Abstract Herein, we report on the synthesis of ultrasmall Pd nanoclusters (∼2 nm) protected by L‐cysteine [HOCOCH(NH2)CH2SH] ligands (Pdn(L‐Cys)m) and supported on the surfaces of CeO2, TiO2, Fe3O4, and ZnO nanoparticles for CO catalytic oxidation. The Pdn(L‐Cys)mnanoclusters supported on the reducible metal oxides CeO2, TiO2and Fe3O4exhibit a remarkable catalytic activity towards CO oxidation, significantly higher than the reported Pd nanoparticle catalysts. The high catalytic activity of the ligand‐protected clusters Pdn(L‐Cys)mis observed on the three reducible oxides where 100 % CO conversion occurs at 93–110 °C. The high activity is attributed to the ligand‐protected Pd nanoclusters where the L‐cysteine ligands aid in achieving monodispersity of the Pd clusters by limiting the cluster size to the active sub‐2‐nm region and decreasing the tendency of the clusters for agglomeration. In the case of the ceria support, a complete removal of the L‐cysteine ligands results in connected agglomerated Pd clusters which are less reactive than the ligand‐protected clusters. However, for the TiO2and Fe3O4supports, complete removal of the ligands from the Pdn(L‐Cys)mclusters leads to a slight decrease in activity where the T100%CO conversion occurs at 99 °C and 107 °C, respectively. The high porosity of the TiO2and Fe3O4supports appears to aid in efficient encapsulation of the bare Pdnnanoclusters within the mesoporous pores of the support.
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This content will become publicly available on January 1, 2026
Impact of Flame Conditions on the Pd‐O Structure and Methane Oxidation Activity over Ceria Support
Abstract In this work, we employed flame spray pyrolysis (FSP), a high‐temperature synthesis method, to control the formation of Pd structures on the CeO2support. Multiple types of Pd structures deposited on CeO2are observed on FSP‐made samples. Our results show that the oxidizing environment during FSP synthesis facilitates the formation of incorporated Pd2+structures, along with highly dispersed Pd2+, Pd0nanoparticles, and Pd° clusters formed under the reducing synthesis condition. Notably, these Pd2+species remained stable at temperatures up to 400 °C. The catalysts containing both highly dispersed Pd2+nanoparticles and incorporated Pd2+species demonstrated superior methane oxidation activity, with higher turnover frequencies than those containing only one type of Pd2+structure. However, hydrothermal pretreatment in the presence of water vapor led to partial deactivation, likely due to structural alterations in the Pd species or the interaction with the CeO2support, which reduced the stability and effectiveness of the active sites. This study underscores the importance of both highly dispersed and incorporated Pd2+species in enhancing catalytic performance and highlights the challenges posed by water‐induced deactivation in practical applications.
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- Award ID(s):
- 2011967
- PAR ID:
- 10590661
- Publisher / Repository:
- Wiley
- Date Published:
- Journal Name:
- ChemCatChem
- Volume:
- 17
- Issue:
- 2
- ISSN:
- 1867-3880
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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