Low-Temperature Catalytic CO₂ Dry Reforming of Methane on Ni-Si/ZrO₂ Catalyst

The activity of a ZrO₂-supported nickel catalyst promoted by silica (Ni-Si/ZrO₂) in CO₂ dry reforming of methane was carried out at 400 and 450 °C. The catalysts were prepared by an impregnation method and characterized by H₂-TPR, XRD, TEM, TG-MS, Raman, XPS, and in situ XPS and DRIFTS. It was discovered that Ni-Si/ZrO₂ showed higher initial conversion of CH₄ (0.50 s^–1) and CO₂ (0.44 s^–1), and stability for low temperature (400 °C) DRM reaction in comparison to an SiO₂-supported nickel catalyst promoted by zirconia (Ni-Zr/SiO₂) (0.32 s^–1 for both CO₂ and CH₄). The Ni-Si/ZrO₂ catalyst featured the formation of active nickel particles with a small size of 6–9 nm and with slightly strong electronic donor ability, stabilization of the initial metal nickel state under the reaction conditions, and the formation of easily removed C₁ coke. However, for the 450 °C DRM reaction, the coke that formed on the Ni-Si/ZrO₂ catalyst was mainly C₂ coke that was difficult to remove, because the CO₂ preferred to combine with H species rather than react with the coke. For the Ni-Zr/SiO₂ catalyst, the Ni⁰ species was oxidized to a NiO species under the reaction conditions at 400 °C and could not be restored, leading to its deactivation

Chemical Space Covered by Applicability Domains of Quantitative Structure–Property Relationships and Semiempirical Relationships in Chemical Assessments

A significant number of chemicals registered in national and regional chemical inventories require assessments of their potential “hazard” concerns posed to humans and ecological receptors. This warrants knowledge of their partitioning and reactivity properties, which are often predicted by quantitative structure–property relationships (QSPRs) and other semiempirical relationships. It is imperative to evaluate the applicability domain (AD) of these tools to ensure their suitability for assessment purpose. Here, we investigate the extent to which the ADs of commonly used QSPRs and semiempirical relationships cover seven partitioning and reactivity properties of a chemical “space” comprising 81,000+ organic chemicals registered in regulatory and academic chemical inventories. Our findings show that around or more than half of the chemicals studied are covered by at least one of the commonly used QSPRs. The investigated QSPRs demonstrate adequate AD coverage for organochlorides and organobromines but limited AD coverage for chemicals containing fluorine and phosphorus. These QSPRs exhibit limited AD coverage for atmospheric reactivity, biodegradation, and octanol–air partitioning, particularly for ionizable organic chemicals compared to nonionizable ones, challenging assessments of environmental persistence, bioaccumulation capability, and long-range transport potential. We also find that a predictive tool’s AD coverage of chemicals depends on how the AD is defined, for example, by the distance of a predicted chemical from the centroid of the training chemicals or by the presence or absence of structural features