In order to better control the assembly of nanorods, knowledge of the pathways by which they form ordered structures is desirable. In this paper, we characterize crystal nucleation in suspensions of spherocylindrical rods with aspect ratio L/D = 2.3 in the presence of both small and large polymer depletants. Using a combination of Langevin dynamics and Monte Carlo simulations, together with biased sampling techniques, we show that the preferred pathway always involves the formation of monolayer assemblies irrespective of the volume fraction of the initial isotropic phase and the diameter of the depletants. This includes the previously neglected case of nucleation from the colloidal liquid phase and shows that the presence of depletion attraction can alter nucleation pathways even when the initial phase is dense.
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January 2025
Dept. of Plant and Environmental Sciences, Weizmann Institute of Science, Rehovot, 7610001, Israel.
Transient amorphous phases are known as functional precursors in the formation of crystalline materials, both in vivo and in vitro. A common route to regulate amorphous calcium carbonate (ACC) crystallization is via direct interactions with negatively charged macromolecules. However, a less explored phenomenon that can influence such systems is the electrostatically driven formation of Ca-macromolecule dense phases.
View Article and Find Full Text PDFNat Commun
January 2025
Department of Civil and Environmental Engineering, Rice University, Houston, TX, USA.
Gypsum (CaSO·2HO) plays a critical role in numerous natural and industrial processes. Nevertheless, the underlying mechanisms governing the formation of gypsum crystals on surfaces with diverse chemical properties remain poorly understood due to a lack of sufficient temporal-spatial resolution. Herein, we use in situ microscopy to investigate the real-time gypsum nucleation on self-assembled monolayers (SAMs) terminated with -CH, -hybrid (a combination of NH and COOH), -COOH, -SO, -NH, and -OH functional groups.
View Article and Find Full Text PDFJ Phys Chem Lett
January 2025
Department of Physics and Astronomy and Thomas Young Centre, University College London, London WC1E 6BT, United Kingdom.
Atomic-scale understanding of important geochemical processes including sorption, dissolution, nucleation, and crystal growth is difficult to obtain from experimental measurements alone and would benefit from strong continuous progress in molecular simulation. To this end, we present a reactive neural network potential-based molecular dynamics approach to simulate the interaction of aqueous ions on mineral surfaces in contact with liquid water, taking Fe(II) on hematite(001) as a model system. We show that a single neural network potential predicts rate constants for water exchange for aqueous Fe(II) and for the exergonic chemisorption of aqueous Fe(II) on hematite(001) in good agreement with experimental observations.
View Article and Find Full Text PDFAdv Mater
January 2025
Michael Grätzel Center for Mesoscopic Solar Cells Wuhan National Laboratory for Optoelectronics Key Laboratory of Materials Chemistry for Energy Conversion and Storage of Ministry of Education, Huazhong University of Science and Technology, Wuhan, Hubei, 430074, P. R. China.
Carbon-based printable mesoscopic solar cells (p-MPSCs) offer significant advantages for industrialization due to their simple fabrication process, low cost, and scalability. Recently, the certified power conversion efficiency of p-MPSCs has exceeded 22%, drawing considerable attention from the community. However, the key challenge in improving device performance is achieving uniform and high-quality perovskite crystallization within the mesoporous structure.
View Article and Find Full Text PDFJ Chem Phys
January 2025
Institute of Photoelectronic Thin Film Devices and Technology, Tianjin Key Laboratory of Thin Film Devices and Technology, Nankai University, Tianjin 300350, China.
Kesterite Cu2ZnSn(S,Se)4 (CZTSSe) has emerged as a promising photovoltaic material due to its low cost and high stability. The CZTSSe film for high-performance solar cells can be obtained by annealing the deposited CZTS precursor films with selenium (a process known as selenization). The design of the selenization process significantly affects the quality of the absorber layer.
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