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Cited by 206Supramolecular Self-Assembly in MaterialsCalcium Carbonate Crystallization and InhibitionSupramolecular Chemistry and Complexes

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Oriented assembly of anisotropic nanoparticles into frame-like superstructures

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Nai, Jianwei, Guan, Bu Yuan, Yu, Le, Lou, Xiong Wen (David)·2017·Science Advances
DOI 10.1126/sciadv.1700732PMC PMC5567758
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Abstract

Cubic frame–like superstructures are constructed via the assembly of nanocuboids on the edges of preformed nanocubes.

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Figures

Fig. 1 Discrete frame-like superstructures of Co-Fe PBA assembled from the attachment of NCBs. (A) FESEM images of the KCoFe-1 NAFSs. Inset: A magnified FESEM image displays a single NAFS. Schematic models of a NAFS from three orientations (B to D), and their corresponding TEM images (E to G) and SAED patterns (H to J) from different zones. The spots located on each ring in (H) to (J) (semirings are marked by blue dots) represent those families of lattice planes with the same interplanar spacing (from the inner to outer ring): {200}, {022}, {400}, {024}, and {600} in (H); {200}, {220}, {222}, {400}, and {600} in (I); and {220}, {440}, and {660} in (J). (K to M) HRTEM images of the white square shown in (E) to (G), respectively. Interplanar spacing of 4.9 and 3.5 Å represents {200} and {220} planes, respectively. Insets: Corresponding FFT images. (N) HRTEM image of a part of two separate edges within a NAFS (marked by a red rectangle) in (E). The dashed line delineates the boundary profile of the upper edge (high contrast on the left) from the nether one (lower contrast on the right). The left arrow reveals the attachment interface between NCB-1 and NCB-2 on the upper edge, whereas the right one reveals that of NCB-3 and NCB-4 on the nether edge. The squares display continuous lattice fringes across the region around the attachment interface of the adjacent NCBs. (O) FFT images from the three squares shown in (N).
Fig. 1 Discrete frame-like superstructures of Co-Fe PBA assembled from the attachment of NCBs. (A) FESEM images of the KCoFe-1 NAFSs. Inset: A magnified FESEM image displays a single NAFS. Schematic models of a NAFS from three orientations (B to D), and their corresponding TEM images (E to G) and SAED patterns (H to J) from different zones. The spots located on each ring in (H) to (J) (semirings are marked by blue dots) represent those families of lattice planes with the same interplanar spacing (from the inner to outer ring): {200}, {022}, {400}, {024}, and {600} in (H); {200}, {220}, {222}, {400}, and {600} in (I); and {220}, {440}, and {660} in (J). (K to M) HRTEM images of the white square shown in (E) to (G), respectively. Interplanar spacing of 4.9 and 3.5 Å represents {200} and {220} planes, respectively. Insets: Corresponding FFT images. (N) HRTEM image of a part of two separate edges within a NAFS (marked by a red rectangle) in (E). The dashed line delineates the boundary profile of the upper edge (high contrast on the left) from the nether one (lower contrast on the right). The left arrow reveals the attachment interface between NCB-1 and NCB-2 on the upper edge, whereas the right one reveals that of NCB-3 and NCB-4 on the nether edge. The squares display continuous lattice fringes across the region around the attachment interface of the adjacent NCBs. (O) FFT images from the three squares shown in (N).CC BY-NC · PubMed Central
Fig. 2 Formation process and mechanism of the KCoFe-1 NAFSs. (A) FESEM images of the samples obtained at 5 s and 2, 6, 9, 18, and 36 hours of the reaction process, showing the morphological change from NCs to NAFSs. (B) Schematic illustration of the formation mechanism of a NAFS, in which four stages were involved: I, site-selected deposition; II, the formation of the new KCoFe-1 phase; III, epitaxial growth of the NCBs; IV, core@satellite superstructure transform to NAFS. (C) Mechanism of the hydroxyl-potassium ion insertion triggered PCET. (D) Ordered arrangement of NCBs on three orthogonal edges of the core@satellite superstructure in (B) (marked by black dashed lines). (E) Two types of outcome from the OA of adjacent NCBs: type I, neck attaching; type II, total integration.
Fig. 2 Formation process and mechanism of the KCoFe-1 NAFSs. (A) FESEM images of the samples obtained at 5 s and 2, 6, 9, 18, and 36 hours of the reaction process, showing the morphological change from NCs to NAFSs. (B) Schematic illustration of the formation mechanism of a NAFS, in which four stages were involved: I, site-selected deposition; II, the formation of the new KCoFe-1 phase; III, epitaxial growth of the NCBs; IV, core@satellite superstructure transform to NAFS. (C) Mechanism of the hydroxyl-potassium ion insertion triggered PCET. (D) Ordered arrangement of NCBs on three orthogonal edges of the core@satellite superstructure in (B) (marked by black dashed lines). (E) Two types of outcome from the OA of adjacent NCBs: type I, neck attaching; type II, total integration.CC BY-NC · PubMed Central
Fig. 3 Schematic illustration of the analogy of 3D assembly from molecules and NPs. (A) Assembly of a typical M8L12 supramolecular cube from the directional coordination bonding of specific molecules. Red arrows represent the coordination vectors. (B) Assembly of an M8L12-type NAFS from the OA of anisotropic NPs. Red arrows represent the normal vectors to the {100} facets. Red polygons represent the facets of NCB for attachment. (C) Features of diverse types of facets of a typical truncated NC for the OA-involved assembly. Arrows represent normal vectors to the corresponding facets. Colored polyhedra outside the NC represent the normal vector geometries of the relevant facets.
Fig. 3 Schematic illustration of the analogy of 3D assembly from molecules and NPs. (A) Assembly of a typical M8L12 supramolecular cube from the directional coordination bonding of specific molecules. Red arrows represent the coordination vectors. (B) Assembly of an M8L12-type NAFS from the OA of anisotropic NPs. Red arrows represent the normal vectors to the {100} facets. Red polygons represent the facets of NCB for attachment. (C) Features of diverse types of facets of a typical truncated NC for the OA-involved assembly. Arrows represent normal vectors to the corresponding facets. Colored polyhedra outside the NC represent the normal vector geometries of the relevant facets.CC BY-NC · PubMed Central
Fig. 4 Morphology and structural characterization of single-crystalline KCoFe-3 NFs. (A and B) FESEM images. Inset of (B) is a schematic model of the NF. (C and D) TEM images. (E) SAED pattern. (F) HRTEM image and the corresponding FFT image (inset).
Fig. 4 Morphology and structural characterization of single-crystalline KCoFe-3 NFs. (A and B) FESEM images. Inset of (B) is a schematic model of the NF. (C and D) TEM images. (E) SAED pattern. (F) HRTEM image and the corresponding FFT image (inset).CC BY-NC · PubMed Central
Fig. 5 Morphology and structural characterization of Co-Fe PBA–derived composites. (A to C) FESEM (A) and TEM (B and C) images of Co-Fe mixed oxides derived from KCoFe-1 NAFSs. Arrows show the interparticle interfaces within the NAFSs. (D to F) FESEM (D) and TEM (E and F) images of Co-Fe mixed oxides derived from KCoFe-3 NFs. The details of the edges of the frame-like structures in the left column of (B), (C), (E), and (F) (red dashed squares) are displayed in the right column.
Fig. 5 Morphology and structural characterization of Co-Fe PBA–derived composites. (A to C) FESEM (A) and TEM (B and C) images of Co-Fe mixed oxides derived from KCoFe-1 NAFSs. Arrows show the interparticle interfaces within the NAFSs. (D to F) FESEM (D) and TEM (E and F) images of Co-Fe mixed oxides derived from KCoFe-3 NFs. The details of the edges of the frame-like structures in the left column of (B), (C), (E), and (F) (red dashed squares) are displayed in the right column.CC BY-NC · PubMed Central
Fig. 6 Electrocatalytic oxygen evolution on Co-Fe mixed oxides. (A) LSV curves of NAFS and NF catalysts. (B) Tafel slopes of NAFS and NF catalysts. RHE, reversible hydrogen electrode. (C) CP response of NAFS and NF catalysts at the current density of 10 mA cm−2.
Fig. 6 Electrocatalytic oxygen evolution on Co-Fe mixed oxides. (A) LSV curves of NAFS and NF catalysts. (B) Tafel slopes of NAFS and NF catalysts. RHE, reversible hydrogen electrode. (C) CP response of NAFS and NF catalysts at the current density of 10 mA cm−2.CC BY-NC · PubMed Central

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Metadata

Authors
Nai, J., Guan, B. Y., Yu, L., & Lou, X. W. (.
Affiliations
Nanyang Technological University (SG)
Corresponding author
Lou, Xiong Wen (David)
ORCID
Venue
Science Advances
Publisher
American Association for the Advancement of Science (AAAS)
Published
2017-08-04
Volume
3
Issue
8
Pages
e1700732-e1700732
ISSN
2375-2548 (ISSN-L)
DOI
10.1126/sciadv.1700732
PMC
PMC5567758
OpenAlex
W2747678498
Cited by
206
References
77
Citations by year
2026: 7 · 2025: 17 · 2024: 21 · 2023: 33 · 2022: 24 · 2021: 28 · 2020: 16 · 2019: 30 · 2018: 26 · 2017: 4
FWCI
7.49
Type
journal article
Language
en
Open access
Licence
cc-by-nc
Locations
  • Science Advances (publishedVersion, cc-by-nc)
  • Europe PMC (PubMed Central) (publishedVersion, cc-by-nc)
  • PubMed Central (publishedVersion, cc-by-nc)
  • PubMed (publishedVersion)
  • DR-NTU (Nanyang Technological University) (submittedVersion, cc-by-nc)
Funders
National Research Foundation of Singapore (award336770, NRF-NRFI2016-04)
Topics
  • Physical Sciences › Materials Science › Biomaterials › Supramolecular Self-Assembly in Materials
  • Physical Sciences › Materials Science › Biomaterials › Calcium Carbonate Crystallization and Inhibition
  • Physical Sciences › Chemistry › Organic Chemistry › Supramolecular Chemistry and Complexes
Keywords
oriented assembly, anisotropic nanoparticles, nanoparticle morphology, annealing, electrocatalysts, bottom-up assembly, directional bonding

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