Hematite (α-Fe2O3) with Oxygen Defects: The Effect of Heating Rate for Photocatalytic Performance.

Hematite (α-Fe2O3) emerges as an enticing material for visible-light-driven photocatalysis owing to its remarkable stability, low toxicity, and abundance. However, its inherent shortcomings, such as a short hole diffusion length and high recombination rate, hinder its practical application. Recently, oxygen vacancies (Vo) within hematite have been demonstrated to modulate its photocatalytic attributes. The effects of Vo can be broadly categorized into two opposing aspects: (1) acting as electron donors, enhancing carrier conductivity, and improving photocatalytic performance and (2) acting as surface carrier traps, accelerating excited carrier recombination, and deteriorating performance. Critically, the generation rate, distribution, role, and behavior of Vo significantly differ for synthesis methods due to differences in formation mechanisms and oxygen diffusion. This complexity hampers simplified discussions of Vo, necessitating careful investigation and nuanced discussion tailored to the specific method and conditions employed. Among various approaches, hydrothermal synthesis offers a simple and cost-effective route. Here, we demonstrate a hydrothermal synthesis method for Vo introduction to hematite using a carbon source, where variations in the heating rate have not been previously explored in terms of their influence on Vo generation. The analyses revealed that the concentration of Vo was maximized at a heating rate of 16 °C/min, indicative of a high density of surface defects. With regard to photocatalytic performance, elevated heating rates (16 °C/min) fostered the formation of Vo primarily on the hematite surface. The photocatalytic activity was 7.1 times greater than that of the sample prepared at a low heating rate (2 °C/min). These findings highlight the crucial role of surface defects, as opposed to bulk defects, in promoting hematite photocatalysis. Furthermore, the facile control over Vo concentration achievable via manipulating the heating rate underscores the promising potential of this approach for optimizing hematite photocatalysts.

Electronic strengthening mechanism of covalent Si via excess electron/hole doping.

Brittle fracture of a covalent material is ultimately governed by the strength of the electronic bonds. Recently, attempts have been made to alter the mechanical properties including fracture strength by excess electron/hole doping. However, the underlying mechanics/mechanism of how these doped electrons/holes interact with the bond and changes its strength is yet to be revealed. Here, we perform first-principles density-functional theory calculations to clarify the effect of excess electrons/holes on the bonding strength of covalent Si. We demonstrate that the bond strength of Si decreases or increases monotonically in correspondence with the doping concentration. Surprisingly, change to the extent of 30-40% at the maximum feasible doping concentration could be observed. Furthermore, we demonstrated that the change in the covalent bond strength is determined by the bonding/antibonding state of the doped excess electrons/holes. In summary, this work explains the electronic strengthening mechanism of covalent Si from a quantum mechanical point of view and provides valuable insights into the electronic-level design of strength in covalent materials.