Activating the PdN4 single-atom sites for 4 electron oxygen reduction reaction via axial oxygen ligand modification

被引:9
作者
Zhou, Shanke [1 ,2 ]
Huang, Shuke [1 ]
Wang, Xiaosha [1 ]
Chen, Shenghua [1 ]
Wang, Lei [2 ]
Zhang, Peixin [1 ]
Zhao, Chenyang [1 ]
机构
[1] Shenzhen Univ, Coll Chem & Environm Engn, Shenzhen 518071, Peoples R China
[2] Shenzhen Univ, Coll Phys & Optoelect Engn, Shenzhen 518060, Peoples R China
关键词
Axial oxygen ligand; Single-atom catalysts; Molten-salt; Electronic structure; Oxygen reduction reaction; METAL-ORGANIC FRAMEWORKS; DOPED POROUS CARBON; MOLTEN-SALT; EFFICIENT; ELECTROCATALYSTS; CATALYST; NANOPARTICLES;
D O I
10.1016/j.cej.2023.145129
中图分类号
X [环境科学、安全科学];
学科分类号
08 ; 0830 ;
摘要
The absence of Pd ensemble sites and weak affinity for O-intermediates in tetracoordinate planar PdN4 sites inhibit O-O bond dissociation and restrict 4e- oxygen reduction reaction (ORR) pathway. Optimizing the adsorption energy between O-intermediates and PdN4 sites is a rational approach for selectively promoting 4eORR electrocatalysis. Herein, we propose a molten-salt strategy for introducing axial oxygen ligand into the PdN4 sites to manipulate the electronic structure and create catalytic O-PdN4 sites (one subsurface axial Pd-O configuration on PdN4 plane) on N-doped graphene nanosheets (O-PdN4-NGS). Density functional theory calculations revealed that the axial Pd-O coordination can induce charge redistribution, downshift the d-band center of Pd and enhance the adsorption affinity of PdN4 site for O-intermediates, thereby leading to superior electrocatalysis activity and selectivity for 4e- ORR process compared to conventional PdN4 sites in 0.1 M KOH (with a positive half-wave potential E1/2 of 0.90 V vs RHE). Moreover, zinc-air battery featuring with O-PdN4 sites delivers a peak power density of 178 mW cm-2 at 227.5 mA cm-2 and stable long-term cycling performance, effectively showcasing the advantages of the axial O ligand modification in practical application. This work provides a constructive strategy to activate the reaction activity and specificity of PdN4 single-atom sites by precisely-tuning the local coordination environment of Pd.
引用
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页数:10
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