Yan Li, Yingnan Liu, Xianyun Peng, Zilin Zhao, Zhongjian Li, Bin Yang, Qinghua Zhang, Lecheng Lei, Liming Dai, Yang Hou
{"title":"通过工程钯亚纳米团簇加速质子耦合电子转移,实现过氧化氢的规模化电合成","authors":"Yan Li, Yingnan Liu, Xianyun Peng, Zilin Zhao, Zhongjian Li, Bin Yang, Qinghua Zhang, Lecheng Lei, Liming Dai, Yang Hou","doi":"10.1002/anie.202413159","DOIUrl":null,"url":null,"abstract":"Electrosynthesis of H2O2 from oxygen reduction reaction via a two-electron pathway is vital as an alternative for the energy-intensive anthraquinone process. However, this process is largely hindered in neutral and alkaline conditions due to sluggish kinetics associated with the transformation of intermediate O2* into OOH* via proton-coupled electron transfer sourced from slow water dissociation. Herein, we developed Pd sub-nanoclusters on the nickel ditelluride nanosheets (Pd SNCs/NiTe2) to enhance the performance of H2O2 electrosynthesis. The newly-developed Pd SNCs/NiTe2 exhibited a H2O2 selectivity of as high as 99% and a positive shift of onset potential up to 0.81 V. Combined theoretical calculations and experimental studies (e.g., X-ray absorption and attenuated total reflectance-Fourier transform infrared spectra measurements) revealed that the Pd sub-nanoclusters supported by NiTe2 nanosheets efficiently reduced the energy barrier of water dissociation to generate more protons, facilitating the proton feeding kinetics. When used in a flow cell, Pd SNCs/NiTe2 cathode efficiently produced H2O2 with a maximum yield rate of 1.75 mmol h-1 cm-2 and current efficiency of 95% at 100 mA cm-2. Further, an accumulated H2O2 concentration of 1.43 mol L-1 was reached after 10 hours of continuous electrolysis, showing the potential for practical H2O2 electrosynthesis.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":null,"pages":null},"PeriodicalIF":16.1000,"publicationDate":"2024-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Accelerated Proton-Coupled Electron Transfer via Engineering Palladium Sub-Nanoclusters for Scalable Electrosynthesis of Hydrogen Peroxide\",\"authors\":\"Yan Li, Yingnan Liu, Xianyun Peng, Zilin Zhao, Zhongjian Li, Bin Yang, Qinghua Zhang, Lecheng Lei, Liming Dai, Yang Hou\",\"doi\":\"10.1002/anie.202413159\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Electrosynthesis of H2O2 from oxygen reduction reaction via a two-electron pathway is vital as an alternative for the energy-intensive anthraquinone process. However, this process is largely hindered in neutral and alkaline conditions due to sluggish kinetics associated with the transformation of intermediate O2* into OOH* via proton-coupled electron transfer sourced from slow water dissociation. Herein, we developed Pd sub-nanoclusters on the nickel ditelluride nanosheets (Pd SNCs/NiTe2) to enhance the performance of H2O2 electrosynthesis. The newly-developed Pd SNCs/NiTe2 exhibited a H2O2 selectivity of as high as 99% and a positive shift of onset potential up to 0.81 V. Combined theoretical calculations and experimental studies (e.g., X-ray absorption and attenuated total reflectance-Fourier transform infrared spectra measurements) revealed that the Pd sub-nanoclusters supported by NiTe2 nanosheets efficiently reduced the energy barrier of water dissociation to generate more protons, facilitating the proton feeding kinetics. When used in a flow cell, Pd SNCs/NiTe2 cathode efficiently produced H2O2 with a maximum yield rate of 1.75 mmol h-1 cm-2 and current efficiency of 95% at 100 mA cm-2. Further, an accumulated H2O2 concentration of 1.43 mol L-1 was reached after 10 hours of continuous electrolysis, showing the potential for practical H2O2 electrosynthesis.\",\"PeriodicalId\":125,\"journal\":{\"name\":\"Angewandte Chemie International Edition\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":16.1000,\"publicationDate\":\"2024-09-10\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Angewandte Chemie International Edition\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1002/anie.202413159\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Angewandte Chemie International Edition","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1002/anie.202413159","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Accelerated Proton-Coupled Electron Transfer via Engineering Palladium Sub-Nanoclusters for Scalable Electrosynthesis of Hydrogen Peroxide
Electrosynthesis of H2O2 from oxygen reduction reaction via a two-electron pathway is vital as an alternative for the energy-intensive anthraquinone process. However, this process is largely hindered in neutral and alkaline conditions due to sluggish kinetics associated with the transformation of intermediate O2* into OOH* via proton-coupled electron transfer sourced from slow water dissociation. Herein, we developed Pd sub-nanoclusters on the nickel ditelluride nanosheets (Pd SNCs/NiTe2) to enhance the performance of H2O2 electrosynthesis. The newly-developed Pd SNCs/NiTe2 exhibited a H2O2 selectivity of as high as 99% and a positive shift of onset potential up to 0.81 V. Combined theoretical calculations and experimental studies (e.g., X-ray absorption and attenuated total reflectance-Fourier transform infrared spectra measurements) revealed that the Pd sub-nanoclusters supported by NiTe2 nanosheets efficiently reduced the energy barrier of water dissociation to generate more protons, facilitating the proton feeding kinetics. When used in a flow cell, Pd SNCs/NiTe2 cathode efficiently produced H2O2 with a maximum yield rate of 1.75 mmol h-1 cm-2 and current efficiency of 95% at 100 mA cm-2. Further, an accumulated H2O2 concentration of 1.43 mol L-1 was reached after 10 hours of continuous electrolysis, showing the potential for practical H2O2 electrosynthesis.
期刊介绍:
Angewandte Chemie, a journal of the German Chemical Society (GDCh), maintains a leading position among scholarly journals in general chemistry with an impressive Impact Factor of 16.6 (2022 Journal Citation Reports, Clarivate, 2023). Published weekly in a reader-friendly format, it features new articles almost every day. Established in 1887, Angewandte Chemie is a prominent chemistry journal, offering a dynamic blend of Review-type articles, Highlights, Communications, and Research Articles on a weekly basis, making it unique in the field.