Alloying Pt Sub-nano-clusters with Boron: Sintering Preventative and Coke Antagonist?

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• 作者：Jonny Dadras ; Elisa Jimenez-Izal ; Anastassia N. Alexandrova
• 刊名：ACS Catalysis
• 出版年：2015
• 出版时间：October 2, 2015
• 年：2015
• 卷：5
• 期：10
• 页码：5719-5727
• 全文大小：560K
• ISSN：2155-5435

文摘

Immobilized Pt clusters are interesting catalysts for dehydrogenation of alkanes. However, surface-deposited Pt clusters deactivate rapidly via sintering and coke deposition. The results reported here suggest that adding boron to oxide-supported Pt clusters could be a 鈥渕agic bullet鈥?against both means of deactivation. The model systems studied herein are pure and B-doped Pt clusters deposited on MgO(100). The nonstoichiometric boride cluster obtained via such alloying is found to anchor to the support via a covalent B鈥揙 bond, and the cluster-surface binding is much stronger than in the case of pure Pt clusters. Additionally, B introduces covalency to the intracluster bonding, leading to structural distortion and stabilization. The energy required to dissociate a Pt atom from a boride cluster is significantly larger than that of pure Pt clusters. These energetic arguments lead to the proposal that sintering via both Ostwald ripening and particle coalescence would be discouraged relative to pure Pt clusters. Finally, it is shown that the affinity to C also drops dramatically for borated clusters, discouraging coking and increasing the selectivity of potential cluster catalysts.