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

Title: Synthesis of Colloidal Pd/Au Dilute Alloy Nanocrystals and Their Potential for Selective Catalytic Oxidations

Abstract

Selective oxidations are crucial for the creation of valuable chemical building blocks but often require expensive and unstable stoichiometric oxidants such as hydroperoxides and peracids. To date, many catalysts that contain a single type of active site have not been able to attain the desired level of selectivity for partially oxidized products over total combustion. However, catalysts containing multiple types of active sites have proven to be successful for selective reactions. One category of such catalysts is bimetallic alloys, in which catalytic activity and selectivity can be tuned by modifying the surface composition. Traditional catalyst synthesis methods using impregnation struggle to create catalysts with sufficient control over surface chemistry to accurately tune the ensemble size of the desired active sites. Here in this paper, we describe the synthesis of colloidal nanocrystals of dilute alloys of palladium and gold. We show that when supported on titania (TiO 2), tuning the composition of the Pd/Au nanocrystal surface provides a synergistic effect in the selective oxidation of 2-propanol to acetone in the presence of H 2 and O 2. In particular, we show that certain Pd/Au surface ratios exhibit activity and selectivity far superior to Pd or Au individually. Through precise structural characterizationmore » we demonstrate that isolated atoms of Pd exist in the most active catalysts. The synergy between isolated Pd atoms and Au allows for the formation of reactive oxidizing species, likely hydroperoxide groups, responsible for selective oxidation while limiting oxygen dissociation and, thus, complete combustion. This work opens the way to more efficient utilization of scarce noble metals and new options for catalyzed selective oxidations.« less

Authors:
 [1];  [2];  [1];  [2];  [2]; ORCiD logo [1]
+ Show Author Affiliations
  1. Stanford Univ., CA (United States). Dept. of Chemical Engineering and SUNCAT Center for Interface Science and Catalysis
  2. SLAC National Accelerator Lab., Menlo Park, CA (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1484845
Grant/Contract Number:  
AC02-76SF00515
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 140; Journal Issue: 40; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Wrasman, Cody J., Boubnov, Alexey, Riscoe, Andrew R., Hoffman, Adam S., Bare, Simon R., and Cargnello, Matteo. Synthesis of Colloidal Pd/Au Dilute Alloy Nanocrystals and Their Potential for Selective Catalytic Oxidations. United States: N. p., 2018. Web. doi:10.1021/jacs.8b07515.
Copy to clipboard
Wrasman, Cody J., Boubnov, Alexey, Riscoe, Andrew R., Hoffman, Adam S., Bare, Simon R., & Cargnello, Matteo. Synthesis of Colloidal Pd/Au Dilute Alloy Nanocrystals and Their Potential for Selective Catalytic Oxidations. United States. https://doi.org/10.1021/jacs.8b07515
Copy to clipboard
Wrasman, Cody J., Boubnov, Alexey, Riscoe, Andrew R., Hoffman, Adam S., Bare, Simon R., and Cargnello, Matteo. Mon . "Synthesis of Colloidal Pd/Au Dilute Alloy Nanocrystals and Their Potential for Selective Catalytic Oxidations". United States. https://doi.org/10.1021/jacs.8b07515. https://www.osti.gov/servlets/purl/1484845.
Copy to clipboard
@article{osti_1484845,
title = {Synthesis of Colloidal Pd/Au Dilute Alloy Nanocrystals and Their Potential for Selective Catalytic Oxidations},
author = {Wrasman, Cody J. and Boubnov, Alexey and Riscoe, Andrew R. and Hoffman, Adam S. and Bare, Simon R. and Cargnello, Matteo},
abstractNote = {Selective oxidations are crucial for the creation of valuable chemical building blocks but often require expensive and unstable stoichiometric oxidants such as hydroperoxides and peracids. To date, many catalysts that contain a single type of active site have not been able to attain the desired level of selectivity for partially oxidized products over total combustion. However, catalysts containing multiple types of active sites have proven to be successful for selective reactions. One category of such catalysts is bimetallic alloys, in which catalytic activity and selectivity can be tuned by modifying the surface composition. Traditional catalyst synthesis methods using impregnation struggle to create catalysts with sufficient control over surface chemistry to accurately tune the ensemble size of the desired active sites. Here in this paper, we describe the synthesis of colloidal nanocrystals of dilute alloys of palladium and gold. We show that when supported on titania (TiO2), tuning the composition of the Pd/Au nanocrystal surface provides a synergistic effect in the selective oxidation of 2-propanol to acetone in the presence of H2 and O2. In particular, we show that certain Pd/Au surface ratios exhibit activity and selectivity far superior to Pd or Au individually. Through precise structural characterization we demonstrate that isolated atoms of Pd exist in the most active catalysts. The synergy between isolated Pd atoms and Au allows for the formation of reactive oxidizing species, likely hydroperoxide groups, responsible for selective oxidation while limiting oxygen dissociation and, thus, complete combustion. This work opens the way to more efficient utilization of scarce noble metals and new options for catalyzed selective oxidations.},
doi = {10.1021/jacs.8b07515},
url = {https://www.osti.gov/biblio/1484845}, journal = {Journal of the American Chemical Society},
issn = {0002-7863},
number = 40,
volume = 140,
place = {United States},
year = {2018},
month = {9}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/jacs.8b07515
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 14 works
Citation information provided by
Web of Science
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referencing / citing this record:

Corrosion Motivated ROS Generation Helps Endow Titanium with Broad‐Spectrum Antibacterial Abilities
journal, July 2019

Corrosion Motivated ROS Generation Helps Endow Titanium with Broad‐Spectrum Antibacterial Abilities
journal, July 2019

Ultrafine PtRu Dilute Alloy Nanodendrites for Enhanced Electrocatalytic Methanol Oxidation
journal, October 2019

The Synergy of Dilute Pd and Surface Oxygen Species for Methane Upgrading on Au 3 Pd(111)
journal, September 2019

Tailoring the Size and Shape of Colloidal Noble Metal Nanocrystals as a Valuable Tool in Catalysis
journal, April 2019

Platinum–copper single atom alloy catalysts with high performance towards glycerol hydrogenolysis
journal, December 2019

A nickel–iridium alloy as an efficient heterogeneous catalyst for hydrogenation of olefins
journal, January 2019

Catalytic activity of palladium-doped silver dilute nanoalloys for formate oxidation from a theoretical perspective
journal, January 2019

Reductive amination of ethyl levulinate to pyrrolidones over AuPd nanoparticles at ambient hydrogen pressure
journal, January 2019

Monodisperse nanoparticles for catalysis and nanomedicine
journal, January 2019

    [ × clear filter / sort ]

    Similar records in OSTI.GOV collections: