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In Situ Dispersion of Palladium on TiO 2 During Reverse Water–Gas Shift Reaction: Formation of Atomically Dispersed Palladium
Author(s) -
Nelson Nicholas C.,
Chen Linxiao,
Meira Debora,
Kovarik Libor,
Szanyi János
Publication year - 2020
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202007576
Subject(s) - palladium , catalysis , water gas shift reaction , dispersion (optics) , in situ , chemistry , cluster (spacecraft) , vacancy defect , materials science , metal , chemical engineering , crystallography , organic chemistry , physics , computer science , optics , programming language , engineering
The application of single‐atom catalysts (SACs) to high‐temperature hydrogenation requires materials that thermodynamically favor metal atom isolation over cluster formation. We demonstrate that Pd can be predominantly dispersed as isolated atoms onto TiO 2 during the reverse water–gas shift (rWGS) reaction at 400 °C. Achieving atomic dispersion requires an artificial increase of the absolute TiO 2 surface area by an order of magnitude and can be accomplished by physically mixing a precatalyst (Pd/TiO 2 ) with neat TiO 2 prior to the rWGS reaction. The in situ dispersion of Pd was reflected through a continuous increase of rWGS activity over 92 h and supported by kinetic analysis, infrared and X‐ray absorption spectroscopies and scanning transmission electron microscopy. The thermodynamic stability of Pd under high‐temperature rWGS conditions is associated with Pd‐Ti coordination, which manifests upon O‐vacancy formation, and the artificial increase in TiO 2 surface area.