Thermal Unequilibrium of PdSn Intermetallic Nanocatalysts: From In Situ Tailored Synthesis to Unexpected Hydrogenation Selectivity

Chen, Minda; Yan, Yu; Gebre, Mebatsion; Ordonez, Claudio; Liu, Fudong; Qi, Long; Lamkins, Andrew; Jing, Dapeng; Dolge, Kevin; Zhang, Biying; Heintz, Patrick M.; Shoemaker, Daniel P.; Wang, Bin; Huang, Wenyu

doi:10.1002/anie.202106515

Cited by 40 publications

(39 citation statements)

References 44 publications

(4 reference statements)

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“…In addition, we recently investigated the formation of the PdSn iNPs (Figure 2d). 21 Although PdSn is a eutectic intermetallic phase on the Pd−Sn binary phase diagram, previous studies mostly focused on the thermodynamically preferred Pd 3 Sn 2 phase. With in situ PXRD and XAS characterization, we discovered that the PdSn phase is metastable.…”

Section: Unique Formation Behavior At the Nanoscalementioning

confidence: 99%

“…These deviations make the iNPs slightly off-stoichiometric but are not sufficient to make them favor other intermetallic phases. 21,32,33 When this off-stoichiometric composition causes more structure changes on the surface than the bulk of iNPs, it could have a profound impact on their catalytic properties.…”

Section: Intermetallic Nanoparticles With Nonstoichiometric Compositionmentioning

confidence: 99%

Section: Structural Design Of Silica-encapsulated Inpsmentioning

confidence: 99%

“…An ideal intermetallic structure has a fixed stoichiometry, and it is interesting how the crystal structure tolerates slight compositional deviations, especially at the nanoscale. These deviations make the iNPs slightly off-stoichiometric but are not sufficient to make them favor other intermetallic phases. ,, When this off-stoichiometric composition causes more structure changes on the surface than the bulk of iNPs, it could have a profound impact on their catalytic properties.…”

Section: Active Site Engineering On Intermetallic Structure To Achiev...mentioning

confidence: 99%

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Silica-Encapsulated Intermetallic Nanoparticles for Highly Active and Selective Heterogeneous Catalysis

2021

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Conspectus Intermetallic nanoparticles (iNPs) have been the subject of many recent reports for their demonstrated applications as highly active and selective heterogeneous catalysts. As a subclass of alloys, intermetallic compounds possess ordered crystal structures and, therefore, well-defined atomic environments, unlike the solid solution of alloys whose atomic arrangements are random and locally unpredictable. Catalytically active iNPs typically contain a group 8–10 transition metals as the “active” metals. They usually also include an “inactive” metal that does not directly participate in the catalytic reaction but can significantly modify the active metal’s behavior. The choice of the inactive metal component can range across the periodic table. A few general challenges remain to design iNPs as heterogeneous catalysts with outstanding performance. Synthetically, the high surface energy of small nanoparticles is prone to their aggregation, while maximizing the surface-to-volume ratios is highly desired for efficient noble metal utilization. Additionally, even though the formation of bulk intermetallic compounds has been extensively studied, the formation of intermetallic phases at the nanoscale can behave differently. For example, the formation temperatures of iNPs are often drastically different from those predicted from the bulk phase diagrams. This behavior often leads to further challenges in the synthesis of iNPs. In addition to synthetic challenges, it is also critical to demonstrate the performance of iNPs in catalysis and establish the structure–property relationships. Instrumental and computational techniques often assist the understanding of catalytic properties. Due to the long-range order of intermetallic structure, various electron and X-ray techniques are often used to precisely determine the structure of iNPs. Structural modeling in density functional theory (DFT) calculation can also benefit from such ordered structures. These techniques have siginificantly improved the understanding of enhanced catalytic properties of iNPs in thermo-, electro-, and photocatalysis. Hydrogenation of furfural to furfuryl alcohol, for example, is a model reaction where PtSn iNPs show enhanced activity and chemoselectivity in hydrogenating CO rather than CC bonds. This superior catalytic performance can be correlated to the change in the geometric and electronic surface structure of the PtSn iNPs based on careful instrumental and computational characterizations. Additionally, intermetallic surfaces can be further modified by ligands or defects. While adding complexity to iNP systems, these modifiers provide additional control over their catalytic properties. In this Account, taking encapsulated iNPs in mesoporous silica as an example, we review the current strategies to develop iNPs as high-performance heterogeneous catalysts, with insights on the distinct formation behavior of iNPs compared to bulk intermetallic materials. We then highlight thermo- and electro-catalysis reactions to which these iNP catalysts a...

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Section: Unique Formation Behavior At the Nanoscalementioning

confidence: 99%

Section: Intermetallic Nanoparticles With Nonstoichiometric Compositionmentioning

confidence: 99%

Section: Structural Design Of Silica-encapsulated Inpsmentioning

confidence: 99%

Section: Active Site Engineering On Intermetallic Structure To Achiev...mentioning

confidence: 99%

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Silica-Encapsulated Intermetallic Nanoparticles for Highly Active and Selective Heterogeneous Catalysis

2021

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“…The crystal structure of nanomaterials has a decisive influence on its physical and chemical properties and applications. − Nanocatalysts with special crystal phases are different from traditional catalysts in catalytic activity, selectivity, and stability because of the unique electronic and energy-level structure in the crystal phase − and have received extensive attention and research in the field of catalysis. At the same time, research has revealed that defect modification is an effective means of regulating catalyst properties.…”

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confidence: 99%

Ordered Vacancies on the Body-Centered Cubic PdCu Nanocatalysts

Wang

Liu

et al. 2021

Nano Lett.

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Defect engineering has become one of the important considerations in today's electrocatalyst design. However, the vacancies in the ordered crystal structure (especially body-centered cubic (bcc) and the effect of ordered vacancies (OVs) on the electronic fabric have not been researched yet. In this work, we report the inaugural time of the generation of OVs in the bcc architecture and discuss the insight of the modulation system of the material and its part in the electrochemical N 2 reduction reaction (NRR). OV-PdCu-2 achieves the highest Faradaic efficiency value of 21.5% at 0.05 V versus RHE. When the potential increases to 0 V versus RHE, the highest ammonia yield is 55.54 μg h −1 mg cat −1 , which is significantly better than the unetched PdCu nanoparticles (12.83 μg h −1 mg cat −1

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Transfer Hydrogenation in Mesoporous Palladium: Polar Hydrogen Engineering to Realize High Selectivity of Alkyne Semi‐Hydrogenation

Qin

Liu

2022

Adv Funct Materials

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Semi-hydrogenation of alkynes to industrially important alkenes is earnestly desirable in the fine chemical industry but energetically unfavorable. Herein, it is reported that mesoporous palladium (meso-Pd) catalyst changes the hydrogenation pathways in ethanol with ammonium borane as the hydrogen source, realizing the high catalytic selectivity of ≈99% in semi-hydrogenation of alkynes. Mechanism studies reveal that the active polar hydrogen can be produced and reserved well in the electron-rich mesoporous channels of meso-Pd catalyst, resulting in a transfer hydrogenation pathway, which selectively semi-hydrogenates alkynes into alkenes without over-hydrogenating alkenes into alkanes. Moreover, it is demonstrated that the polar hydrogen engineering of meso-Pd catalyst is highly efficient in various alkyne semihydrogenation and chemoselective hydrogenation reactions. The results thus establish metal catalyst mesostructuring as an alternative route for engineering polar hydrogen in the transfer hydrogenation reactions, thus realizing the high catalytic selectivity in various selective catalysis.

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Thermal Unequilibrium of PdSn Intermetallic Nanocatalysts: From In Situ Tailored Synthesis to Unexpected Hydrogenation Selectivity

Cited by 40 publications

References 44 publications

Silica-Encapsulated Intermetallic Nanoparticles for Highly Active and Selective Heterogeneous Catalysis

Silica-Encapsulated Intermetallic Nanoparticles for Highly Active and Selective Heterogeneous Catalysis

Ordered Vacancies on the Body-Centered Cubic PdCu Nanocatalysts

Transfer Hydrogenation in Mesoporous Palladium: Polar Hydrogen Engineering to Realize High Selectivity of Alkyne Semi‐Hydrogenation

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