Tailoring reactivity of small Ag/Pt bimetallic cluster for ORR: A comprehensive study using density functional theory approach

IF 5.2 2区 化学 Q1 CHEMISTRY, APPLIED Catalysis Today Pub Date : 2024-10-22 DOI:10.1016/j.cattod.2024.115102
Sandeep Nigam , Chiranjib Majumder
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Abstract

Bimetallic clusters, as the name suggests, are known to act as bifunctional catalyst. Therefore, it is possible to tune the composition of the catalyst to achieve the best performance for a specific reaction. In the first part of this work, we explore the geometric and electronic structures of various Ag-Pt bimetallic clusters and find the right composition for ORR, one of the most sought-after reactions in the field of energy materials. We have considered Ag-Pt bimetallic clusters in both free and on Al2O3(0001) support. The results reveal that the equilibrium structures of the bimetallic AgnPtm (n+m ≤ 12 atoms) clusters are governed by a balance of competing interactions (Pt-Pt vs Ag-Pt vs cluster-support interactions). Whilst the isolated decamer cluster with 5:5 or 6:4 composition (Ag6Pt4 and Ag5Pt5) shows atomically segregated structures, Ag rich clusters (Ag9Pt1–3) prefer to form core-shell pattern where Pt forms the core surrounded by Ag atoms. In general, these clusters adopt pseudo-planar structure on alumina support following the surface template. Analysis of the electronic structure shows that Al2O3 surface induces significant broadening in the energy states of the bimetallic cluster, which in turn facilitates higher mixing between d-states of the Ag and Pt in the complex. Finally, the d-band centre descriptor model has been utilized to underscore the chemical reactivity of these bimetallic clusters. Remarkably, the Ag6Pt4@Al2O3 cluster with d-band centre at −2.68 eV is found to be in “just right” zone for ORR. This is further corroborated by the reduction (∼ 25 %) in oxidation reaction enthalpy of the Ag6Pt4@Al2O3 than standard Pt(111) catalytic surface.
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调整小型 Ag/Pt 双金属团簇在 ORR 中的反应活性:利用密度泛函理论方法进行的综合研究
双金属团簇,顾名思义,具有双功能催化剂的作用。因此,可以通过调节催化剂的组成来实现特定反应的最佳性能。在这项工作的第一部分,我们探索了各种银铂双金属团簇的几何和电子结构,并找到了用于 ORR(能源材料领域最热门的反应之一)的合适成分。我们研究了游离和Al2O3(0001)支撑下的银铂双金属团簇。研究结果表明,双金属 AgnPtm(n+m ≤ 12 个原子)团簇的平衡结构受相互竞争的相互作用(Pt-Pt 与 Ag-Pt 之间的相互作用以及团簇与支撑物之间的相互作用)的影响。组成比例为 5:5 或 6:4 的孤立十聚体团簇(Ag6Pt4 和 Ag5Pt5)显示出原子隔离结构,而富含 Ag 的团簇(Ag9Pt1-3)则倾向于形成核壳模式,其中铂形成核心,周围环绕着 Ag 原子。一般来说,这些团簇在氧化铝载体上按照表面模板采用伪平面结构。对电子结构的分析表明,Al2O3 表面使双金属团簇的能态显著拓宽,这反过来又促进了复合物中银和铂的 d 态之间的混合。最后,利用 d 带中心描述模型强调了这些双金属簇的化学反应活性。值得注意的是,发现 d 波段中心在 -2.68 eV 的 Ag6Pt4@Al2O3 簇处于 ORR 的 "恰到好处 "区域。与标准铂(111)催化表面相比,Ag6Pt4@Al2O3 的氧化反应焓降低了 25%,进一步证实了这一点。
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来源期刊
Catalysis Today
Catalysis Today 化学-工程:化工
CiteScore
11.50
自引率
3.80%
发文量
573
审稿时长
2.9 months
期刊介绍: Catalysis Today focuses on the rapid publication of original invited papers devoted to currently important topics in catalysis and related subjects. The journal only publishes special issues (Proposing a Catalysis Today Special Issue), each of which is supervised by Guest Editors who recruit individual papers and oversee the peer review process. Catalysis Today offers researchers in the field of catalysis in-depth overviews of topical issues. Both fundamental and applied aspects of catalysis are covered. Subjects such as catalysis of immobilized organometallic and biocatalytic systems are welcome. Subjects related to catalysis such as experimental techniques, adsorption, process technology, synthesis, in situ characterization, computational, theoretical modeling, imaging and others are included if there is a clear relationship to catalysis.
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