Adarsh Koovakattil Surendran, Elija Veenman, Jana Roithová
{"title":"碱金属离子调节冠醚添加型卟啉的电催化二氧化碳还原作用","authors":"Adarsh Koovakattil Surendran, Elija Veenman, Jana Roithová","doi":"10.1002/ejic.202400259","DOIUrl":null,"url":null,"abstract":"Iron‐porphyrin systems are among the best catalysts to reduce selectively CO2 to CO. Electronic modification of the porphyrin skeleton by substituents can enhance the catalytic efficiency of the complexes. In this work, we modified the iron porphyrin complex with crown‐ether auxiliaries and tested the effect of complexation with alkali metals on their electrocatalytic properties for CO2 reduction. The presence of Na+ or K+ resulted in a positive shift of the onset potential by 210 mV while not compromising the catalytic current. This effect was maintained after the immobilization at the vulcanized carbon support, and the catalyst showed the Faradaic efficiency above 90% for CO2 to CO reduction in aqueous solution of NaHCO3 or KHCO3 in a wide range of overpotentials. Hence, host‐guest chemistry at the periphery of the CO2 reduction catalysts can tune the electronic properties of the catalysts and thereby increase the catalytic efficiency.","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":2.2000,"publicationDate":"2024-08-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Alkali Metal Ion Tuning of a Crown Ether‐Appended Porphyrin for Electrocatalytic CO2 Reduction\",\"authors\":\"Adarsh Koovakattil Surendran, Elija Veenman, Jana Roithová\",\"doi\":\"10.1002/ejic.202400259\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Iron‐porphyrin systems are among the best catalysts to reduce selectively CO2 to CO. Electronic modification of the porphyrin skeleton by substituents can enhance the catalytic efficiency of the complexes. In this work, we modified the iron porphyrin complex with crown‐ether auxiliaries and tested the effect of complexation with alkali metals on their electrocatalytic properties for CO2 reduction. The presence of Na+ or K+ resulted in a positive shift of the onset potential by 210 mV while not compromising the catalytic current. This effect was maintained after the immobilization at the vulcanized carbon support, and the catalyst showed the Faradaic efficiency above 90% for CO2 to CO reduction in aqueous solution of NaHCO3 or KHCO3 in a wide range of overpotentials. Hence, host‐guest chemistry at the periphery of the CO2 reduction catalysts can tune the electronic properties of the catalysts and thereby increase the catalytic efficiency.\",\"PeriodicalId\":38,\"journal\":{\"name\":\"European Journal of Inorganic Chemistry\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":2.2000,\"publicationDate\":\"2024-08-26\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"European Journal of Inorganic Chemistry\",\"FirstCategoryId\":\"1\",\"ListUrlMain\":\"https://doi.org/10.1002/ejic.202400259\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, INORGANIC & NUCLEAR\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"European Journal of Inorganic Chemistry","FirstCategoryId":"1","ListUrlMain":"https://doi.org/10.1002/ejic.202400259","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
引用次数: 0
摘要
铁-卟啉系统是将 CO2 选择性还原为 CO 的最佳催化剂之一。通过取代基对卟啉骨架进行电子修饰可以提高络合物的催化效率。在这项工作中,我们用冠醚助剂修饰了铁卟啉配合物,并测试了与碱金属络合对其还原 CO2 的电催化性能的影响。Na+ 或 K+ 的存在导致起始电位正移 210 mV,同时不会影响催化电流。在硫化碳载体上固定后,这种效果得以保持,催化剂在 NaHCO3 或 KHCO3 水溶液中将 CO2 还原为 CO 时,在很宽的过电位范围内,法拉第效率都超过了 90%。因此,二氧化碳还原催化剂外围的主客体化学反应可以调节催化剂的电子特性,从而提高催化效率。
Alkali Metal Ion Tuning of a Crown Ether‐Appended Porphyrin for Electrocatalytic CO2 Reduction
Iron‐porphyrin systems are among the best catalysts to reduce selectively CO2 to CO. Electronic modification of the porphyrin skeleton by substituents can enhance the catalytic efficiency of the complexes. In this work, we modified the iron porphyrin complex with crown‐ether auxiliaries and tested the effect of complexation with alkali metals on their electrocatalytic properties for CO2 reduction. The presence of Na+ or K+ resulted in a positive shift of the onset potential by 210 mV while not compromising the catalytic current. This effect was maintained after the immobilization at the vulcanized carbon support, and the catalyst showed the Faradaic efficiency above 90% for CO2 to CO reduction in aqueous solution of NaHCO3 or KHCO3 in a wide range of overpotentials. Hence, host‐guest chemistry at the periphery of the CO2 reduction catalysts can tune the electronic properties of the catalysts and thereby increase the catalytic efficiency.
期刊介绍:
The European Journal of Inorganic Chemistry (2019 ISI Impact Factor: 2.529) publishes Full Papers, Communications, and Minireviews from the entire spectrum of inorganic, organometallic, bioinorganic, and solid-state chemistry. It is published on behalf of Chemistry Europe, an association of 16 European chemical societies.
The following journals have been merged to form the two leading journals, European Journal of Inorganic Chemistry and European Journal of Organic Chemistry:
Chemische Berichte
Bulletin des Sociétés Chimiques Belges
Bulletin de la Société Chimique de France
Gazzetta Chimica Italiana
Recueil des Travaux Chimiques des Pays-Bas
Anales de Química
Chimika Chronika
Revista Portuguesa de Química
ACH—Models in Chemistry
Polish Journal of Chemistry
The European Journal of Inorganic Chemistry continues to keep you up-to-date with important inorganic chemistry research results.