Connecting energetics to dynamics in particle growth by oriented attachment using real-time observations

Abstract

The interplay between crystal and solvent structure, interparticle forces and ensemble particle response dynamics governs the process of crystallization by oriented attachment (OA), yet a quantitative understanding is lacking. Using ZnO as a model system, we combine in situ TEM observations of single particle and ensemble assembly dynamics with simulations of interparticle forces and responses to relate experimentally derived interparticle potentials to the underlying interactions. We show that OA is driven by forces and torques due to a combination of electrostatic ion-solvent correlations and dipolar interactions that act at separations well beyond 5 nm. Importantly, coalignment is achieved before particles reach separations at which strong attractions drive the final jump to contact. The observed barrier to attachment is negligible, while dissipative factors in the quasi-2D confinement of the TEM fluid cell lead to abnormal diffusivities with timescales for rotation much less than for translation, thus enabling OA to dominate.

Selective Homoepitaxial Growth of ZnO Layers on c(+)-Surface by Solvothermal Reaction in Water–Ethylene Glycol Solvent

“…Similar oriented growth of attachments has been reported for various inorganic materials, such as TiO 2 , 31 , 32 FeOOH, 33 and ZnO. 34 − 36 It is considered that Brownian motion may allow adjacent particles to rotate to find assume a low-energy configuration represented by a coherent particle–particle interface. 32 A dipole–dipole interaction would enhance the attachment.…”

Recent Advances in Electrochemical CO2 Reduction on Indium‐Based Catalysts

“…On the other hand, it has been widely accepted that the catalyst morphology could undergo dynamic reconstructions under operational conditions. [80][81][82] Therefore, it is essential to investigate the Reproduced with permission. [56] Copyright 2018, Elsevier.…”

“…Controllable synthesis of indium‐based catalysts, as well as the elucidation of their structure‐activity relationships, are important and emerging research directions. On the other hand, it has been widely accepted that the catalyst morphology could undergo dynamic reconstructions under operational conditions [80–82] . Therefore, it is essential to investigate the reconstruction process of the catalysts during activation, reaction and deactivation steps.…”

Crystallization by Amorphous Particle Attachment: On the Evolution of Texture

“…Recently, significant efforts have been directed into studying and modeling the different CPA pathways. [ 12–14 ] A mechanistic understanding of each step has the potential to generate a comprehensive toolkit for the design and synthesis of novel materials systems liberated from the limitations of classical crystallization models. However, many knowledge gaps still remain.…”