Researchers used advanced microscopy techniques to watch mesocrystals form in real-time. Image: Mike Perkins/Pacific Northwest National Laboratory.When materials reach extremely small size scales, strange things begin to happen. One of those strange things is the formation of mesocrystals.
Despite being composed of separate individual crystals, mesocrystals come together to form a larger, fused structure that behaves as a pure, single crystal. However, these processes happen at scales far too small for the human eye to see and their creation is extremely challenging to observe. Because of these challenges, scientists had not been able to confirm exactly how mesocrystals form.
Now, a team led by researchers at Pacific Northwest National Laboratory (PNNL) has used advanced transmission electron microscopy (TEM) techniques to see mesocrystals form in solution in real time. What they saw runs contrary to conventional wisdom, and their insights could one day help scientists design materials for energy storage and understand how minerals in soil form.
Rather than individual crystals nucleating, which is the first step in crystal formation, and then randomly aggregating into mesocrystals in two unrelated steps, the researchers observed that nucleation and attachment were closely coupled in forming these highly uniform structures. The researchers report their findings in a paper in Nature.
"Our findings identify an important new pathway of crystallization by particle attachment and resolve key questions about mesocrystal formation," said Guomin Zhu, a materials scientist at PNNL and the University of Washington. "We suspect this is a widespread phenomenon with significant implications both for the synthesis of designed nanomaterials and for understanding natural mineralization." Zhu was part of a research team led by Jim De Yoreo, PNNL materials scientist and co-director of the Northwest Institute for Materials Physics, Chemistry, and Technology.
The project took years to execute and required significant problem solving. For the microscopy experiments, the scientific team chose a model crystal system that included hematite, an iron compound commonly found in the Earth's crust, and oxalate, a naturally abundant compound in soil.
They visualized the hematite crystallization process using in situ TEM, which gives researchers the ability to see crystallization at the nanometer scale as it happens. They combined this real-time method with 'freeze-and-look' TEM, which allowed them to follow an individual crystal at different points during its growth. Theoretical calculations helped complete the picture, allowing the PNNL team to piece together how the mesocrystals grew.
Researchers generally run most in situ TEM experiments at room temperature to simplify the experimental setup and minimize the potential for damaging the sensitive instrument, but mesocrystal formation rapid enough to observe occurs at around 80°C.
"The additional equipment used to heat the samples made the experiments extremely challenging, but we knew the data would be key to understanding how the mesocrystals were forming," said Zhu. Once heated, the new hematite nanocrystals rapidly attach together, which leads, on average, to final mesocrystals of approximately the same size and shape.
The chemical key to this rapid, reliable attachment is the oxalate molecules present in the solution. After the first few small crystals form, the oxalate additives help create a chemical gradient at the interface of the liquid and the growing crystal. More chemical components necessary for particle nucleation linger near the crystals, which dramatically increases the likelihood that new particles will form near existing ones.
While the researchers observed this crystal growth pathway in controlled conditions at very small scales, they say it likely also occurs in natural systems. Some mineral deposits, including an Australian hematite deposit, contain mesocrystals. Given the natural abundance of oxalate and the PNNL team's observation that hematite can become mesocrystals at temperatures as low as 40°C, it seems plausible that this formation route occurs in nature.
Because mesocrystals are found throughout nature, these findings can be applied to understanding nutrient cycling in the environment, among other applications. Moreover, the route to creating near-uniform complex structures requires an understanding of how methods for forming such materials work and how to control them. Thus, this work also opens new possibilities for intentionally creating mesocrystals or mesocrystal-like materials.
This story is adapted from material from Pacific Northwest National Laboratory, with editorial changes made by Materials Today. The views expressed in this article do not necessarily represent those of Elsevier. Link to original source.