Search

Hematite nanostructures are strong candidates for the development of sustainable water splitting technologies. However, major challenges exist in improving charge density and minimizing charge recombination rates for a competitive photoelectrochemical performance based on hematite without compromising sustainability aspects. Here we develop a synthetic strategy to leverage earth-abundant Al3+ and Zr4+ in a dual-chemical modification to synergistically minimize small polaron effects and interfacial charge recombination. The solution-based method simultaneously induces Al3+ doping of the hematite crystal lattice while Zr4+ forms interfacial excess, creating a single-phased homogeneous nanostructured thin film. The engineered photoanode increased photocurrent from 0.7 mA cm−2 for pristine hematite up to 4.5 mA cm−2 at 1.23 V and beyond 6.0 mA cm−2 when applying an overpotential of 300 mV under simulated sunlight illumination (100 mW cm−2). The results demonstrate the potential of dual-modification design using solution-based processes to enable sustainable energy technologies. [ABSTRACT FROM AUTHOR]

Interface segregation plays a governing role in nanocrystalline ceramics properties due to the relative increase in the interfacial volume fraction. However, due to the complexity of the detection and quantification of interfacial excesses at the nanoscale, the role of ionic dopants or additives on microstructural evolution and thermodynamics can be easily underestimated. In this work, we address the spatial distribution of Li+ as a dopant in magnesium aluminate spinel nanoparticles. This is achieved through a novel method for the detection and quantification of Li+ across the surface, grain boundary, and bulk (crystal lattice). Based on selective lixiviation combined with chemical analysis, we were able to quantify the amount of Li+ forming surface excess, whereas the quantitative solid‐state nuclear magnetic resonance technique enabled the quantification of Li+ segregated in the grain boundaries and dissolved in the lattice. This comprehensive understanding of the Li+ distribution across the nanoparticles makes possible an unprecedented interpretation of coarsening and sintering, with a clear correlation between the microstructure and the Li+ distribution. Although the work focuses on MgAl2O4, the proposed combination of techniques is expected to have a positive impact on the understanding of other multicomponent nanoscale systems. [ABSTRACT FROM AUTHOR]

The increase in hardness with decreasing grain size is a well‐established size effect known as the Hall‐Petch relationship. In ceramics, there has been controversy surrounding the existence of a low size limit below which size‐induced hardening no longer occurs and softening is observed instead. Here, this so‐called inverse Hall‐Petch relationship was observed in quasi‐stoichiometric dense nanocrystalline zinc aluminate while an extension of the normal Hall‐Petch behavior was demonstrated by Al‐rich zinc aluminate nanoceramics. Vickers hardness increased with grain refinement for quasi‐stoichiometric samples prepared by High Pressure Spark Plasma Sintering, exhibiting a maximum of 18.6 GPa at a grain size of 21.4 nm. Conversely, Al‐rich zinc aluminate produced by the same technique strengthened up to 19.2 GPa at 12.6 nm grain sizes. Cross‐sections of Vickers indentation imprints showed that while quasi‐stoichiometric zinc aluminate showed a change in sub‐surface cracking pattern from larger to smaller grain sizes (before and after the inverse Hall‐Petch), the Al‐rich samples had sub‐surface cracking similar to those found in large grain sizes in quasi‐stoichiometric samples. These results suggest that softening at small grain sizes is driven by the activation of shear and fracture at weak grain boundaries which can be mitigated by Al enrichment. [ABSTRACT FROM AUTHOR]

This work investigates the effects of doping on both the thermodynamics and kinetics of sintering in aluminum‐doped yttrium oxide nanoparticles (Al‐doped Y2O3), with the objective of delineating their interdependent effects at different stages of the process. Direct measurements of surface and grain boundary energies using differential scanning calorimetry showed that Al‐doping decreases both interfacial energies, leading to an increase in dihedral angle (from 152.7 ± 5.6° to 165.8 ± 5.5°) and, therefore, sintering stress. Densification and grain growth analyses showed that despite this increase in sintering stress, the onset of sintering is delayed for the Al‐doped samples, demonstrating that a large dihedral angle is a necessary but not sufficient condition for densification. The measurements of activation energies for densification and grain growth point out that Al suppresses grain boundary mobility by increasing the activation energy from 400 to 448 kJ/mol, hindering densification at the intermediate stages of sintering. At temperatures above 1150℃, grain growth is activated in the Al‐doped samples, which rapidly releases the accumulated sintering stress and exhibits a higher densification rate than in undoped Y2O3. This study demonstrates a complex interconnectivity between the thermodynamics and kinetics at different temperature ranges of sintering and reinforces the need for a comprehensive description for proper design of sintering aids. [ABSTRACT FROM AUTHOR]

Surface energy (γS) and grain boundary energy (γGB) of yttrium oxide (Y2O3) were determined by analyzing the heat of sintering (ΔHsintering) using differential scanning calorimetry (DSC). The data allowed quantification of sintering driving forces, which when combined with a thorough kinetic analysis of the process, provide better understanding of Y2O3 densification as well as insights into effective strategies to improve its sinterability. The quantitative thermodynamic study revealed moderate thermodynamic driving force for densification in Y2O3 (as compared to other oxides) represented by a dihedral angle of 152.7° calculated from its surface and grain boundary energies. The activation energy was determined as 307 ± 61 kJ/mol, consistent with activation energies previously reported for processes relevant to sintering of Y2O3, such as Y3+ diffusion and grain boundary mobility. Finally, we propose that a refined deconvolution study on the DSC curve for Y2O3 sintering, combined with the associated material's microstructure evolution, may help identify shifts in sintering mechanisms, and therefore, specific activation energies at increasing temperatures. [ABSTRACT FROM AUTHOR]

Surface energy (γS) and grain boundary energy (γGB) of yttrium oxide (Y2O3) were determined by analyzing the heat of sintering (ΔHsintering) using differential scanning calorimetry (DSC). The data allowed quantification of sintering driving forces, which when combined with a thorough kinetic analysis of the process, provide better understanding of Y2O3 densification as well as insights into effective strategies to improve its sinterability. The quantitative thermodynamic study revealed moderate thermodynamic driving force for densification in Y2O3 (as compared to other oxides) represented by a dihedral angle of 152.7° calculated from its surface and grain boundary energies. The activation energy was determined as 307 ± 61 kJ/mol, consistent with activation energies previously reported for processes relevant to sintering of Y2O3, such as Y3+ diffusion and grain boundary mobility. Finally, we propose that a refined deconvolution study on the DSC curve for Y2O3 sintering, combined with the associated material's microstructure evolution, may help identify shifts in sintering mechanisms, and therefore, specific activation energies at increasing temperatures. [ABSTRACT FROM AUTHOR]

The process of CO2 and H2O adsorption on the surface of nano-oxide semiconductors is important in the overall performance of artificial photosynthesis and other applications. In this study, we explored the thermodynamics of CO2 and H2O adsorption on TiO2 as a function of surface chemistry. We applied gas adsorption calorimetry to investigate the energetics of adsorption of those molecules on the surface of anatase nanoparticles. In an attempt to increase TiO2 surface affinity to CO2 and H2O, TiO2 was doped with alkaline earth metals (MgO, CaO, SrO, and BaO) by manipulating the chemical synthesis. Adsorption studies using diffuse reflectance infrared spectroscopy at different temperatures indicate that due to the segregation of alkaline earth metals on the surface of TiO2 nanoparticles, both CO2 and subsequent H2O adsorption amounts could be increased. CO2 adsorbs in two different manners, forming carbonates which can be removed at temperatures lower than 700 °C, and a more stable linear adsorption that remains even at 700 °C. Additionally to the surface energetic effects, doping also increased specific surface area, resulting in further improvement in net gas adsorption. [ABSTRACT FROM AUTHOR]

A straight-forward set of experiments using differential scanning calorimetry was used to obtain the average grain boundary enthalpy at high temperatures for 10 mol. % yttria-stabilized zirconia (10YSZ) by exploiting the heat of grain growth on nanograined dense samples consolidated by spark plasma sintering. The heat of grain growth was measured and correlated with the quantified microstructure evolution during the process. The average grain boundary enthalpy of 10YSZ was found to be 1.00 ± 0.29 J m-2 for the temperature range 900-1300 °C. Comparing this result with room temperature data in the literature, small temperature dependence of the grain boundary enthalpy could be found outside the experimental uncertainties in both experiments. [ABSTRACT FROM AUTHOR]