{"title":"多孔配位笼的电荷操纵调节电化学合成的效率和选择性","authors":"Zhifang Su, Kang-Kai Liu, Yu-Qi Xu, Bing Yan, Shuangyin Wang, Zong-Jie Guan, Yuqin Zou, Yu Fang","doi":"10.1002/anie.202420945","DOIUrl":null,"url":null,"abstract":"<p>Electrocatalytic synthesis of high-value chemicals has been attracting growing interest owing to its environmentally benign reaction pathways. Among these processes, the electrocatalytic reduction of nitrate (NO<sub>3</sub><sup>−</sup>) to ammonia (NH<sub>3</sub>), known as NO<sub>3</sub>RR, and the oxidation of 5-hydroxymethylfurfural (HMFOR) stand out as two cornerstone reactions; yet, their efficiency and selectivity pose ongoing challenges. In this study, we introduce a charge manipulation approach for the design of highly efficient electrocatalysts tailored for the simultaneous coupling of NO<sub>3</sub>RR and HMFOR. We have synthesized a range of porous coordination cages (PCCs) that share the same topology and Co/Ni metal centers but incorporate different charged moieties, imparting them with distinct surface net charges. Electrocatalytic evaluations revealed that <b>PCC-Co</b> demonstrated a voltage-dependent activity in NO<sub>3</sub>RR. Conversely, <b>PCC-Ni</b> exhibited a precisely adjustable product selectivity in HMFOR, contingent upon the cage‘s charge state. In situ analysis and Density functional theory (DFT) calculations underscored the profound impact of catalyst charge on the differential adsorption of reaction intermediates and the lowest free energy change (ΔG) during the pivotal reaction step, resulting in alterations to both activity and selectivity. These discoveries provide invaluable insights into the “structure-performance relationship” of NO<sub>3</sub>RR/HMFOR catalysts, highlighting PCCs as promising contenders for advanced electrocatalysts.</p>","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"64 9","pages":""},"PeriodicalIF":16.9000,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Charge Manipulation of Porous Coordination Cages Tunes the Efficiency and Selectivity in Electrochemical Synthesis\",\"authors\":\"Zhifang Su, Kang-Kai Liu, Yu-Qi Xu, Bing Yan, Shuangyin Wang, Zong-Jie Guan, Yuqin Zou, Yu Fang\",\"doi\":\"10.1002/anie.202420945\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>Electrocatalytic synthesis of high-value chemicals has been attracting growing interest owing to its environmentally benign reaction pathways. Among these processes, the electrocatalytic reduction of nitrate (NO<sub>3</sub><sup>−</sup>) to ammonia (NH<sub>3</sub>), known as NO<sub>3</sub>RR, and the oxidation of 5-hydroxymethylfurfural (HMFOR) stand out as two cornerstone reactions; yet, their efficiency and selectivity pose ongoing challenges. In this study, we introduce a charge manipulation approach for the design of highly efficient electrocatalysts tailored for the simultaneous coupling of NO<sub>3</sub>RR and HMFOR. We have synthesized a range of porous coordination cages (PCCs) that share the same topology and Co/Ni metal centers but incorporate different charged moieties, imparting them with distinct surface net charges. Electrocatalytic evaluations revealed that <b>PCC-Co</b> demonstrated a voltage-dependent activity in NO<sub>3</sub>RR. Conversely, <b>PCC-Ni</b> exhibited a precisely adjustable product selectivity in HMFOR, contingent upon the cage‘s charge state. In situ analysis and Density functional theory (DFT) calculations underscored the profound impact of catalyst charge on the differential adsorption of reaction intermediates and the lowest free energy change (ΔG) during the pivotal reaction step, resulting in alterations to both activity and selectivity. These discoveries provide invaluable insights into the “structure-performance relationship” of NO<sub>3</sub>RR/HMFOR catalysts, highlighting PCCs as promising contenders for advanced electrocatalysts.</p>\",\"PeriodicalId\":125,\"journal\":{\"name\":\"Angewandte Chemie International Edition\",\"volume\":\"64 9\",\"pages\":\"\"},\"PeriodicalIF\":16.9000,\"publicationDate\":\"2024-12-23\",\"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://onlinelibrary.wiley.com/doi/10.1002/anie.202420945\",\"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://onlinelibrary.wiley.com/doi/10.1002/anie.202420945","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Charge Manipulation of Porous Coordination Cages Tunes the Efficiency and Selectivity in Electrochemical Synthesis
Electrocatalytic synthesis of high-value chemicals has been attracting growing interest owing to its environmentally benign reaction pathways. Among these processes, the electrocatalytic reduction of nitrate (NO3−) to ammonia (NH3), known as NO3RR, and the oxidation of 5-hydroxymethylfurfural (HMFOR) stand out as two cornerstone reactions; yet, their efficiency and selectivity pose ongoing challenges. In this study, we introduce a charge manipulation approach for the design of highly efficient electrocatalysts tailored for the simultaneous coupling of NO3RR and HMFOR. We have synthesized a range of porous coordination cages (PCCs) that share the same topology and Co/Ni metal centers but incorporate different charged moieties, imparting them with distinct surface net charges. Electrocatalytic evaluations revealed that PCC-Co demonstrated a voltage-dependent activity in NO3RR. Conversely, PCC-Ni exhibited a precisely adjustable product selectivity in HMFOR, contingent upon the cage‘s charge state. In situ analysis and Density functional theory (DFT) calculations underscored the profound impact of catalyst charge on the differential adsorption of reaction intermediates and the lowest free energy change (ΔG) during the pivotal reaction step, resulting in alterations to both activity and selectivity. These discoveries provide invaluable insights into the “structure-performance relationship” of NO3RR/HMFOR catalysts, highlighting PCCs as promising contenders for advanced electrocatalysts.
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.