journal article·2022-03-16

Two-Dimensional Palladium Phosphoronitride for Oxygen Reduction

See Wee Koh, Jie Hu, Hoje Chun, Peng Yu, Junyu Ge, Zixu Sun, Wei Hong, Qiunan Liu, Kyungju Nam, Byungchan Han, Zheng Liu, Hong Li

ACS Applied Materials & Interfaces· Volume 14· Issue 10
Publisher page

Abstract

Two-dimensional (2D) catalysts often show extraordinary activity at low mass loading since almost all their atoms are exposed to electrolyte. Palladium (Pd) holds great promise for catalyzing oxygen reduction reaction (ORR) but 2D Pd-based ORR catalyst has rarely been reported. Herein, 2D ternary palladium phosphoronitride (Pd3P2Nx) is synthesized, for the first time, for ORR catalysis. The synthesis is guided by a rational design using first-principles density functional theory calculations, and then realized via a postsynthesis substitutional doping of ternary palladium thiophosphate (Pd3P2S8), which almost completely replaces sulfur atoms by nitrogen atoms without destroying the 2D morphology. The doping process exposes the interlocked Pd atoms of Pd3P2S8 and introduces ligands that improve the affinity of oxygen intermediates, resulting in greater kinetics and lower activation energy for ORR. The mass activity of the pristine Pd3P2S8 is dramatically increased as much as 5-fold (from 0.03 to 0.151 mA μg–1 Pd in Pd3P2Nx). The ORR diffusion-limited current density of Pd3P2Nx (6.2 mA cm–2) exceeds that of commercial Pt/C, and it shows fast kinetics and robust long-term stability. Our theoretical calculations not only guide the experimental doping process, but also provides insights into the underlying mechanism of the outstanding ORR activity and stability.
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Research context

OpenAlex topics: Electrocatalysts for Energy Conversion · Fuel Cells and Related Materials · Advanced Photocatalysis Techniques

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

Affiliations

School of Mechanical and Aerospace Engineering, Nanyang Technological University, 639798, Singapore

State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao 066004, P. R. China

Department of Chemical and Biomolecular Engineering, Yonsei University, Seoul 03722, Republic of Korea

State Key Laboratory of Optoelectronic Materials and Technologies, Guangzhou Key Laboratory of Flexible Electronic Materials and Wearable Devices, School of Materials Science and Engineering, Sun Yat-sen University, Guangzhou 510275, People’s Republic of China

Nano Energy Center, State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao 066004, P. R. China

Institute of Fundamental and Advanced Technology, R&D Division, Hyundai Motor Company, Uiwang 16082, Republic of Korea

Department of Vehicle Convergence Engineering, Yonsei University, Seoul 03722, Republic of Korea

School of Material Sciences and Engineering, Nanyang Technological University, 639798, Singapore

CINTRA CNRS/NTU/THALES, UMI 3288, Research Techno Plaza, 637553, Singapore

Funding

Sun Yat-sen University · Natural Science Foundation of Hebei Province · Ministry of Science and Technology of the People's Republic of China · Ministry of Education - Singapore · National Research Foundation of Korea · National Natural Science Foundation of China · Natural Science Foundation of Guangdong Province · Nanyang Technological University · Guangzhou Science and technology project

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