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通过共振能量转移提高Pt-Ru团簇的甲醇氧化反应活性

Boosting the Methanol Oxidation Reaction Activity of Pt-Ru Clusters via Resonance Energy Transfer.

作者信息

Liang Jiahui, Cheng Heyun, Zhao Bolin, Hu Qiong, Xing Zihao, Zhang Yuwei, Niu Li

机构信息

Guangzhou Key Laboratory of Sensing Materials & Devices /Center for Advanced Analytical Science/School of Chemistry and Chemical Engineering, Guangzhou University, Guangzhou Higher Education Mega Center, No. 230 Wai Huan Xi Road, Guangzhou, 510006, P. R. China.

Key Laboratory of Polyoxometalate and Reticular Material Chemistry of Ministry of Education, Faculty of Chemistry, Northeast Normal University, Changchun, 130024, P. R. China.

出版信息

Small. 2023 Sep;19(38):e2302149. doi: 10.1002/smll.202302149. Epub 2023 May 17.

Abstract

The sluggish kinetics of the methanol oxidation reaction (MOR) with PtRu electrocatalyst severely hinder the commercialization of direct methanol fuel cells (DMFCs). The electronic structure of Pt is of significant importance for its catalytic activity. Herein, it is reported that low-cost fluorescent carbon dots (CDs) can regulate the behavior of the D-band center of Pt in PtRu clusters through resonance energy transfer (RET), resulting in a significant increase in the catalytic activity of the catalyst participating in methanol electrooxidation. For the first time, the bifunction of RET is used to provide unique strategy for fabrication of PtRu electrocatalysts, not only tunes the electronic structure of metals, but also provides an important role in anchoring metal clusters. Density functional theory calculations further prove that charge transfer between CDs and Pt promotes the dehydrogenation of methanol on PtRu catalysts and reduces the free energy barrier of the reaction associated with the oxidation of CO to CO . This helps to improve the catalytic activity of the systems participating in MOR. The performance of the best sample is 2.76 times higher than that of commercial PtRu/C (213.0 vs 76.99  ). The fabricated system can be potentially used for the efficient fabrication of DMFCs.

摘要

铂钌电催化剂上甲醇氧化反应(MOR)缓慢的动力学严重阻碍了直接甲醇燃料电池(DMFC)的商业化。铂的电子结构对其催化活性至关重要。在此,据报道低成本荧光碳点(CDs)可通过共振能量转移(RET)调节铂钌簇中铂的D带中心行为,从而使参与甲醇电氧化的催化剂催化活性显著提高。首次利用RET的双功能为铂钌电催化剂的制备提供了独特策略,不仅调节了金属的电子结构,还在锚定金属簇方面发挥了重要作用。密度泛函理论计算进一步证明,碳点与铂之间的电荷转移促进了铂钌催化剂上甲醇的脱氢反应,并降低了与CO氧化为CO₂相关反应的自由能垒。这有助于提高参与MOR的体系的催化活性。最佳样品的性能比商业铂钌/C高出2.76倍(213.0对76.99 )。所制备的体系有望用于高效制备DMFC。

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