Volcano-like Activity Trends in Au@Pd Catalysts: The Role of Pd Loading and Nanoparticle Size.

IF 2.3 3区 化学 Q3 CHEMISTRY, PHYSICAL
Adriano H Braga, Jhonatan L Fiorio, Ofelia Yang, Karla L C Silva, Tiago A Silva, Adam S Hoffman, Simon R Bare, Jefferson Bettini, Naga Vishnu V Mogili, Liane M Rossi
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Abstract

The addition of palladium (Pd) to preformed gold nanoparticles (Au NPs) enables the formation of core-shell structures with enhanced catalytic performance in oxidation reactions. However, predicting the precise palladium content required to achieve maximum catalytic activity remains difficult based on current understanding. Herein, Pd was systematically introduced onto titania-supported Au NPs (2, 6, and 10 nm) to evaluate their performance in benzyl alcohol oxidation. A volcano-like trend in catalytic activity was observed, where activity increased with Pd addition, peaked, and then declined. The Pd loading required for maximum activity depended on Au NP size: ≈40 at% Pd/Au for 2.6 nm, ≈20 at% Pd/Au for 6.4 nm, and ≈12.5 at% Pd/Au for 10.6 nm. For Au NPs > 6 nm, peak activity aligned with monolayer Pd coverage, while for smaller NPs (2-3 nm), optimal Pd content was below monolayer predictions. X-ray absorption spectroscopy revealed a core-shell structure at low Pd content, but higher Pd loadings led to Pd diffusion into the Au core. This structural transformation likely caused activity decline, indicating that AuPd alloying negatively impacts catalysis. These results highlight that core-shell Au@Pd catalysts outperform AuPd alloys and provide crucial insights for designing highly active bimetallic catalysts.

Au@Pd催化剂的火山样活性趋势:Pd负载和纳米颗粒大小的作用。
将钯(Pd)添加到预制金纳米颗粒(Au NPs)中,可以形成具有增强氧化反应催化性能的核壳结构。然而,根据目前的了解,预测达到最大催化活性所需的精确钯含量仍然很困难。本文将Pd系统地引入到钛负载的Au NPs(2,6和10 nm)上,以评估其在苯甲醇氧化中的性能。观察到催化活性呈火山样趋势,随着Pd的加入,活性增加,达到峰值,然后下降。最大活性所需的钯负载取决于Au NP大小:在2.6 nm≈40 % Pd/Au,在6.4 nm≈20 % Pd/Au,在10.6 nm≈12.5 % Pd/Au。对于Au NPs,峰值活性与单层Pd覆盖率一致,而对于较小的NPs (2-3 nm),最佳Pd含量低于单层预测。x射线吸收光谱显示低Pd含量时为核壳结构,但高Pd负载导致Pd扩散到Au核中。这种结构转变可能导致活性下降,表明AuPd合金化对催化产生负面影响。这些结果表明,核壳Au@Pd催化剂优于AuPd合金,并为设计高活性双金属催化剂提供了重要见解。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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来源期刊
Chemphyschem
Chemphyschem 化学-物理:原子、分子和化学物理
CiteScore
4.60
自引率
3.40%
发文量
425
审稿时长
1.1 months
期刊介绍: ChemPhysChem is one of the leading chemistry/physics interdisciplinary journals (ISI Impact Factor 2018: 3.077) for physical chemistry and chemical physics. It is published on behalf of Chemistry Europe, an association of 16 European chemical societies. ChemPhysChem is an international source for important primary and critical secondary information across the whole field of physical chemistry and chemical physics. It integrates this wide and flourishing field ranging from Solid State and Soft-Matter Research, Electro- and Photochemistry, Femtochemistry and Nanotechnology, Complex Systems, Single-Molecule Research, Clusters and Colloids, Catalysis and Surface Science, Biophysics and Physical Biochemistry, Atmospheric and Environmental Chemistry, and many more topics. ChemPhysChem is peer-reviewed.
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