In:
Angewandte Chemie, Wiley, Vol. 135, No. 52 ( 2023-12-21)
Abstract:
The active‐site density, intrinsic activity, and durability of Pd−based materials for oxygen reduction reaction (ORR) are critical to their application in industrial energy devices. This work constructs a series of carbon‐based rare‐earth (RE) oxides (Gd 2 O 3 , Sm 2 O 3 , Eu 2 O 3 , and CeO 2 ) by using RE metal–organic frameworks to tune the ORR performance of the Pd sites through the Pd−RE x O y interface interaction. Taking Pd−Gd 2 O 3 /C as a representative, it is identified that the strong coupling between Pd and Gd 2 O 3 induces the formation of the Pd−O−Gd bridge, which triggers charge redistribution of Pd and Gd 2 O 3 . The screened Pd−Gd 2 O 3 /C exhibits impressive ORR performance with high onset potential (0.986 V RHE ), half‐wave potential (0.877 V RHE ), and excellent stability. Similar ORR results are also found for Pd−Sm 2 O 3 /C, Pd−Eu 2 O 3 /C, and Pd−CeO 2 /C catalysts. Theoretical analyses reveal that the coupling between Pd and Gd 2 O 3 promotes electron transfer through the Pd−O−Gd bridge, which induces the antibonding‐orbital occupancy of Pd−*OH for the optimization of *OH adsorption in the rate‐determining step of ORR. The pH‐dependent microkinetic modeling shows that Pd−Gd 2 O 3 is close to the theoretical optimal activity for ORR, outperforming Pt under the same conditions. By its ascendancy in ORR, the Pd−Gd 2 O 3 /C exhibits superior performance in Zn‐air battery as an air cathode, implying its excellent practicability.
Type of Medium:
Online Resource
ISSN:
0044-8249
,
1521-3757
DOI:
10.1002/ange.v135.52
DOI:
10.1002/ange.202314565
Language:
English
Publisher:
Wiley
Publication Date:
2023
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