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Evolution of Calcite Nanocrystals through Oriented Attachment and Fragmentation: Multistep Pathway Involving Bottom-Up and Break-Down Stages.

ABSTRACT: A nonclassical multistep pathway involving bottom-up and break-down stages for the evolution of calcite nanograins ∼50 nm in size was demonstrated in a basic aqueous system. Calcite nanofibrils ∼10 nm wide were produced as the initial crystalline phase via amorphous calcium carbonate through ion-by-ion assembly by the carbonation of Ca(OH)₂ at a high pH of ∼13. Bundles ∼50 nm in diameter were then formed by the subsequent oriented attachment of the nanofibrils. Monodispersed calcite nanograins were finally obtained through spontaneous fragmentation of the fibrous forms via a decrease in pH by further carbonation.

SUBMITTER: Takasaki M

PROVIDER: S-EPMC6645547 | biostudies-literature | 2017 Dec

REPOSITORIES: biostudies-literature

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Evolution of Calcite Nanocrystals through Oriented Attachment and Fragmentation: Multistep Pathway Involving Bottom-Up and Break-Down Stages.

Takasaki Mihiro M Kezuka Yuki Y Tajika Masahiko M Oaki Yuya Y Imai Hiroaki H

ACS omega 20171215 12

A nonclassical multistep pathway involving bottom-up and break-down stages for the evolution of calcite nanograins ∼50 nm in size was demonstrated in a basic aqueous system. Calcite nanofibrils ∼10 nm wide were produced as the initial crystalline phase via amorphous calcium carbonate through ion-by-ion assembly by the carbonation of Ca(OH)<sub>2</sub> at a high pH of ∼13. Bundles ∼50 nm in diameter were then formed by the subsequent oriented attachment of the nanofibrils. Monodispersed calcite n ...[more]

PMID: 31457424

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Project description:Augmenting the oriented attachment (OA) crystal growth phenomena, herein, we demonstrate fabrication of ultrathin CuO nanowires from self-assembled one-dimensional (1D) nanowires of Cu(OH)2 nanocrystals. A facile environmentally benign sol-gel approach, which utilizes base-catalyzed hydrolysis followed by directed self-assembly and crystal growth of nanocrystals, is developed to prepare Cu(OH)2 nanowires. The sol of Cu(OH)2 nanocrystals shows aggregative self-assembly guided by the OA crystal growth process to form ultrathin Cu(OH)2 nanowires, with an average length of 675 ± 4 nm and diameter of 6 ± 2 nm. The time-dependent UV-visible spectral traces, along with real-time imaging of nanocrystals self-assembly and growth under the transmission electron microscope, are evidenced the concept of the OA crystal growth directed self-assembly, yielding 1D colloidal nanoarrays of Cu(OH)2. The powder XRD traces collected during the self-assembly and crystal growth process reveal the directional aggregative crystal growth along the facet of [001], confirming the OA directed crystal growth and fusion of nanocrystals to yield 1D nanostructures. The gradual blue-shift in optical absorption maxima from 770 nm in initial precursor solution, to 670 nm for Cu(OH)2 nanocrystals sol, and finally to 647 nm for self-assembled 1D Cu(OH)2 nanowires have further evidenced the formation of Cu(OH)2 nanowires. Upon subjecting self-assembled Cu(OH)2 nanowires for post-annealing treatment, ultrathin CuO nanowires with average length of 7 ± 0.50 μm and diameter of 27 ± 2 nm is obtained in high purity. The experimental powder XRD patterns of Cu(OH)2 and CuO nanowires match the simulated XRD patterns, indexing the crystal unit cell structures to orthorhombic and monoclinic, respectively. The tailored narrow optical band gaps for Cu(OH)2 and CuO nanowires are found to be 1.51 eV and 1.10 eV. The theoretical band gap predicted for Cu(OH)2 nanowires is 1.52 eV and is in good agreement with its optical band gap, whereas theoretical band computed for CuO nanowires is 0.13 eV lower than from its optical band gap.

Dataset Information

Evolution of Calcite Nanocrystals through Oriented Attachment and Fragmentation: Multistep Pathway Involving Bottom-Up and Break-Down Stages.

Publications

Evolution of Calcite Nanocrystals through Oriented Attachment and Fragmentation: Multistep Pathway Involving Bottom-Up and Break-Down Stages.

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