K+ ions, however Li+ ions cannot synthesize TiO2(B). The amounts of TiO2(B) in thin films increase with increasing alkali metal (K+ and Na+) concentration. According to experimental and DFT calculations, the hypothesized TiO2(B) production mechanism happened via the meta-stable intermediate alkaline titanate transformation caused by alkali-metal ion diffusion. The mixed phase of TiO2(B) and anatase TiO2 on the fixed substrate (1 × 1 cm2) obtained from Na+ pre-treated procedures showed significant photocatalytic activity for the degradation of methylene blue. K2Ti6O12, Li2TiO3, Rutile TiO2, and Brookite TiO2 phase formations produced by K+ and Li + pretreatment are low activity photocatalysts. Photocatalytic activities were more prevalent in NaOH pre-treated samples (59.1% dye degradation) than in LiOH and KOH pre-treated samples (49.6% and 34.2%, respectively). This revealed that our developed CVD might generate good photocatalytic thin films of mixed-phase TiO2(B)/anatase TiO2 on any substrate, accelerating progress in future applications

Theoretical Investigation of H2Oxidation on the Sr2Fe1.5Mo0.5O6(001) Perovskite Surface under Anodic Solid Oxide Fuel Cell Conditions

Periodic density functional theory (DFT) calculations and microkinetic modeling are used to investigate the electrochemical oxidation of H2 fuel on the (001) surface of Sr2Fe1.5Mo 0.5O6 (SFMO) perovskite under anodic solid oxide fuel cell conditions. Three surface models with different Fe/Mo ratios in the topmost layer-identified by ab initio thermodynamic analysis-are used to investigate the H2 oxidation mechanism. A microkinetic analysis that considers the effects of anode bias potential suggests that a higher Mo concentration in the surface increases the activity of the surface toward H2 oxidation. At operating voltage and anodic SOFC conditions, the model predicts that water desorption is rate-controlling and that stabilizing the oxygen vacancy structure increases the overall rate for H2 oxidation. Although we find that Mo plays a crucial role in improving catalytic activity of SFMO, under fuel cell operating conditions, the Mo content in the surface layer tends to be very low. On the basis of these results and in agreement with previous experimental observations, a strategy for improving the overall electrochemical performance of SFMO is increasing the Mo content or adding small amounts of an active transition metal, such as Ni, to the surface to lower the oxygen vacancy formation energy of the SFMO surface