Active Palladium Structures on Ceria Obtained by Tuning Pd–Pd Distance for Efficient Methane Combustion

Yang, Weiwei; Song, Haohong; Zhang, Lihua; Zhang, Junyan; Polo-Garzon, Felipe; Wang, Haodong; Meyer, Harry; Jiang, De-en; Wu, Zili; Li, Yuanyuan

doi:10.1021/acscatal.4c04985

Title: Active Palladium Structures on Ceria Obtained by Tuning Pd–Pd Distance for Efficient Methane Combustion

Journal Article · 23 October 2024 · ACS Catalysis

DOI: https://doi.org/10.1021/acscatal.4c04985 · OSTI ID:2480017

^[1]; Song, Haohong ^[2];

^[3]; Zhang, Junyan ^[4];

^[4]; Wang, Haodong ^[5];

^[4];

^[2];

^[4];

^[4]

Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Guangdong University of Technology, Guangzhou (China)
Vanderbilt University, Nashville, TN (United States)
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Stony Brook University, NY (United States)

Efficiently removing/converting methane via methane combustion imposes challenges on catalyst design: how to design local structures of a catalytic site so that it has both high intrinsic activity and atomic efficiency? By manipulating the atomic distance of isolated Pd atoms, herein we show that the intrinsic activity of Pd catalysts can be significantly improved for methane combustion via a stable Pd₂ structure on a ceria nanorod support. Guided by theory and confirmed by experiment, we find that the turnover frequency (TOF) of the Pd₂ structure with the Pd–Pd distance of 2.99 Å is higher than that of the Pd₂ structure with the Pd–Pd distance of 2.75 Å; at least 26 times that of ceria supported Pd single atoms and 4 times that of ceria supported PdO nanoparticles. The high intrinsic activity of the 2.99 Å Pd–Pd structure is attributed to the conductive local redox environment from the two O atoms bridging the two Pd²⁺ ions, which facilitates both methane adsorption and activation as well as the production of water and carbon dioxide during the methane oxidation process. In conclusion, this work highlights the sensitivity of catalytic behavior on the local structure of active sites and the fine-tuning of the metal–metal distance enabled by a support local environment for guiding the design of efficient catalysts for reactions that highly rely on Pt-group metals.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-05CH11231; AC05-00OR22725; SC0012704

OSTI ID:: 2480017

Report Number(s):: BNL--227560-2025-JAAM

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 21 Vol. 14; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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