A Computational Mechanistic Study on Copper Autoreduction in Cu-CHA Zeolite Catalysts.

IF 3.5 3区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY
Miao Wen, Zhuyang Liu, Chong Liu, Wei Zhuang
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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.

Cu-CHA 沸石催化剂中的铜自还原计算机理研究
铜沸石催化剂在活化过程中会发生自还原反应,其中一部分铜(II)会自发还原成铜(I)。有人提出了自还原反应的化学计量学原理,即在释放一个 O2 的同时,四个 Cu(II) 被还原成 Cu(I),但这种自还原反应的具体机理仍不清楚。在这项工作中,我们利用 DFT 计算研究了 Cu-CHA 沸石中的自还原机制。我们系统地研究了 CHA 型沸石中 [CuOH]+ 对 Cu+ 的两种还原机制。在机理 I 中,两个 [CuOH]+ 通过脱水反应生成 [Cu-O-Cu]2+,两个 [Cu-O-Cu]2+ 进一步反应生成 O2 是最关键的一步,这需要四个电荷补偿框架 Al 靠近。在机制 II 中,O2 的生成是通过 [CuO]+ 中间体进行的,而可能的 [CuO]+ 的生成是最关键的一步。在具有不同 Al 坐标的各种 Cu-CHA 模型中对自还原反应的探索表明,两个中间前体(即机制 I 中的两个 [Cu-O-Cu]2+ 或机制 II 中的两个 [CuO]+)之间的 O-O 距离是决定自还原过程中产生 O2 的活化障碍的关键因素。
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来源期刊
Chemistry - An Asian Journal
Chemistry - An Asian Journal 化学-化学综合
CiteScore
7.00
自引率
2.40%
发文量
535
审稿时长
1.3 months
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).
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