Structure and reactivity of Pt–In intermetallic alloy nanoparticles: Highly selective catalysts for ethane dehydrogenation

Wegener, Evan C.; Wu, Zhenwei; Tseng, Han-Ting; Gallagher, James R.; Ren, Yang; Diaz, Rosa E.; Ribeiro, Fabio H.; Miller, Jeffrey T.

doi:10.1016/j.cattod.2017.03.054

Cited by 131 publications

(112 citation statements)

References 58 publications

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“…The increased olefin selectivities observed for the PtÀ Fe catalysts are consistent with previously reported IMC alkane dehydrogenation catalysts. [43][44][45][46][47][48][49][50][51] It has been proposed that the increased olefin selectivity arises from the elimination of large active-metal ensembles by incorporation of the noncatalytic promoter metals into the active surface. Segregation of the active atoms reduces hydrogenolysis, which is thought to require ensemble active sites.…”

Section: Resultsmentioning

confidence: 99%

Intermetallic Compounds as an Alternative to Single‐atom Alloy Catalysts: Geometric and Electronic Structures from Advanced X‐ray Spectroscopies and Computational Studies

et al. 2020

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Pt−Fe intermetallic compound (IMC) catalysts, including Pt3Fe, PtFe and PtFe3, are shown to have advantageous catalytic properties similar to those reported for single‐atom alloy catalysts. Suppresion of the Pt ensembles responsible for hydrogenolysis results in high olefin selectivity during propane dehydrogenation. In situ resonant inelastic X‐ray scattering (RIXS) results and density functional theory calculations show that these changes are associated with a decrease in the average energy of the filled 5d states of Pt in the Pt−Fe intermetallic compound structures compared to monometallic Pt, accompanied by an increase in the average energy of the unfilled valence bands. The decrease in energy of the filled Pt 5d orbitals increases with increasing Fe content in the IMC, i.e. PtFe3>PtFe>Pt3Fe. These results demonstrate that by altering the stoichiometry of IMC catalysts it is possible to control both the ensemble size and electronic properties of active sites, which affords another mechanism for tuning catalytic properties, in addition to changing promoter metals. The present study demonstrates the potential of ordered intermetallic compounds as an alternative to traditional solid‐solution single‐atom alloys to serve as catalysts with well‐defined and uniform active sites.

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Section: Resultsmentioning

confidence: 99%

Intermetallic Compounds as an Alternative to Single‐atom Alloy Catalysts: Geometric and Electronic Structures from Advanced X‐ray Spectroscopies and Computational Studies

et al. 2020

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“…The reduced Mn diffused onto the Pt surface and then into the Pt lattice in a kinetically limited fashion, as has been observed for many other bimetallic catalysts prepared in similar way. [25][26][27][28][29] Transformation from Pt to Pt3Mn intermetallic compounds occurred starting from the surface of the NPs. Manipulating the amount of Mn precursor resulted in partial or full intermetallic transformation, forming core-shell or full-body intermetallic NPs (named as Pt3Mn-s (s stands for surface) and Pt3Mn, respectively).…”

Section: Resultsmentioning

confidence: 99%

Changes in Catalytic and Adsorptive Properties of 2 nm Pt₃Mn Nanoparticles by Subsurface Atoms

et al. 2018

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Supported multimetallic nanoparticles (NPs) are widely used in industrial catalytic processes, where the relation between surface structure and function is well-known. However, the effect of subsurface layers on such catalysts remains mostly unstudied. Here, we demonstrate a clear subsurface effect on supported 2 nm core-shell NPs with atomically precise and high temperature stable Pt3Mn intermetallic surface measured by in situ synchrotron X-ray Diffraction, difference X-ray Absorption Spectroscopy, and Energy Dispersive X-ray Spectroscopy. The NPs with a Pt3Mn subsurface have 98% selectivity to C-H over CC bond activation during propane dehydrogenation at 550 °C compared with 82% for core-shell NPs with a Pt subsurface. The difference is correlated with significant reduction in the heats of reactant adsorption due to the Pt3Mn intermetallic subsurface as discerned by theory as well as experiment. The findings of this work highlight the importance of subsurface for supported NP catalysts, which can be tuned via controlled intermetallic formation. Such approach is generally applicable to modifying multimetallic NPs, adding another dimension to the tunability of their catalytic performance. Disciplines

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“…Such Pt‐In catalysts show great promise for alkane dehydrogenation, hydroconversion of bio‐based oxygenates, and as direct methanol and ethanol fuel cells . Additionally, efforts have been undertaken recently by our groups and others to understand their formation and control their intermetallic composition. To monitor the kinetic habits of these catalysts in situ with high time resolution, QXAS spectra are recorded at the Pt L 3 ‐edge with one second time resolution (Figure a).…”

Section: Figurementioning

confidence: 99%

Kinetics of Lifetime Changes in Bimetallic Nanocatalysts Revealed by Quick X‐ray Absorption Spectroscopy

et al. 2018

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Alloyed metal nanocatalysts are of environmental and economic importance in a plethora of chemical technologies. During the catalyst lifetime, supported alloy nanoparticles undergo dynamic changes which are well‐recognized but still poorly understood. High‐temperature O2–H2 redox cycling was applied to mimic the lifetime changes in model Pt13In9 nanocatalysts, while monitoring the induced changes by in situ quick X‐ray absorption spectroscopy with one‐second resolution. The different reaction steps involved in repeated Pt13In9 segregation‐alloying are identified and kinetically characterized at the single‐cycle level. Over longer time scales, sintering phenomena are substantiated and the intraparticle structure is revealed throughout the catalyst lifetime. The in situ time‐resolved observation of the dynamic habits of alloyed nanoparticles and their kinetic description can impact catalysis and other fields involving (bi)metallic nanoalloys.

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Structure and reactivity of Pt–In intermetallic alloy nanoparticles: Highly selective catalysts for ethane dehydrogenation

Cited by 131 publications

References 58 publications

Intermetallic Compounds as an Alternative to Single‐atom Alloy Catalysts: Geometric and Electronic Structures from Advanced X‐ray Spectroscopies and Computational Studies

Intermetallic Compounds as an Alternative to Single‐atom Alloy Catalysts: Geometric and Electronic Structures from Advanced X‐ray Spectroscopies and Computational Studies

Changes in Catalytic and Adsorptive Properties of 2 nm Pt₃Mn Nanoparticles by Subsurface Atoms

Kinetics of Lifetime Changes in Bimetallic Nanocatalysts Revealed by Quick X‐ray Absorption Spectroscopy

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Structure and reactivity of Pt–In intermetallic alloy nanoparticles: Highly selective catalysts for ethane dehydrogenation

Cited by 131 publications

References 58 publications

Intermetallic Compounds as an Alternative to Single‐atom Alloy Catalysts: Geometric and Electronic Structures from Advanced X‐ray Spectroscopies and Computational Studies

Intermetallic Compounds as an Alternative to Single‐atom Alloy Catalysts: Geometric and Electronic Structures from Advanced X‐ray Spectroscopies and Computational Studies

Changes in Catalytic and Adsorptive Properties of 2 nm Pt3Mn Nanoparticles by Subsurface Atoms

Kinetics of Lifetime Changes in Bimetallic Nanocatalysts Revealed by Quick X‐ray Absorption Spectroscopy

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Changes in Catalytic and Adsorptive Properties of 2 nm Pt₃Mn Nanoparticles by Subsurface Atoms