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Residual ZnNx moieties in ZIF-8 derived catalysts: Protective and synergistic effects for oxygen reduction

JOURNAL OF CATALYSIS [2024]
Yun-Fei Xia, Bo Liu, Pan Guo, Feng-Di Tu, Li-Xiao Shen, Miao Ma, Yun-Kun Dai, Jing Liu, Bin Xu, Yun-Long Zhang, Lei Zhao, Yan Wang, Zhen-Bo Wang
ABSTRACT

ZIF-8 derived carbons demonstrate admirable application prospects in electrocatalytic fields, while ZnN x remaining in those materials are overlooked, crippling the validity of theoretic studies in researches. Herein, the residual Zn in ZIF-8 derived carbons are found could exceed 10 wt% even at carbonization temperatures over 900℃, and Zn-NCs with various Zn contents are adopted as supports to synthesize low-platinum ORR catalysts. Substantial characterizations manifest that ZnN x in Zn-NC can not only provide Zn source for L1 0 -PtZn intermetallic, but act as ‘spatial barriers’ to prevent the formation of inactive PtN x , elevating the active Pt proportion in catalyst by ∼104%. The resultant Zn-NC-Ar-PtZn exhibits a mass activity of 0.557 mA/g Pt and a peak density of 1.485 W/cm 2 . DFT calculations show the strong thermodynamic tendency of forming PtN 4 without the protection of ZnN 4 , and the superior durability and activity of Zn-NC-Ar-PtZn should be attributed to its Zn-derived ligand effects and the SMSI.

MATERIALS

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