Unraveling Molecular Fingerprints of Catalytic Sulfur Poisoning at the Nanometer Scale with Near-Field Infrared Spectroscopy
Artikel i vetenskaplig tidskrift, 2022
Fundamental understanding of catalytic deactivation phenomena such as sulfur poisoning occurring on metal/metal-oxide interfaces is essential for the development of high-performance heterogeneous catalysts with extended lifetimes. Unambiguous identification of catalytic poisoning species requires experimental methods simultaneously delivering accurate information regarding adsorption sites and adsorption geometries of adsorbates with nanometer-scale spatial resolution, as well as their detailed chemical structure and surface functional groups. However, to date, it has not been possible to study catalytic sulfur poisoning of metal/metal-oxide interfaces at the nanometer scale without sacrificing chemical definition. Here, we demonstrate that near-field nano-infrared spectroscopy can effectively identify the chemical nature, adsorption sites, and adsorption geometries of sulfur-based catalytic poisons on a Pd(nanodisk)/Al2O3 (thin-film) planar model catalyst surface at the nanometer scale. The current results reveal striking variations in the nature of sulfate species from one nanoparticle to another, vast alterations of sulfur poisoning on a single Pd nanoparticle as well as at the assortment of sulfate species at the active metal-metal-oxide support interfacial sites. These findings provide critical molecular-level insights crucial for the development of long-lifetime precious metal catalysts resistant toward deactivation by sulfur.
Författare
Zafer Say
Bilkent Universitesi
Chalmers, Fysik, Kemisk fysik
TOBB University of Economics and Technology
Melike Kaya
Ankara Universitesi
Turkish Accelerator and Radiation Laboratory
Çaǧll Kaderoǧlu
Ankara Universitesi
Turkish Accelerator and Radiation Laboratory
Yusuf Kocak
Bilkent Universitesi
Kerem Emre Ercan
Bilkent Universitesi
Abel Tetteh Sika-Nartey
Bilkent Universitesi
Ahsan Jalal
Bilkent Universitesi
Ahmet Arda Turk
Bilkent Universitesi
Christoph Langhammer
Chalmers, Fysik, Kemisk fysik
Mirali Jahangirzadeh Varjovi
Bilkent Universitesi
Engin Durgun
Bilkent Universitesi
Emrah Ozensoy
Bilkent Universitesi
Journal of the American Chemical Society
0002-7863 (ISSN) 1520-5126 (eISSN)
Vol. 144 19 8848-8860Ämneskategorier
Oorganisk kemi
Materialkemi
Annan kemi
DOI
10.1021/jacs.2c03088
PubMed
35486918