Crystalline Lattice‐Confined Atomic Pt in Metal Carbides to Match Electronic Structures and Hydrogen Evolution Behaviors of Platinum

Platinum‐based catalysts occupy a pivotal position in diverse catalytic applications in hydrogen chemistry and electrochemistry, for instance, the hydrogen evolution reactions (HER). While adsorbed Pt atoms on supports often cause severe mismatching on electronic structures and HER behaviors from me...

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Published in:Advanced materials (Weinheim) Vol. 34; no. 41; pp. e2206368 - n/a
Main Authors: Ma, Tian, Cao, Hao, Li, Shuang, Cao, Sujiao, Zhao, Zhenyang, Wu, Zihe, Yan, Rui, Yang, Chengdong, Wang, Yi, Aken, Peter A., Qiu, Li, Wang, Yang‐Gang, Cheng, Chong
Format: Journal Article
Language:English
Published: Weinheim Wiley Subscription Services, Inc 01.10.2022
Subjects:
atomic catalysts
Atomic radius
Bonding strength
Catalysts
Covalent bonds
Crystal structure
Crystallinity
electrocatalysts
Electrochemistry
Electron orbitals
Energy distribution
Energy levels
Hydrogen
hydrogen evolution reaction
Hydrogen evolution reactions
Lattice design
Metal carbides
Platinum
Polyoxometallates
Tungsten carbide
Valence
water splitting
ISSN:0935-9648, 1521-4095, 1521-4095
Online Access:Get full text
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Summary:Platinum‐based catalysts occupy a pivotal position in diverse catalytic applications in hydrogen chemistry and electrochemistry, for instance, the hydrogen evolution reactions (HER). While adsorbed Pt atoms on supports often cause severe mismatching on electronic structures and HER behaviors from metallic Pt due to the different energy level distribution of electron orbitals. Here, the design of crystalline lattice‐confined atomic Pt in metal carbides using the Pt‐centered polyoxometalate frameworks with strong PtO‐metal covalent bonds is reported. Remarkably, the lattice‐confined atomic Pt in the tungsten carbides (Ptdoped@WCx, both Pt and W have atomic radii of 1.3 Å) exhibit near‐zero valence states and similar electronic structures as metallic Pt, thus delivering matched energy level distributions of the Pt 5dz2 and H 1s orbitals and similar acidic hydrogen evolution behaviors. In alkaline conditions, the Ptdoped@WCx exhibits 40 times greater mass activity (49.5 A mgPt−1 at η = 150 mV) than the Pt@C because of the favorable water dissociation and H* transport. These findings offer a universal pathway to construct urgently needed atomic‐scale catalysts for broad catalytic reactions. Crystalline lattice‐confined atomic Pt in metal carbides with “real” matched properties as metallic platinum are developed using Pt‐centered polyoxometalate frameworks with strong PtOW/Mo covalent bonds. The WC lattice‐confined Pt atoms exhibit near‐zero valence states, similar electronic structures, and matched hydrogen evolution behaviors as Pt(111) surface; remarkably, they offer 40 times greater mass activity than Pt@C‐20% in alkaline conditions.
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ISSN:0935-9648
1521-4095
1521-4095
DOI:10.1002/adma.202206368