TY - JOUR
T1 - Reversible Atomization and Nano-Clustering of Pt as a Strategy for Designing Ultra-Low-Metal-Loading Catalysts
AU - Chakraborty, Debasish
AU - Smitshuysen, Thomas Erik Lyck
AU - Kakekhani, Arvin
AU - Jespersen, Sebastian Pirel Fredsgaard
AU - Banerjee, Sayan
AU - Krabbe, Alexander
AU - Hagen, Nicolai
AU - Silva, Hugo
AU - Just, Justus
AU - Damsgaard, Christian Danvad
AU - Helveg, Stig
AU - Rappe, Andrew M.
AU - Nørskov, Jens K.
AU - Chorkendorff, Ib
N1 - Publisher Copyright:
©
PY - 2022
Y1 - 2022
N2 - Noble metal-based catalysts have numerous industrial uses, and maximum utilization of the precious metals by lowering the metal loading is of significant interest in heterogeneous catalysis research. However, lowering the metal loading could lead to single-Atom metal species formation, which may not be active for important reactions like propylene oxidation. We report a way to drastically reduce precious metal loading of catalysts by judiciously choosing an active metal/support pair and using the reversible atomization-nanoparticulate formation of transition metal on a high-surface area support. Here, Pt and MgAl2O4 are used as the transition metal and high-surface area support, respectively. Through catalytic testing and characterization using scanning transmission electron microscopy and synchrotron X-ray absorption spectroscopy, a reversible change between atomization and nano-cluster formation under oxidizing and reducing conditions has been found. Via density functional theory, favorable sites for reversible Pt adsorption are identified, including ionic Pt4+ sites that can serve to nucleate nanoclusters. Catalytic reaction modeling also rationalizes the catalytic inertness of atomic Pt sites. Finally, a re-Activation mechanism for the atomized Pt based on gases present during reaction has been formulated and demonstrated.
AB - Noble metal-based catalysts have numerous industrial uses, and maximum utilization of the precious metals by lowering the metal loading is of significant interest in heterogeneous catalysis research. However, lowering the metal loading could lead to single-Atom metal species formation, which may not be active for important reactions like propylene oxidation. We report a way to drastically reduce precious metal loading of catalysts by judiciously choosing an active metal/support pair and using the reversible atomization-nanoparticulate formation of transition metal on a high-surface area support. Here, Pt and MgAl2O4 are used as the transition metal and high-surface area support, respectively. Through catalytic testing and characterization using scanning transmission electron microscopy and synchrotron X-ray absorption spectroscopy, a reversible change between atomization and nano-cluster formation under oxidizing and reducing conditions has been found. Via density functional theory, favorable sites for reversible Pt adsorption are identified, including ionic Pt4+ sites that can serve to nucleate nanoclusters. Catalytic reaction modeling also rationalizes the catalytic inertness of atomic Pt sites. Finally, a re-Activation mechanism for the atomized Pt based on gases present during reaction has been formulated and demonstrated.
U2 - 10.1021/acs.jpcc.2c05213
DO - 10.1021/acs.jpcc.2c05213
M3 - Journal article
AN - SCOPUS:85138768260
VL - 126
SP - 16194
EP - 16203
JO - The Journal of Physical Chemistry Part C
JF - The Journal of Physical Chemistry Part C
SN - 1932-7447
IS - 38
ER -