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Title: Tuning Precursor Reactivity toward Nanometer-Size Control in Palladium Nanoparticles Studied by in Situ Small Angle X-ray Scattering

Synthesis of monodisperse nanoparticles (NPs) with precisely controlled size is critical for understanding their size-dependent properties. Although significant synthetic developments have been achieved, it is still challenging to synthesize well-defined NPs in a predictive way due to a lack of in-depth mechanistic understanding of reaction kinetics. Here we use synchrotron-based small-angle X-ray scattering (SAXS) to monitor in situ the formation of palladium (Pd) NPs through thermal decomposition of Pd–TOP (TOP: trioctylphosphine) complex via the “heat-up” method. We systematically study the effects of different ligands, including oleylamine, TOP, and oleic acid, on the formation kinetics of Pd NPs. Through quantitative analysis of the real-time SAXS data, we are able to obtain a detailed picture of the size, size distribution, and concentration of Pd NPs during the syntheses, and these results show that different ligands strongly affect the precursor reactivity. We find that oleylamine does not change the reactivity of the Pd–TOP complex but promote the formation of nuclei due to strong ligand–NP binding. On the other hand, TOP and oleic acid substantially change the precursor reactivity over more than an order of magnitude, which controls the nucleation kinetics and determines the final particle size. A theoretical model is used to demonstratemore » that the nucleation and growth kinetics are dependent on both precursor reactivity and ligand–NP binding affinity, thus providing a framework to explain the synthesis process and the effect of the reaction conditions. Quantitative understanding of the impacts of different ligands enables the successful synthesis of a series of monodisperse Pd NPs in the broad size range from 3 to 11 nm with nanometer-size control, which serve as a model system to study their size-dependent catalytic properties. Furthermore, the in situ SAXS probing can be readily extended to other functional NPs to greatly advance their synthetic design.« less
Authors:
 [1] ;  [2] ;  [2] ;  [2] ;  [2] ; ORCiD logo [2] ;  [3] ; ORCiD logo [2]
  1. SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., Stanford, CA (United States)
  2. Stanford Univ., Stanford, CA (United States)
  3. SLAC National Accelerator Lab., Menlo Park, CA (United States)
Publication Date:
Grant/Contract Number:
DGE-1656518; AC02-76SF00515
Type:
Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 30; Journal Issue: 3; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Research Org:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org:
USDOE
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1457140

Wu, Liheng, Lian, Huada, Willis, Joshua J., Goodman, Emmett D., McKay, Ian Salmon, Qin, Jian, Tassone, Christopher J., and Cargnello, Matteo. Tuning Precursor Reactivity toward Nanometer-Size Control in Palladium Nanoparticles Studied by in Situ Small Angle X-ray Scattering. United States: N. p., Web. doi:10.1021/acs.chemmater.7b05186.
Wu, Liheng, Lian, Huada, Willis, Joshua J., Goodman, Emmett D., McKay, Ian Salmon, Qin, Jian, Tassone, Christopher J., & Cargnello, Matteo. Tuning Precursor Reactivity toward Nanometer-Size Control in Palladium Nanoparticles Studied by in Situ Small Angle X-ray Scattering. United States. doi:10.1021/acs.chemmater.7b05186.
Wu, Liheng, Lian, Huada, Willis, Joshua J., Goodman, Emmett D., McKay, Ian Salmon, Qin, Jian, Tassone, Christopher J., and Cargnello, Matteo. 2018. "Tuning Precursor Reactivity toward Nanometer-Size Control in Palladium Nanoparticles Studied by in Situ Small Angle X-ray Scattering". United States. doi:10.1021/acs.chemmater.7b05186.
@article{osti_1457140,
title = {Tuning Precursor Reactivity toward Nanometer-Size Control in Palladium Nanoparticles Studied by in Situ Small Angle X-ray Scattering},
author = {Wu, Liheng and Lian, Huada and Willis, Joshua J. and Goodman, Emmett D. and McKay, Ian Salmon and Qin, Jian and Tassone, Christopher J. and Cargnello, Matteo},
abstractNote = {Synthesis of monodisperse nanoparticles (NPs) with precisely controlled size is critical for understanding their size-dependent properties. Although significant synthetic developments have been achieved, it is still challenging to synthesize well-defined NPs in a predictive way due to a lack of in-depth mechanistic understanding of reaction kinetics. Here we use synchrotron-based small-angle X-ray scattering (SAXS) to monitor in situ the formation of palladium (Pd) NPs through thermal decomposition of Pd–TOP (TOP: trioctylphosphine) complex via the “heat-up” method. We systematically study the effects of different ligands, including oleylamine, TOP, and oleic acid, on the formation kinetics of Pd NPs. Through quantitative analysis of the real-time SAXS data, we are able to obtain a detailed picture of the size, size distribution, and concentration of Pd NPs during the syntheses, and these results show that different ligands strongly affect the precursor reactivity. We find that oleylamine does not change the reactivity of the Pd–TOP complex but promote the formation of nuclei due to strong ligand–NP binding. On the other hand, TOP and oleic acid substantially change the precursor reactivity over more than an order of magnitude, which controls the nucleation kinetics and determines the final particle size. A theoretical model is used to demonstrate that the nucleation and growth kinetics are dependent on both precursor reactivity and ligand–NP binding affinity, thus providing a framework to explain the synthesis process and the effect of the reaction conditions. Quantitative understanding of the impacts of different ligands enables the successful synthesis of a series of monodisperse Pd NPs in the broad size range from 3 to 11 nm with nanometer-size control, which serve as a model system to study their size-dependent catalytic properties. Furthermore, the in situ SAXS probing can be readily extended to other functional NPs to greatly advance their synthetic design.},
doi = {10.1021/acs.chemmater.7b05186},
journal = {Chemistry of Materials},
number = 3,
volume = 30,
place = {United States},
year = {2018},
month = {1}
}