Real-Time Multiscale Imaging of Heterogeneous Multistage Reactions: Insights into Nanoscale TiO2 Synthesis.

Hydrothermal methods are widely used to synthesize functional inorganic materials. The interplay between the reactive species, solution chemistry, and the nanoscale product makes it challenging to control the reaction pathway to achieve a uniform product. Here, we resolve the heterogeneity that arises during hydrothermal synthesis across different length scales. We combine spatially resolved in situ X-ray pair distribution function (PDF) and small-angle X-ray scattering analysis, which are sensitive to structure on the atomic and nanoscale, with a novel time-lapse optical imaging strategy that reveals heterogeneity and phase separations across the entire reaction. For TiO2 synthesis via hydrothermal hydrolysis of TiCl4, we identify multiple cycles of TiO2 formation and separation that contribute to nonuniformity in the polymorphic product. The PDF data show that the characteristics of TiO2 formed during each formation-separation cycle differ, contributing to the ongoing challenge of precisely identifying reaction controls. The imaging strategy pioneered here provides an efficient in situ means to systematically compare how the reaction evolves under different chemical conditions, thereby advancing our understanding of functional inorganic material synthesis.

Resolving Fast Relative Kinetics in Inorganic Solid-State Synthesis.

Solid-state syntheses are generally regarded as being slow, limited by transport, and, as such, are often only stopped to check the products after many hours at high temperature. Here, using a custom-designed reactor to rapidly initiate solid-state syntheses, we are able to capture the earliest stages of a reaction using in situ X-ray scattering. For the reaction of TiO2 and Li2CO3 to form spinel lithium titanate (Li4Ti5O12)─an anode material for fast-charging applications─we capture two distinct kinetic regimes, including fast initial kinetics in the first seconds-minutes of the reaction that account for significant product formation. We use an Avrami model to compare the reaction at high temperatures (700-750 °C), which results in the rapid formation of Li4Ti5O12 within minutes, and lower temperatures (482 °C), consistent with conditions that might be chosen based on "Tamman's rule", a common heuristic. Our analysis reveals characteristic Avrami slopes (i.e., dimensionalities) for each step in the chemical transformation. We anticipate that the fast initial reaction kinetics found here are likely to be common in the synthesis of other materials used in battery electrodes, solid-state electrolytes, ion-conductive membranes, etc. where ion transport is a prerequisite for functionality.