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Title: Relating adatom emission to improved durability of Pt-Pd diesel oxidation catalysts

Journal Article · · Journal of Catalysis
 [1];  [2];  [1];  [3];  [3];  [4];  [5];  [5];  [1]
  1. Univ. of New Mexico, Albuquerque, NM (United States)
  2. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
  3. Einhoven Univ. of Technology, Eindhoven (The Netherlands)
  4. New Mexico State Univ., Las Cruces, NM (United States)
  5. General Motors Global R&D, Warren, MI (United States)

Sintering of nanoparticles is an important contributor to loss of activity in heterogeneous catalysts, such as those used for controlling harmful emissions from automobiles. But mechanistic details, such as the rates of atom emission or the nature of the mobile species, remain poorly understood. Herein we report a novel approach that allows direct measurement of atom emission from nanoparticles. We use model catalyst samples and a novel reactor that allows the same region of the sample to be observed after short-term heat treatments (seconds) under conditions relevant to diesel oxidation catalysts (DOCs). Monometallic Pd is very stable and does not sinter when heated in air (T ≤ 800 °C). Pt sinters readily in air, and at high temperatures (≥800 °C) mobile Pt species emitted to the vapor phase cause the formation of large, faceted particles. In Pt–Pd nanoparticles, Pd slows the rate of emission of atoms to the vapor phase due to the formation of an alloy. However, the role of Pd in Pt DOCs in air is quite complex: at low temperatures, Pt enhances the rate of Pd sintering (which otherwise would be stable as an oxide), while at higher temperature Pd helps to slow the rate of Pt sintering. DFT calculations show that the barrier for atom emission to the vapor phase is much greater than the barrier for emitting atoms to the support. Thus, vapor-phase transport becomes significant only at high temperatures while diffusion of adatoms on the support dominates at lower temperatures.

Research Organization:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Organization:
USDOE National Nuclear Security Administration (NNSA)
Grant/Contract Number:
AC04-94AL85000
OSTI ID:
1235327
Alternate ID(s):
OSTI ID: 1434176
Report Number(s):
SAND-2015-4863J; 594892
Journal Information:
Journal of Catalysis, Vol. 328, Issue C; ISSN 0021-9517
Publisher:
ElsevierCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 60 works
Citation information provided by
Web of Science

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In Situ XPS and MS Study of Methane Oxidation on the Pd–Pt/Al2O3 Catalysts journal January 2020
Supercritical flow synthesis of PtPdFe alloyed nanoparticles with enhanced low-temperature activity and thermal stability for propene oxidation under lean exhaust gas conditions journal January 2019
Transformation of a Pt-CeO 2 Mechanical Mixture of Pulsed-Laser-Ablated Nanoparticles to a Highly Active Catalyst for Carbon Monoxide Oxidation journal March 2018
Thermally stable single-atom platinum-on-ceria catalysts via atom trapping journal July 2016
Atomically dispersed platinum on low index and stepped ceria surfaces: phase diagrams and stability analysis journal January 2020
Three-Dimensional Probing of Catalyst Ageing on Different Length Scales: A Case Study of Changes in Microstructure and Activity for CO Oxidation of a Pt-Pd/Al 2 O 3 Catalyst journal June 2017
Theoretical Study of Ripening Mechanisms of Pd Clusters on Ceria journal October 2017
Palladium Intercalated into the Walls of Mesoporous Silica as Robust and Regenerable Catalysts for Hydrodeoxygenation of Phenolic Compounds journal July 2018