Yaling Chen, Xiang Liu, Shiyu Li, Jianjun Li, Mengyang Fan, Song Shu
{"title":"内置电场的结晶-非晶异质结构增强了硝酸盐的串联电还原制氨","authors":"Yaling Chen, Xiang Liu, Shiyu Li, Jianjun Li, Mengyang Fan, Song Shu","doi":"10.1002/adfm.202521409","DOIUrl":null,"url":null,"abstract":"Electrochemical nitrate reduction to ammonia (NO<jats:sub>3</jats:sub><jats:sup>−</jats:sup>RR) presents dual opportunities for sustainable ammonia synthesis and environmental nitrate remediation. However, the catalytic efficiency of the NO<jats:sub>3</jats:sub><jats:sup>−</jats:sup>RR is hindered by the slow kinetics and substantial side reactions. Herein, a crystal‐amorphous (c‐a) heterostructure catalyst, c‐Co<jats:sub>3</jats:sub>O<jats:sub>4</jats:sub>/a‐CuO is reported, that delivers an NH<jats:sub>3</jats:sub> yield rate of 412.5 µmol h<jats:sup>−1</jats:sup> mg<jats:sup>−1</jats:sup> and a Faradaic efficiency of 90% at−0.8 V<jats:sub>RHE</jats:sub> in neutral electrolyte. Specifically, the catalyst operates via a tandem catalysis pathway: a‐CuO facilitates the initial adsorption and deoxygenation of NO<jats:sub>3</jats:sub><jats:sup>−</jats:sup> to promote <jats:sup>*</jats:sup>NO<jats:sub>2</jats:sub> formation, while the resulting <jats:sup>*</jats:sup>NO<jats:sub>2</jats:sub> species are subsequently converted to NH<jats:sub>3</jats:sub> at the c‐Co<jats:sub>3</jats:sub>O<jats:sub>4</jats:sub> sites. Structural and spectroscopic analyses further reveal that the c‐a interface induces charge redistribution and built‐in electric fields, accelerating electron transfer and lowering the energy barrier of the rate‐determining step. Moreover, integration of the c‐Co<jats:sub>3</jats:sub>O<jats:sub>4</jats:sub>/a‐CuO into a Zn‐NO<jats:sub>3</jats:sub><jats:sup>−</jats:sup> battery demonstrates simultaneous environmental remediation, energy storage, and sustainable NH<jats:sub>3</jats:sub> synthesis.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":"40 1","pages":""},"PeriodicalIF":19.0000,"publicationDate":"2025-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Crystalline‐Amorphous Heterostructures with Built‐In Electric Fields Enhance the Tandem Electroreduction of Nitrate to Ammonia\",\"authors\":\"Yaling Chen, Xiang Liu, Shiyu Li, Jianjun Li, Mengyang Fan, Song Shu\",\"doi\":\"10.1002/adfm.202521409\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Electrochemical nitrate reduction to ammonia (NO<jats:sub>3</jats:sub><jats:sup>−</jats:sup>RR) presents dual opportunities for sustainable ammonia synthesis and environmental nitrate remediation. However, the catalytic efficiency of the NO<jats:sub>3</jats:sub><jats:sup>−</jats:sup>RR is hindered by the slow kinetics and substantial side reactions. Herein, a crystal‐amorphous (c‐a) heterostructure catalyst, c‐Co<jats:sub>3</jats:sub>O<jats:sub>4</jats:sub>/a‐CuO is reported, that delivers an NH<jats:sub>3</jats:sub> yield rate of 412.5 µmol h<jats:sup>−1</jats:sup> mg<jats:sup>−1</jats:sup> and a Faradaic efficiency of 90% at−0.8 V<jats:sub>RHE</jats:sub> in neutral electrolyte. Specifically, the catalyst operates via a tandem catalysis pathway: a‐CuO facilitates the initial adsorption and deoxygenation of NO<jats:sub>3</jats:sub><jats:sup>−</jats:sup> to promote <jats:sup>*</jats:sup>NO<jats:sub>2</jats:sub> formation, while the resulting <jats:sup>*</jats:sup>NO<jats:sub>2</jats:sub> species are subsequently converted to NH<jats:sub>3</jats:sub> at the c‐Co<jats:sub>3</jats:sub>O<jats:sub>4</jats:sub> sites. Structural and spectroscopic analyses further reveal that the c‐a interface induces charge redistribution and built‐in electric fields, accelerating electron transfer and lowering the energy barrier of the rate‐determining step. Moreover, integration of the c‐Co<jats:sub>3</jats:sub>O<jats:sub>4</jats:sub>/a‐CuO into a Zn‐NO<jats:sub>3</jats:sub><jats:sup>−</jats:sup> battery demonstrates simultaneous environmental remediation, energy storage, and sustainable NH<jats:sub>3</jats:sub> synthesis.\",\"PeriodicalId\":112,\"journal\":{\"name\":\"Advanced Functional Materials\",\"volume\":\"40 1\",\"pages\":\"\"},\"PeriodicalIF\":19.0000,\"publicationDate\":\"2025-10-11\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Advanced Functional Materials\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://doi.org/10.1002/adfm.202521409\",\"RegionNum\":1,\"RegionCategory\":\"材料科学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Advanced Functional Materials","FirstCategoryId":"88","ListUrlMain":"https://doi.org/10.1002/adfm.202521409","RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Crystalline‐Amorphous Heterostructures with Built‐In Electric Fields Enhance the Tandem Electroreduction of Nitrate to Ammonia
Electrochemical nitrate reduction to ammonia (NO3−RR) presents dual opportunities for sustainable ammonia synthesis and environmental nitrate remediation. However, the catalytic efficiency of the NO3−RR is hindered by the slow kinetics and substantial side reactions. Herein, a crystal‐amorphous (c‐a) heterostructure catalyst, c‐Co3O4/a‐CuO is reported, that delivers an NH3 yield rate of 412.5 µmol h−1 mg−1 and a Faradaic efficiency of 90% at−0.8 VRHE in neutral electrolyte. Specifically, the catalyst operates via a tandem catalysis pathway: a‐CuO facilitates the initial adsorption and deoxygenation of NO3− to promote *NO2 formation, while the resulting *NO2 species are subsequently converted to NH3 at the c‐Co3O4 sites. Structural and spectroscopic analyses further reveal that the c‐a interface induces charge redistribution and built‐in electric fields, accelerating electron transfer and lowering the energy barrier of the rate‐determining step. Moreover, integration of the c‐Co3O4/a‐CuO into a Zn‐NO3− battery demonstrates simultaneous environmental remediation, energy storage, and sustainable NH3 synthesis.
期刊介绍:
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