Catalytic Reaction Rates Controlled by Metal Oxidation State: C−H Bond Cleavage in Methane over Nickel‐Based Catalysts. (27th February 2017)

• Record Type: Journal Article
• Authors: Che, Fanglin; Ha, Su; McEwen, Jean‐Sabin
• Is Part Of: Angewandte Chemie. Volume 129:Number 13(2017)
• Page Start: 3611
• Page End: 3615
• Publication Date: 2017-02-27
• Subjects: C-H-Aktivierung -- Elektrische Felder -- Kohlenstoffspezies -- Methan -- Nickel; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201611796
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: The role of low concentrations of carbon complexes in hydrocarbon decomposition over transition metal surfaces has been a topic of much debate over the past decades. It is also a mystery as to whether or not electric fields can enhance hydrocarbon conversion in an electrochemical device at lower than normal reforming temperatures. To provide a "bottom‐up" fundamental insight, C−H bond cleavage in methane over Ni‐based catalysts was investigated. Our theoretical results show that the presence of carbon or carbide‐like species at the interface between the Ni cluster and its metal‐oxide support, as well as the application of an external positive electric field, can significantly increase the Ni oxidation state. Furthermore, the first C−H bond cleavage in methane is favored as the local oxidation state of Ni increases. Thus, the presence of a low concentration of carbon species, or the addition of a positive electric field will improve the hydrocarbon activation process. Abstract : Von Grund auf analysiert : Die katalytische Aktivität für die erste C‐H‐Bindungsspaltung von Methan wird einer theoretischen Untersuchung zufolge durch den lokalen Oxidationszustand des Nickel‐Katalysators bestimmt. Eine Zunahme der Feldstärke (A) oder der Einschluss geringer Mengen an Kohlenstoff‐Grenzflächenspezies (B) führt zu positiven Partialladungen in den Nickelclustern, welche die C‐H‐Bindungsspaltung beschleunigen.