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Title: Bioinspired Synthesis of Quasi-Two-Dimensional Monocrystalline Oxides

Abstract

Controllable synthesis of two-dimensional (2D) monocrystalline oxide nanomaterials beyond van der Waals solids is intriguing but very challenging. Inspired by the biomineralization processes that commonly implement organic templates with both positive and negative charges for regulating the crystal nucleation and growth, we adapted mix-charges amphiphilic monolayer to the ionic layer epitaxy and enabled the growth of monocrystalline 2D nanosheets. In situ grazing incidence X-ray diffraction and ex situ crystal and elemental analyses revealed that mixing charge in the template is able to tune the 2D crystal nucleation rate and promote the growth of monocrystalline domains. Molecular dynamics simulations suggested that mixing charges could yield a stable, flatter, and more ordered monolayer template with a nonuniform distribution of charges, which are favorable for the growth of monocrystalline nanosheets. As a result, designing the mixed amphiphilic monolayers resulted in the creation of ultrathin nanosheets from various oxides including CoO, Bi2O3, MnO2, and Fe3O4 as well as doped ones, opening up an opportunity to broaden the 2D nanomaterial family to functional oxides.

Authors:
ORCiD logo [1];  [1]; ORCiD logo [1];  [1];  [1];  [1]; ORCiD logo [1];  [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Univ. of Wisconsin-Madison, WI (United States)
Publication Date:
Research Org.:
Univ. of Wisconsin-Madison, WI (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
Contributing Org.:
ChemMatCARS Sector 15; Advanced Photon Source
OSTI Identifier:
1635637
Grant/Contract Number:  
FG02-08ER46547; AC02-06CH11357; DMR-1709025; NSF/CHE-1346572
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 31; Journal Issue: 21; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; interfaces; crystallization; two dimensional materials; monolayers; surfactants

Citation Formats

Wang, Yizhan, Shi, Yeqi, Zhang, Ziyi, Carlos, Corey, Zhang, Chenyu, Bhawnani, Karishma, Li, Jun, Wang, Jingyu, Voyles, Paul M., Szlufarska, Izabela, and Wang, Xudong. Bioinspired Synthesis of Quasi-Two-Dimensional Monocrystalline Oxides. United States: N. p., 2019. Web. https://doi.org/10.1021/acs.chemmater.9b03307.
Wang, Yizhan, Shi, Yeqi, Zhang, Ziyi, Carlos, Corey, Zhang, Chenyu, Bhawnani, Karishma, Li, Jun, Wang, Jingyu, Voyles, Paul M., Szlufarska, Izabela, & Wang, Xudong. Bioinspired Synthesis of Quasi-Two-Dimensional Monocrystalline Oxides. United States. https://doi.org/10.1021/acs.chemmater.9b03307
Wang, Yizhan, Shi, Yeqi, Zhang, Ziyi, Carlos, Corey, Zhang, Chenyu, Bhawnani, Karishma, Li, Jun, Wang, Jingyu, Voyles, Paul M., Szlufarska, Izabela, and Wang, Xudong. Fri . "Bioinspired Synthesis of Quasi-Two-Dimensional Monocrystalline Oxides". United States. https://doi.org/10.1021/acs.chemmater.9b03307. https://www.osti.gov/servlets/purl/1635637.
@article{osti_1635637,
title = {Bioinspired Synthesis of Quasi-Two-Dimensional Monocrystalline Oxides},
author = {Wang, Yizhan and Shi, Yeqi and Zhang, Ziyi and Carlos, Corey and Zhang, Chenyu and Bhawnani, Karishma and Li, Jun and Wang, Jingyu and Voyles, Paul M. and Szlufarska, Izabela and Wang, Xudong},
abstractNote = {Controllable synthesis of two-dimensional (2D) monocrystalline oxide nanomaterials beyond van der Waals solids is intriguing but very challenging. Inspired by the biomineralization processes that commonly implement organic templates with both positive and negative charges for regulating the crystal nucleation and growth, we adapted mix-charges amphiphilic monolayer to the ionic layer epitaxy and enabled the growth of monocrystalline 2D nanosheets. In situ grazing incidence X-ray diffraction and ex situ crystal and elemental analyses revealed that mixing charge in the template is able to tune the 2D crystal nucleation rate and promote the growth of monocrystalline domains. Molecular dynamics simulations suggested that mixing charges could yield a stable, flatter, and more ordered monolayer template with a nonuniform distribution of charges, which are favorable for the growth of monocrystalline nanosheets. As a result, designing the mixed amphiphilic monolayers resulted in the creation of ultrathin nanosheets from various oxides including CoO, Bi2O3, MnO2, and Fe3O4 as well as doped ones, opening up an opportunity to broaden the 2D nanomaterial family to functional oxides.},
doi = {10.1021/acs.chemmater.9b03307},
journal = {Chemistry of Materials},
number = 21,
volume = 31,
place = {United States},
year = {2019},
month = {10}
}

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Figures / Tables:

Figure 1 Figure 1: Nanosheets synthesis under mixed surfactants with opposite charges. a, Layered structure of hexagonal aragonite platelets alternating with organic matrix in the nacreous layer of pearl and the schematic representation of protein surface structure with well-mixed positive (red) and negative (blue) charged amino acid residues directing the biomineralization ofmore » aragonite; b, Schematic illustration of the formation of monocrystalline nanosheets with the mixed monolayer bared positive (red) and negative (blue) charges on the interface of precursor solution and air; c, SEM image of continuous film of Co(OH)2 synthesized with mono SOS as-transferred to a SiO2/Si substrate surface. The inset is the SAED pattern of the synthesized film, which indicated the polycrystallinity of the film; d, SEM image of triangular Co(OH)2 nanosheet synthesized with mixed monolayer (SOS/OAM = 9:1) as-transferred to a SiO2/Si substrate surface; e, Low-magnification TEM image and the selected area electron diffraction (SAED) pattern (inset) of the triangular nanosheet rest on a holy carbon TEM grid; f, Triangle nanosheets after 10 min of O2 plasma treatment. Inset is the SAED pattern, which matches well with the CoO structure; g, High-resolution TEM image showing the crystal lattice of CoO after plasma treatment of the triangle nanosheets. Elemental mapping of (h) cobalt and (i) oxygen in the area of triangle nanosheets marked by the orange box in f; j, Topography AFM image showing the nanometer thickness and good surface flatness of the nanosheets. Inset is the height profile along the red line revealing the thickness is 2.1 nm.« less

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