Abstract
Supported Pd single atom catalysts (SACs) have triggered great research interest in methane combustion yet with contradicting views on their activity and stability. Here, we show that the Pd SAs can take different electronic structure and atomic geometry on ceria support, resulting in different catalytic properties. By a simple thermal pretreatment to ceria prior to Pd deposition, a unique anchoring site is created. The Pd SA, taking this site, can be activated to Pdδ+ (0<δ<2) that has greatly enhanced activity for methane oxidation: T50 lowered by up to 130 °C and almost 10 times higher turnover frequency compared to the untreated catalyst. The enhanced activity of Pdδ+ site is related to its oxygen-deficient local structure and elongated interacting distance with ceria, leading to enhanced capability in delivering reactive oxygen species and decomposing reaction intermediates. This work provides insights into designing highly efficient Pd SACs for oxidation reactions.
Original language | English |
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Article number | e202217323 |
Journal | Angewandte Chemie - International Edition |
Volume | 62 |
Issue number | 5 |
DOIs | |
State | Published - Jan 26 2023 |
Funding
Note: This manuscript has been authored in part by UT‐Battelle, LLC, under contract DE‐AC05‐00OR22725 with the US Department of Energy (DOE). The US government retains and the publisher, by accepting the article for publication, acknowledges that the US government retains a nonexclusive, paid‐up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for US government purposes. DOE will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan ( http://energy.gov/downloads/doe‐public‐access‐plan ). This research is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, Catalysis Science Program. The sample preparation, reaction test, IR/Raman and STEM studies were conducted as part of a user project at the Center for Nanophase Materials Sciences, which is a Department of Energy, Office of Science User Facility at Oak Ridge National Laboratory. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science user facility at Argonne National Laboratory and is based on research supported by the U.S. DOE Office of Science-Basic Energy Sciences, under Contract No. DE-AC02-06CH11357. W.Y. acknowledges the fellowship from China Scholarship Council. Note: This manuscript has been authored in part by UT-Battelle, LLC, under contract DE-AC05-00OR22725 with the US Department of Energy (DOE). The US government retains and the publisher, by accepting the article for publication, acknowledges that the US government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for US government purposes. DOE will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan (http://energy.gov/downloads/doe-public-access-plan). This research is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, Catalysis Science Program. The sample preparation, reaction test, IR/Raman and STEM studies were conducted as part of a user project at the Center for Nanophase Materials Sciences, which is a Department of Energy, Office of Science User Facility at Oak Ridge National Laboratory. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science user facility at Argonne National Laboratory and is based on research supported by the U.S. DOE Office of Science‐Basic Energy Sciences, under Contract No. DE‐AC02‐06CH11357. W.Y. acknowledges the fellowship from China Scholarship Council.
Keywords
- Ceria
- Methane Oxidation
- Palladium
- Single Atoms
- Thermal Pretreatment