{"title":"A Computational Mechanistic Study on Copper Autoreduction in Cu-CHA Zeolite Catalysts.","authors":"Miao Wen, Zhuyang Liu, Chong Liu, Wei Zhuang","doi":"10.1002/asia.202400973","DOIUrl":null,"url":null,"abstract":"<p><p>The activation of Cu-zeolite catalysts is accompanied by an autoreduction reaction, in which a part of Cu(II) species is spontaneously reduced to Cu(I) species. The stoichiometry of autoreduction in which the release of one O<sub>2</sub> is accompanied by the reduction of four Cu(II) to Cu(I) has been proposed, but the detailed mechanism of this autoreduction remains unclear. In this work, we used DFT calculations to study the autoreduction mechanism in Cu-CHA zeolites. The two reduction mechanisms of [CuOH]<sup>+</sup> to Cu<sup>+</sup> in CHA-type zeolite were systematically studied. In Mechanism I, two [CuOH]<sup>+</sup> react via dehydration to form [Cu-O-Cu]<sup>2+</sup>, and the further reaction of two [Cu-O-Cu]<sup>2+</sup> to produce O<sub>2</sub> is the most critical step, which requires four charge-compensating framework Al in close proximity. In Mechanism II, the production of O<sub>2</sub> occurs via [CuO]<sup>+</sup> intermediates, and the generation of possible [CuO]<sup>+</sup> is the most critical step. The exploration of autoreduction reactions in a variety of Cu-CHA models with different Al sittings shows that the O-O distances between two intermediate precursors, i. e., two [Cu-O-Cu]<sup>2+</sup> in Mechanism I, or two [CuO]<sup>+</sup> in Mechanism II, are key factors determining the activation barriers of O<sub>2</sub> production during autoreduction.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e202400973"},"PeriodicalIF":3.5000,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Chemistry - An Asian Journal","FirstCategoryId":"1","ListUrlMain":"https://doi.org/10.1002/asia.202400973","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
The activation of Cu-zeolite catalysts is accompanied by an autoreduction reaction, in which a part of Cu(II) species is spontaneously reduced to Cu(I) species. The stoichiometry of autoreduction in which the release of one O2 is accompanied by the reduction of four Cu(II) to Cu(I) has been proposed, but the detailed mechanism of this autoreduction remains unclear. In this work, we used DFT calculations to study the autoreduction mechanism in Cu-CHA zeolites. The two reduction mechanisms of [CuOH]+ to Cu+ in CHA-type zeolite were systematically studied. In Mechanism I, two [CuOH]+ react via dehydration to form [Cu-O-Cu]2+, and the further reaction of two [Cu-O-Cu]2+ to produce O2 is the most critical step, which requires four charge-compensating framework Al in close proximity. In Mechanism II, the production of O2 occurs via [CuO]+ intermediates, and the generation of possible [CuO]+ is the most critical step. The exploration of autoreduction reactions in a variety of Cu-CHA models with different Al sittings shows that the O-O distances between two intermediate precursors, i. e., two [Cu-O-Cu]2+ in Mechanism I, or two [CuO]+ in Mechanism II, are key factors determining the activation barriers of O2 production during autoreduction.
期刊介绍:
Chemistry—An Asian Journal is an international high-impact journal for chemistry in its broadest sense. The journal covers all aspects of chemistry from biochemistry through organic and inorganic chemistry to physical chemistry, including interdisciplinary topics.
Chemistry—An Asian Journal publishes Full Papers, Communications, and Focus Reviews.
A professional editorial team headed by Dr. Theresa Kueckmann and an Editorial Board (headed by Professor Susumu Kitagawa) ensure the highest quality of the peer-review process, the contents and the production of the journal.
Chemistry—An Asian Journal is published on behalf of the Asian Chemical Editorial Society (ACES), an association of numerous Asian chemical societies, and supported by the Gesellschaft Deutscher Chemiker (GDCh, German Chemical Society), ChemPubSoc Europe, and the Federation of Asian Chemical Societies (FACS).