Theoretical Study of the Deposition of Pt Clusters on Defective Hexagonal Boron Nitride (h-BN) Sheets: Morphologies, Electronic Structures, and Interactions with O

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• 作者：Duo Xu ; Yue-jie Liu ; Jing-xiang Zhao ; Qing-hai Cai ; Xuan-zhang Wang
• 刊名：Journal of Physical Chemistry C
• 出版年：2014
• 出版时间：May 1, 2014
• 年：2014
• 卷：118
• 期：17
• 页码：8868-8876
• 全文大小：578K
• 年卷期：v.118,no.17(May 1, 2014)
• ISSN：1932-7455

文摘

Recent studies have shown that two-dimensional nanomaterials can serve as excellent candidates for the support of metal nanoparticles, thus rendering them to have potential applications for developing novel electrocatalysts in the oxygen reduction reaction (ORR). In this work, by performing density functional theory calculations, we investigate the structural and electronic properties of Pt clusters deposited on several defective hexagonal boron nitride (h-BN) sheets as well as their interaction with O that is closely related to the electrocatalytic activity of these composites in ORR. As compared with the pristine h-BN sheet, we find that the binding strength of Pt clusters on defective h-BN sheets is significantly enhanced, which is attributed to their strong hybridization with the sp² dangling bonds at the vacancy site. Thus, the point defect on h-BN sheets plays a key role on anchoring Pt clusters, ensuring their high stability. More importantly, the interfacial interaction can effectively modify the averaged d-band center of the deposited Pt clusters, greatly influencing their interaction with O. The adsorption energies of O on Pt₁₃ clusters deposited on h-BN sheets with V^B, V^N, and V^B+N vacancies are 鈭?.32, 鈭?.77, and 鈭?.86 eV, respectively, which are weaker than that on a free Pt₁₃ cluster (鈭?.70 eV), suggesting that the kinetics over these composites in ORR will be promoted. Thus, we expect that Pt nanoclusters deposited on defective h-BN sheets would exhibit good catalytic performance in ORR.