Calixarene-mediated synthesis of cobalt nanoparticles: An accretion model for separate control over nucleation and growth

Zhenguo Chen, Jie Liu, Andrew J. Evans, Laura Alberch, Alexander Wei

Research output: Contribution to journalArticle

7 Citations (Scopus)

Abstract

The nucleation and growth of crystalline cobalt nanoparticles (Co NPs) under solvothermal conditions can be separated into distinct stages by using (i) polynuclear clusters with multivalent capping ligands to initiate nucleation, and (ii) thermolabile organometallic complexes with low autonucleation potential to promote crystalline growth. Both nucleation and growth take place within an amorphous accretion, formed in the presence of polyvalent surfactants. At the prenucleation stage, a calixarene complex with multiple Co2-alkyne ligands (Co16-calixarene 1) undergoes thermal decomposition above 130 C to form "capped cluster" intermediates that coalesce into well-defined Co nanoclusters, but are resistant to further aggregation. At the postnucleation stage, a monomer (pentyne-Co4(CO)10, or PTC) with a low thermal activation threshold but a high barrier to autonucleation is introduced, yielding ε-Co NPs with a linear relationship between particle volume and the Co mole ratio ([Cofinal]/[Co seed]). Co nanocrystals can be produced up to 40 nm with a 10-12% size dispersity within the accretion, but their growth rate depends on the activity of the supporting surfactant, with an octapropargyl calixarene derivative (OP-C11R) providing the most efficient transport of reactive Co species through the amorphous matrix. Postgrowth digestion with oleic acid releases the Co NPs from the residual accretion, which can then self-assemble by magnetic dipolar interactions into flux-closure rings when stabilized by calixarene-based surfactants. These studies demonstrate that organometallic complexes can be designed to establish rational control over the nucleation and growth of crystalline NPs within an intermediate accretion phase.

Original languageEnglish (US)
Pages (from-to)941-950
Number of pages10
JournalChemistry of Materials
Volume26
Issue number2
DOIs
StatePublished - Jan 28 2014

Fingerprint

Calixarenes
Cobalt
Nucleation
Surface-Active Agents
Nanoparticles
Surface active agents
Organometallics
Crystalline materials
Ligands
Factor IX
Alkynes
Oleic acid
Nanoclusters
Oleic Acid
Nanocrystals
Seed
Pyrolysis
Agglomeration
Monomers
Chemical activation

Keywords

  • cobalt
  • growth
  • magnetic properties
  • nucleation
  • organometallic

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)
  • Materials Chemistry

Cite this

Calixarene-mediated synthesis of cobalt nanoparticles : An accretion model for separate control over nucleation and growth. / Chen, Zhenguo; Liu, Jie; Evans, Andrew J.; Alberch, Laura; Wei, Alexander.

In: Chemistry of Materials, Vol. 26, No. 2, 28.01.2014, p. 941-950.

Research output: Contribution to journalArticle

Chen, Zhenguo ; Liu, Jie ; Evans, Andrew J. ; Alberch, Laura ; Wei, Alexander. / Calixarene-mediated synthesis of cobalt nanoparticles : An accretion model for separate control over nucleation and growth. In: Chemistry of Materials. 2014 ; Vol. 26, No. 2. pp. 941-950.
@article{da82409d89054afdaf899e7c4163d004,
title = "Calixarene-mediated synthesis of cobalt nanoparticles: An accretion model for separate control over nucleation and growth",
abstract = "The nucleation and growth of crystalline cobalt nanoparticles (Co NPs) under solvothermal conditions can be separated into distinct stages by using (i) polynuclear clusters with multivalent capping ligands to initiate nucleation, and (ii) thermolabile organometallic complexes with low autonucleation potential to promote crystalline growth. Both nucleation and growth take place within an amorphous accretion, formed in the presence of polyvalent surfactants. At the prenucleation stage, a calixarene complex with multiple Co2-alkyne ligands (Co16-calixarene 1) undergoes thermal decomposition above 130 C to form {"}capped cluster{"} intermediates that coalesce into well-defined Co nanoclusters, but are resistant to further aggregation. At the postnucleation stage, a monomer (pentyne-Co4(CO)10, or PTC) with a low thermal activation threshold but a high barrier to autonucleation is introduced, yielding ε-Co NPs with a linear relationship between particle volume and the Co mole ratio ([Cofinal]/[Co seed]). Co nanocrystals can be produced up to 40 nm with a 10-12{\%} size dispersity within the accretion, but their growth rate depends on the activity of the supporting surfactant, with an octapropargyl calixarene derivative (OP-C11R) providing the most efficient transport of reactive Co species through the amorphous matrix. Postgrowth digestion with oleic acid releases the Co NPs from the residual accretion, which can then self-assemble by magnetic dipolar interactions into flux-closure rings when stabilized by calixarene-based surfactants. These studies demonstrate that organometallic complexes can be designed to establish rational control over the nucleation and growth of crystalline NPs within an intermediate accretion phase.",
keywords = "cobalt, growth, magnetic properties, nucleation, organometallic",
author = "Zhenguo Chen and Jie Liu and Evans, {Andrew J.} and Laura Alberch and Alexander Wei",
year = "2014",
month = "1",
day = "28",
doi = "10.1021/cm402484x",
language = "English (US)",
volume = "26",
pages = "941--950",
journal = "Chemistry of Materials",
issn = "0897-4756",
publisher = "American Chemical Society",
number = "2",

}

TY - JOUR

T1 - Calixarene-mediated synthesis of cobalt nanoparticles

T2 - An accretion model for separate control over nucleation and growth

AU - Chen, Zhenguo

AU - Liu, Jie

AU - Evans, Andrew J.

AU - Alberch, Laura

AU - Wei, Alexander

PY - 2014/1/28

Y1 - 2014/1/28

N2 - The nucleation and growth of crystalline cobalt nanoparticles (Co NPs) under solvothermal conditions can be separated into distinct stages by using (i) polynuclear clusters with multivalent capping ligands to initiate nucleation, and (ii) thermolabile organometallic complexes with low autonucleation potential to promote crystalline growth. Both nucleation and growth take place within an amorphous accretion, formed in the presence of polyvalent surfactants. At the prenucleation stage, a calixarene complex with multiple Co2-alkyne ligands (Co16-calixarene 1) undergoes thermal decomposition above 130 C to form "capped cluster" intermediates that coalesce into well-defined Co nanoclusters, but are resistant to further aggregation. At the postnucleation stage, a monomer (pentyne-Co4(CO)10, or PTC) with a low thermal activation threshold but a high barrier to autonucleation is introduced, yielding ε-Co NPs with a linear relationship between particle volume and the Co mole ratio ([Cofinal]/[Co seed]). Co nanocrystals can be produced up to 40 nm with a 10-12% size dispersity within the accretion, but their growth rate depends on the activity of the supporting surfactant, with an octapropargyl calixarene derivative (OP-C11R) providing the most efficient transport of reactive Co species through the amorphous matrix. Postgrowth digestion with oleic acid releases the Co NPs from the residual accretion, which can then self-assemble by magnetic dipolar interactions into flux-closure rings when stabilized by calixarene-based surfactants. These studies demonstrate that organometallic complexes can be designed to establish rational control over the nucleation and growth of crystalline NPs within an intermediate accretion phase.

AB - The nucleation and growth of crystalline cobalt nanoparticles (Co NPs) under solvothermal conditions can be separated into distinct stages by using (i) polynuclear clusters with multivalent capping ligands to initiate nucleation, and (ii) thermolabile organometallic complexes with low autonucleation potential to promote crystalline growth. Both nucleation and growth take place within an amorphous accretion, formed in the presence of polyvalent surfactants. At the prenucleation stage, a calixarene complex with multiple Co2-alkyne ligands (Co16-calixarene 1) undergoes thermal decomposition above 130 C to form "capped cluster" intermediates that coalesce into well-defined Co nanoclusters, but are resistant to further aggregation. At the postnucleation stage, a monomer (pentyne-Co4(CO)10, or PTC) with a low thermal activation threshold but a high barrier to autonucleation is introduced, yielding ε-Co NPs with a linear relationship between particle volume and the Co mole ratio ([Cofinal]/[Co seed]). Co nanocrystals can be produced up to 40 nm with a 10-12% size dispersity within the accretion, but their growth rate depends on the activity of the supporting surfactant, with an octapropargyl calixarene derivative (OP-C11R) providing the most efficient transport of reactive Co species through the amorphous matrix. Postgrowth digestion with oleic acid releases the Co NPs from the residual accretion, which can then self-assemble by magnetic dipolar interactions into flux-closure rings when stabilized by calixarene-based surfactants. These studies demonstrate that organometallic complexes can be designed to establish rational control over the nucleation and growth of crystalline NPs within an intermediate accretion phase.

KW - cobalt

KW - growth

KW - magnetic properties

KW - nucleation

KW - organometallic

UR - http://www.scopus.com/inward/record.url?scp=84893495023&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84893495023&partnerID=8YFLogxK

U2 - 10.1021/cm402484x

DO - 10.1021/cm402484x

M3 - Article

C2 - 25960603

AN - SCOPUS:84893495023

VL - 26

SP - 941

EP - 950

JO - Chemistry of Materials

JF - Chemistry of Materials

SN - 0897-4756

IS - 2

ER -