Deep Electron Redistributions Induced by Dual Junctions Facilitating Electroreduction of Dilute Nitrate to Ammonia

The electronic states of metal catalysts can be redistributed by the rectifying contact between metal and semiconductor e.g., N‐doped carbon (NC), while the interfacial regulation degree is very limited. Herein, a deep electronic state regulation is achieved by constructing a novel double‐heterojunc...

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Published in:	Small (Weinheim an der Bergstrasse, Germany) Vol. 20; no. 35; pp. e2402430 - n/a
Main Authors:	Zhang, Lu‐Hua, Zhang, Bo, Hong, Yaohua, You, Yang, Zhou, Yuzhuo, Zhan, Jiayu, Alonzo Poole, David, Yu, Fengshou
Format:	Journal Article
Language:	English
Published:	Germany Wiley Subscription Services, Inc 01-08-2024
Subjects:	Ammonia Catalysts Chemical reduction Cobalt oxides deep electron redistributions Dilution dual junctions Electrocatalysts electrochemical nitrate reduction electron deficient Co Electron states Electron transfer Heterojunctions Nitrates State regulation deep electron redistributions electrochemical nitrate reduction electron deficient Co dual junctions
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Summary:	The electronic states of metal catalysts can be redistributed by the rectifying contact between metal and semiconductor e.g., N‐doped carbon (NC), while the interfacial regulation degree is very limited. Herein, a deep electronic state regulation is achieved by constructing a novel double‐heterojunctional Co/Co3O4@NC catalyst containing Co/Co3O4 and Co3O4/NC heterojunctions. When used for dilute electrochemical NO3− reduction reaction (NO3RR), the as‐prepared Co/Co3O4@NC exhibits an outstanding Faradaic efficiency for NH3 formation (FENH3) of 97.9%, –0.4 V versus RHE and significant NH3 yield of 303.5 mmol h−1 gcat−1 at –0.6 V at extremely low nitrate concentrations (100 ppm NO3−‐N). Experimental and theoretical results reveal that the dual junctions of Co/Co3O4 and Co3O4/NC drive a unidirectional electron transfer from Co to NC (Co→Co3O4→NC), resulting in electron‐deficient Co atoms. The electron‐deficient Co promotes NO3− adsorption, the rate‐determining step (RDS) for NO3RR, facilitating the dilute NO3RR to NH3. The design strategy provides a novel reference for unidirectional multistage regulation of metal electronic states boosting electrochemical dilute NO3RR, which opens up an avenue for deep electronic state regulation of electrocatalyst breaking the limitation of the electronic regulation degree by rectifying contact. By constructing the ternary catalyst Co/Co3O4@NC, the electron transfer is relayed through the double heterojunction of Co@Co3O4 and Co3O4@NC, resulting in the deep electronic regulation of Co. As a result, Co/Co3O4@NC exhibits superior performance for diluting electrochemical NO3− reduction reaction (NO3RR) over ever‐reported Co‐based electrocatalysts. This work provides a promising strategy for deep electronic state regulation of electrocatalysts.
Bibliography:	ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23
ISSN:	1613-6810 1613-6829 1613-6829
DOI:	10.1002/smll.202402430