skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: The role of nanoparticle size and ligand coverage in size focusing of colloidal metal nanoparticles

Abstract

Controlling the size distribution of nanoparticles is important for many applications and typically involves the use of ligands during synthesis. In this study, we show that the mechanism of size focusing involves a dependence of the growth rate on the size of the nanoparticles and the ligand coverage on the surface of the nanoparticles. To demonstrate these effects, we used in situ small angle X-ray scattering (SAXS) and population balance kinetic modeling (PBM) to investigate the evolution of size distribution during the synthesis of colloidal Pd metal nanoparticles. Despite temporal overlap of nucleation and growth, our in situ SAXS show size focusing of the distribution under different synthetic conditions (different concentrations of metal and ligand as well as solvent type). To understand the mechanism of size focusing using PBM, we systematically studied how the evolution of the nanoparticle size distribution is affected by nucleation rate, and dependence of the growth rate constant on ligand surface coverage, and size of the nanoparticles. We show that continuous nucleation contributes to size defocusing. However, continuous nucleation results in different reaction times for the nanoparticle population leading to time and size-dependent ligand surface coverage. Using density functional theory (DFT) calculations and Brønsted–Evans–Polanyi relations, wemore » show that as the population grows, larger nanoparticles grow more slowly than smaller ones due to lower intrinsic activity and higher ligand coverage on the surface. Therefore, despite continuous nucleation, the faster growth of smaller nanoparticles in the population leads to size focusing. The size focusing behaviour (due to faster growth of smaller nanoparticles) was found to be model independent and similar results were demonstrated under different nucleation and growth pathways (e.g. growth via ion reduction on the surface and/or monomer addition). Our results provide a microscopic connection between kinetics and thermodynamics of nanoparticle growth and metal–ligand binding, and their effect on the size distribution of colloidal nanoparticles.« less

Authors:
 [1];  [1]; ORCiD logo [2];  [3]; ORCiD logo [4];  [5]; ORCiD logo [2]; ORCiD logo [1]
  1. Department of Chemical Engineering, Virginia Polytechnic Institute and State University, Blacksburg, USA
  2. Department of Chemical Engineering, University of Pittsburgh, Pittsburgh, USA
  3. Advanced Photon Source, Argonne National Laboratory, Argonne, USA
  4. X-ray Science Division, Argonne National Laboratory, Argonne, USA
  5. Environmental Molecular Science Laboratory, Pacific Northwest National Laboratory, Richland, USA
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1562321
Alternate Identifier(s):
OSTI ID: 1781316
Report Number(s):
PNNL-SA-161898
Journal ID: ISSN 2516-0230; NAADAI
Grant/Contract Number:  
AC02-06CH11357; AC05-76RL01830
Resource Type:
Journal Article: Published Article
Journal Name:
Nanoscale Advances
Additional Journal Information:
Journal Name: Nanoscale Advances Journal Volume: 1 Journal Issue: 10; Journal ID: ISSN 2516-0230
Publisher:
Royal Society of Chemistry (RSC)
Country of Publication:
United Kingdom
Language:
English
Subject:
77 NANOSCIENCE AND NANOTECHNOLOGY

Citation Formats

Mozaffari, Saeed, Li, Wenhui, Dixit, Mudit, Seifert, Soenke, Lee, Byeongdu, Kovarik, Libor, Mpourmpakis, Giannis, and Karim, Ayman M. The role of nanoparticle size and ligand coverage in size focusing of colloidal metal nanoparticles. United Kingdom: N. p., 2019. Web. doi:10.1039/C9NA00348G.
Mozaffari, Saeed, Li, Wenhui, Dixit, Mudit, Seifert, Soenke, Lee, Byeongdu, Kovarik, Libor, Mpourmpakis, Giannis, & Karim, Ayman M. The role of nanoparticle size and ligand coverage in size focusing of colloidal metal nanoparticles. United Kingdom. https://doi.org/10.1039/C9NA00348G
Mozaffari, Saeed, Li, Wenhui, Dixit, Mudit, Seifert, Soenke, Lee, Byeongdu, Kovarik, Libor, Mpourmpakis, Giannis, and Karim, Ayman M. 2019. "The role of nanoparticle size and ligand coverage in size focusing of colloidal metal nanoparticles". United Kingdom. https://doi.org/10.1039/C9NA00348G.
@article{osti_1562321,
title = {The role of nanoparticle size and ligand coverage in size focusing of colloidal metal nanoparticles},
author = {Mozaffari, Saeed and Li, Wenhui and Dixit, Mudit and Seifert, Soenke and Lee, Byeongdu and Kovarik, Libor and Mpourmpakis, Giannis and Karim, Ayman M.},
abstractNote = {Controlling the size distribution of nanoparticles is important for many applications and typically involves the use of ligands during synthesis. In this study, we show that the mechanism of size focusing involves a dependence of the growth rate on the size of the nanoparticles and the ligand coverage on the surface of the nanoparticles. To demonstrate these effects, we used in situ small angle X-ray scattering (SAXS) and population balance kinetic modeling (PBM) to investigate the evolution of size distribution during the synthesis of colloidal Pd metal nanoparticles. Despite temporal overlap of nucleation and growth, our in situ SAXS show size focusing of the distribution under different synthetic conditions (different concentrations of metal and ligand as well as solvent type). To understand the mechanism of size focusing using PBM, we systematically studied how the evolution of the nanoparticle size distribution is affected by nucleation rate, and dependence of the growth rate constant on ligand surface coverage, and size of the nanoparticles. We show that continuous nucleation contributes to size defocusing. However, continuous nucleation results in different reaction times for the nanoparticle population leading to time and size-dependent ligand surface coverage. Using density functional theory (DFT) calculations and Brønsted–Evans–Polanyi relations, we show that as the population grows, larger nanoparticles grow more slowly than smaller ones due to lower intrinsic activity and higher ligand coverage on the surface. Therefore, despite continuous nucleation, the faster growth of smaller nanoparticles in the population leads to size focusing. The size focusing behaviour (due to faster growth of smaller nanoparticles) was found to be model independent and similar results were demonstrated under different nucleation and growth pathways (e.g. growth via ion reduction on the surface and/or monomer addition). Our results provide a microscopic connection between kinetics and thermodynamics of nanoparticle growth and metal–ligand binding, and their effect on the size distribution of colloidal nanoparticles.},
doi = {10.1039/C9NA00348G},
url = {https://www.osti.gov/biblio/1562321}, journal = {Nanoscale Advances},
issn = {2516-0230},
number = 10,
volume = 1,
place = {United Kingdom},
year = {2019},
month = {10}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at https://doi.org/10.1039/C9NA00348G

Save / Share:

Works referenced in this record:

Experimental Evaluation of Kinetic and Thermodynamic Reaction Parameters of Colloidal Nanocrystals
journal, May 2016


Palladium Nanoparticle Size Effect in 1-Hexyne Selective Hydrogenation
journal, August 2007


Generalized Gradient Approximation Made Simple
journal, October 1996


Chemisorption of CO and Mechanism of CO Oxidation on Supported Platinum Nanoclusters
journal, March 2011


Size-, Shape-, and Composition-Dependent Model for Metal Nanoparticle Stability Prediction
journal, March 2018


Turkevich in New Robes: Key Questions Answered for the Most Common Gold Nanoparticle Synthesis
journal, June 2015


Oxidative Etching and Its Role in Manipulating the Nucleation and Growth of Noble-Metal Nanocrystals
journal, August 2013


Kinetics of cesium lead halide perovskite nanoparticle growth; focusing and de-focusing of size distribution
journal, January 2016


Size/Shape-Controlled Synthesis of Colloidal CdSe Quantum Disks: Ligand and Temperature Effects
journal, May 2011


Mechanism of Gold Nanoparticle Formation in the Classical Citrate Synthesis Method Derived from Coupled In Situ XANES and SAXS Evaluation
journal, February 2010


Thermodynamic stability of ligand-protected metal nanoclusters
journal, July 2017


Kinetics of II-VI and III-V Colloidal Semiconductor Nanocrystal Growth:  “Focusing” of Size Distributions
journal, June 1998


Focusing Nanocrystal Size Distributions via Production Control
journal, May 2011


Further considerations on the thermodynamics of chemical equilibria and reaction rates
journal, January 1936


Investigation of Indium Phosphide Nanocrystal Synthesis Using a High-Temperature and High-Pressure Continuous Flow Microreactor
journal, December 2010


Digestive Ripening: A Fine Chemical Machining Process on the Nanoscale
journal, June 2017


On the Mechanism of Metal Nanoparticle Synthesis in the Brust–Schiffrin Method
journal, July 2013


Colloidal Nanocrystals with Inorganic Halide, Pseudohalide, and Halometallate Ligands
journal, June 2014


Kinetics and Mechanisms of Aggregative Nanocrystal Growth
journal, September 2013


Enhanced Nanoparticle Size Control by Extending LaMer’s Mechanism
journal, August 2015


Nucleation and Growth of Metal Nanoparticles during Photoreduction Using In Situ Time-Resolved SAXS Analysis
journal, June 2011


Quickstep: Fast and accurate density functional calculations using a mixed Gaussian and plane waves approach
journal, April 2005


Ultrastable silver nanoparticles
journal, September 2013


Nucleation Control of Size and Dispersity in Aggregative Nanoparticle Growth. A Study of the Coarsening Kinetics of Thiolate-Capped Gold Nanocrystals
journal, May 2010


A Size Threshold for Enhanced Magnetoresistance in Colloidally Prepared CoFe 2 O 4 Nanoparticle Solids
journal, August 2018


Atomically Precise Colloidal Metal Nanoclusters and Nanoparticles: Fundamentals and Opportunities
journal, September 2016


Investigation of Catalytic Finite-Size-Effects of Platinum Metal Clusters
journal, December 2012


Structure Sensitivity of Alkynol Hydrogenation on Shape- and Size-Controlled Palladium Nanocrystals: Which Sites Are Most Active and Selective?
journal, August 2011


Just Add Ligands: Self-Sustained Size Focusing of Colloidal Semiconductor Nanocrystals
journal, February 2018


A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
journal, April 2010


Preparing water-dispersed palladium nanoparticles via polyelectrolyte nanoreactors
journal, January 2010


Shape-Controlled Synthesis of Colloidal Metal Nanocrystals: Thermodynamic versus Kinetic Products
journal, June 2015


Size-Controlled Synthesis of Sub-10-nanometer Citrate-Stabilized Gold Nanoparticles and Related Optical Properties.
journal, February 2016


Size- and shape-dependent catalytic performances of oxidation and reduction reactions on nanocatalysts
journal, January 2016


Gold nanorods with conjugated polymer ligands: sintering-free conductive inks for printed electronics
journal, January 2016


Insights into the modeling of adsorption isotherm systems
journal, January 2010


Detection and identification of designer drugs by nanoparticle-based NMR chemosensing
journal, January 2018


Real-Time Imaging of Pt3Fe Nanorod Growth in Solution
journal, May 2012


Hydrotalcite-Supported Gold Catalyst for the Oxidant-Free Dehydrogenation of Benzyl Alcohol: Studies on Support and Gold Size Effects
journal, December 2010


Ligand and Solvation Effects on the Structural and Electronic Properties of Small Gold Clusters
journal, February 2014


Size Dependence of the Adsorption Energy of CO on Metal Nanoparticles: A DFT Search for the Minimum Value
journal, January 2012


Ligand-Mediated Nanocrystal Growth
journal, February 2018


Digestive ripening in the formation of monodisperse silver nanospheres
journal, January 2018


Redox reaction induced Ostwald ripening for size- and shape-focusing of palladium nanocrystals
journal, January 2015


Continuum tuning of nanoparticle interfacial properties by dynamic covalent exchange
journal, January 2018


Ligand effect on the catalytic activity of porphyrin-protected gold clusters in the electrochemical hydrogen evolution reaction
journal, January 2018


Insights into the Kinetics of Semiconductor Nanocrystal Nucleation and Growth
journal, April 2009


The Growth of Uniform Colloidal Dispersions
journal, April 1951


Size Focusing of Nanoparticles by Thermodynamic Control through Ligand Interactions. Molecular Clusters Compared with Nanoparticles of Metals
journal, March 2012


The thermodynamics of nitrogen adsorption on nickel clusters: Ni19–Ni71
journal, March 1998


Chemistry and Structure of Silver Molecular Nanoparticles
journal, November 2018


McSAS : software for the retrieval of model parameter distributions from scattering patterns
journal, May 2015


Controlled growth of imine-linked two-dimensional covalent organic framework nanoparticles
journal, January 2019


Improvements and considerations for size distribution retrieval from small-angle scattering data by Monte Carlo methods
journal, February 2013


Dependence on size of supported Rh nanoclusters for CO adsorption
journal, January 2016


The role of electron irradiation history in liquid cell transmission electron microscopy
journal, April 2018


Size-dependent activity and selectivity of carbon dioxide photocatalytic reduction over platinum nanoparticles
journal, March 2018


Noble-Metal Nanocrystals with Concave Surfaces: Synthesis and Applications
journal, May 2012


Strongest π–metal orbital coupling in a porphyrin/gold cluster system
journal, January 2014


Small Angle X-ray Scattering for Nanoparticle Research
journal, April 2016


Colloidal CdSe Quantum Rings
journal, July 2016


Quantitative Analysis of Thiolated Ligand Exchange on Gold Nanoparticles Monitored by 1 H NMR Spectroscopy
journal, February 2015


Manipulating Local Ligand Environments for the Controlled Nucleation of Metal Nanoparticles and their Assembly into Nanodendrites
journal, October 2012


Fast and Slow Ligand Exchange at the Surface of Colloidal Gold Nanoparticles
journal, January 2016


The effect of surface coverage on N 2 , NO and N 2 O formation over Pt(111)
journal, January 2018


Preparation of monodispersed colloidal particles
journal, January 1987


Transition-Metal Nanocluster Size vs Formation Time and the Catalytically Effective Nucleus Number: A Mechanism-Based Treatment
journal, September 2008


Trade-Off between Accuracy and Universality in Linear Energy Relations for Alcohol Dehydrogenation on Transition Metals
journal, June 2015


On the Size-Dependent Behavior of Nanocrystal−Ligand Bonds
journal, June 2006


Stability, surface features, and atom leaching of palladium nanoparticles: toward prediction of catalytic functionality
journal, January 2013


Thermochemical Measurements of Cation Exchange in CdSe Nanocrystals Using Isothermal Titration Calorimetry
journal, August 2018


Rigid bidentate ligands focus the size of gold nanoparticles
journal, January 2013


Strongly emissive perovskite nanocrystal inks for high-voltage solar cells
journal, December 2016


Probing in situ the Nucleation and Growth of Gold Nanoparticles by Small-Angle X-ray Scattering
journal, June 2007


Simple theory for the electronic and atomic structure of small clusters
journal, July 1983


Prospects of Colloidal Nanocrystals for Electronic and Optoelectronic Applications
journal, January 2010


Coverage-Dependent CO Adsorption Energy from First-Principles Calculations
journal, March 2009


Theory, Production and Mechanism of Formation of Monodispersed Hydrosols
journal, November 1950


On the Two-Step Mechanism for Synthesis of Transition-Metal Nanoparticles
journal, October 2014