Impact of Transition Metal Carbide and Nitride Supports on the Electronic Structure of Thin Platinum Overlayers

Aaron Garg, Danielle S. Goncalves, Yusu Liu, Zhenshu Wang, Linxi Wang, Jong Suk Yoo, Alexie Kolpak, Robert Martin Rioux, Jr., Daniela Zanchet, Yuriy Román-Leshkov

Research output: Contribution to journalArticle

Abstract

Atomically thin platinum (Pt) shells on titanium tungsten carbide (TiWC) and titanium tungsten nitride (TiWN) core nanoparticles display substantially modified catalytic performance compared to commercial Pt nanoparticles. In situ X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) analyses indicate these differences are primarily caused by ligand effects from the hybridization of Pt and W d states at the core-shell interface. The heterometallic bonding between the shell and the core elements leads to broadening of the Pt valence d-band, a downshift of the d-band center, and greatly reduced adsorbate binding energies, as verified by density functional theory calculations and microcalorimetry of CO adsorption. In situ XANES measurements during reduction treatment demonstrated how surface oxides disrupt the bonding interactions between Pt and W. Changes to the Pt electronic structure from different core materials correlated with ethylene hydrogenation reactivity, where increased Pt d-band broadening was associated with weaker adsorbate binding and consequently lower turnover frequency. The significant electronic structure modification of Pt by the TiWC and TiWN cores exemplifies how core-shell nanoparticle architectures can be used to tune catalyst reactivity.

Original languageEnglish (US)
Pages (from-to)7090-7098
Number of pages9
JournalACS Catalysis
Volume9
Issue number8
DOIs
StatePublished - Aug 2 2019

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Platinum
Nitrides
Electronic structure
Transition metals
Carbides
X ray absorption
Adsorbates
Nanoparticles
Titanium carbide
Tungsten
Tungsten carbide
Carbon Monoxide
Titanium
Binding energy
Oxides
Hydrogenation
Density functional theory
Ethylene
Ligands
Adsorption

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)

Cite this

Garg, A., Goncalves, D. S., Liu, Y., Wang, Z., Wang, L., Yoo, J. S., ... Román-Leshkov, Y. (2019). Impact of Transition Metal Carbide and Nitride Supports on the Electronic Structure of Thin Platinum Overlayers. ACS Catalysis, 9(8), 7090-7098. https://doi.org/10.1021/acscatal.9b01272
Garg, Aaron ; Goncalves, Danielle S. ; Liu, Yusu ; Wang, Zhenshu ; Wang, Linxi ; Yoo, Jong Suk ; Kolpak, Alexie ; Rioux, Jr., Robert Martin ; Zanchet, Daniela ; Román-Leshkov, Yuriy. / Impact of Transition Metal Carbide and Nitride Supports on the Electronic Structure of Thin Platinum Overlayers. In: ACS Catalysis. 2019 ; Vol. 9, No. 8. pp. 7090-7098.
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Garg, A, Goncalves, DS, Liu, Y, Wang, Z, Wang, L, Yoo, JS, Kolpak, A, Rioux, Jr., RM, Zanchet, D & Román-Leshkov, Y 2019, 'Impact of Transition Metal Carbide and Nitride Supports on the Electronic Structure of Thin Platinum Overlayers', ACS Catalysis, vol. 9, no. 8, pp. 7090-7098. https://doi.org/10.1021/acscatal.9b01272

Impact of Transition Metal Carbide and Nitride Supports on the Electronic Structure of Thin Platinum Overlayers. / Garg, Aaron; Goncalves, Danielle S.; Liu, Yusu; Wang, Zhenshu; Wang, Linxi; Yoo, Jong Suk; Kolpak, Alexie; Rioux, Jr., Robert Martin; Zanchet, Daniela; Román-Leshkov, Yuriy.

In: ACS Catalysis, Vol. 9, No. 8, 02.08.2019, p. 7090-7098.

Research output: Contribution to journalArticle

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T1 - Impact of Transition Metal Carbide and Nitride Supports on the Electronic Structure of Thin Platinum Overlayers

AU - Garg, Aaron

AU - Goncalves, Danielle S.

AU - Liu, Yusu

AU - Wang, Zhenshu

AU - Wang, Linxi

AU - Yoo, Jong Suk

AU - Kolpak, Alexie

AU - Rioux, Jr., Robert Martin

AU - Zanchet, Daniela

AU - Román-Leshkov, Yuriy

PY - 2019/8/2

Y1 - 2019/8/2

N2 - Atomically thin platinum (Pt) shells on titanium tungsten carbide (TiWC) and titanium tungsten nitride (TiWN) core nanoparticles display substantially modified catalytic performance compared to commercial Pt nanoparticles. In situ X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) analyses indicate these differences are primarily caused by ligand effects from the hybridization of Pt and W d states at the core-shell interface. The heterometallic bonding between the shell and the core elements leads to broadening of the Pt valence d-band, a downshift of the d-band center, and greatly reduced adsorbate binding energies, as verified by density functional theory calculations and microcalorimetry of CO adsorption. In situ XANES measurements during reduction treatment demonstrated how surface oxides disrupt the bonding interactions between Pt and W. Changes to the Pt electronic structure from different core materials correlated with ethylene hydrogenation reactivity, where increased Pt d-band broadening was associated with weaker adsorbate binding and consequently lower turnover frequency. The significant electronic structure modification of Pt by the TiWC and TiWN cores exemplifies how core-shell nanoparticle architectures can be used to tune catalyst reactivity.

AB - Atomically thin platinum (Pt) shells on titanium tungsten carbide (TiWC) and titanium tungsten nitride (TiWN) core nanoparticles display substantially modified catalytic performance compared to commercial Pt nanoparticles. In situ X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) analyses indicate these differences are primarily caused by ligand effects from the hybridization of Pt and W d states at the core-shell interface. The heterometallic bonding between the shell and the core elements leads to broadening of the Pt valence d-band, a downshift of the d-band center, and greatly reduced adsorbate binding energies, as verified by density functional theory calculations and microcalorimetry of CO adsorption. In situ XANES measurements during reduction treatment demonstrated how surface oxides disrupt the bonding interactions between Pt and W. Changes to the Pt electronic structure from different core materials correlated with ethylene hydrogenation reactivity, where increased Pt d-band broadening was associated with weaker adsorbate binding and consequently lower turnover frequency. The significant electronic structure modification of Pt by the TiWC and TiWN cores exemplifies how core-shell nanoparticle architectures can be used to tune catalyst reactivity.

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