In situ spectroscopic characterization of Ni1- xZnx/ZnO catalysts and their selectivity for acetylene semihydrogenation in excess ethylene

Charles S. Spanjers, Richard S. Sim, Nicholas P. Sturgis, Bernd C. Kabius, Robert Martin Rioux, Jr.

Research output: Contribution to journalArticle

13 Citations (Scopus)

Abstract

The structures of ZnO-supported Ni catalysts were explored with in situ X-ray absorption spectroscopy, temperature-programmed reduction, X-ray diffraction, high-resolution transmission electron microscopy (HRTEM), scanning transmission electron microscopy, and electron energy loss spectroscopy. Calcination of nickel nitrate on a nanoparticulate ZnO support at 450 °C results in the formation of Zn-doped NiO (ca. Ni0.85Zn0.15O) nanoparticles with the rock salt crystal structure. Subsequent in situ reduction monitored by X-ray absorption near-edge structure (XANES) at the Ni K edge reveals a direct transformation of the Zn-doped NiO nanoparticles to a face-centered cubic alloy, Ni1-xZnx, at ∼400 °C with x increasing with increasing temperature. Both in situ XANES and ex situ HRTEM provide evidence for intermetallic β1-NiZn formation at ∼550 °C. In comparison to a Ni/SiO2 catalyst, Ni/ZnO necessitates a higher temperature for the reduction of NiII to Ni0, which highlights the strong interaction between Ni and the ZnO support. The catalytic activity for acetylene removal from an ethylene feed stream is decreased by a factor of 20 on Ni/ZnO in comparison to Ni/SiO2. The decrease in catalytic activity of Ni/ZnO is accompanied by a reduced absolute selectivity to ethylene. H-D exchange measurements demonstrate a reduced ability of Ni/ZnO to dissociate hydrogen in comparison to Ni/SiO2. These results of the catalytic experiments suggest that the catalytic properties are controlled, in part, by the zinc oxide support and stress the importance of reporting absolute ethylene selectivity for the catalytic semihydrogenation of acetylene in excess ethylene.

Original languageEnglish (US)
Pages (from-to)3304-3315
Number of pages12
JournalACS Catalysis
Volume5
Issue number6
DOIs
StatePublished - Jun 5 2015

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Acetylene
Catalyst selectivity
Ethylene
Catalysts
X ray absorption
High resolution transmission electron microscopy
Catalyst activity
Nanoparticles
Zinc Oxide
X ray absorption spectroscopy
Electron energy loss spectroscopy
Zinc oxide
Catalyst supports
Calcination
Temperature
Intermetallics
Hydrogen
Nitrates
Salts
Crystal structure

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)

Cite this

Spanjers, Charles S. ; Sim, Richard S. ; Sturgis, Nicholas P. ; Kabius, Bernd C. ; Rioux, Jr., Robert Martin. / In situ spectroscopic characterization of Ni1- xZnx/ZnO catalysts and their selectivity for acetylene semihydrogenation in excess ethylene. In: ACS Catalysis. 2015 ; Vol. 5, No. 6. pp. 3304-3315.
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abstract = "The structures of ZnO-supported Ni catalysts were explored with in situ X-ray absorption spectroscopy, temperature-programmed reduction, X-ray diffraction, high-resolution transmission electron microscopy (HRTEM), scanning transmission electron microscopy, and electron energy loss spectroscopy. Calcination of nickel nitrate on a nanoparticulate ZnO support at 450 °C results in the formation of Zn-doped NiO (ca. Ni0.85Zn0.15O) nanoparticles with the rock salt crystal structure. Subsequent in situ reduction monitored by X-ray absorption near-edge structure (XANES) at the Ni K edge reveals a direct transformation of the Zn-doped NiO nanoparticles to a face-centered cubic alloy, Ni1-xZnx, at ∼400 °C with x increasing with increasing temperature. Both in situ XANES and ex situ HRTEM provide evidence for intermetallic β1-NiZn formation at ∼550 °C. In comparison to a Ni/SiO2 catalyst, Ni/ZnO necessitates a higher temperature for the reduction of NiII to Ni0, which highlights the strong interaction between Ni and the ZnO support. The catalytic activity for acetylene removal from an ethylene feed stream is decreased by a factor of 20 on Ni/ZnO in comparison to Ni/SiO2. The decrease in catalytic activity of Ni/ZnO is accompanied by a reduced absolute selectivity to ethylene. H-D exchange measurements demonstrate a reduced ability of Ni/ZnO to dissociate hydrogen in comparison to Ni/SiO2. These results of the catalytic experiments suggest that the catalytic properties are controlled, in part, by the zinc oxide support and stress the importance of reporting absolute ethylene selectivity for the catalytic semihydrogenation of acetylene in excess ethylene.",
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In situ spectroscopic characterization of Ni1- xZnx/ZnO catalysts and their selectivity for acetylene semihydrogenation in excess ethylene. / Spanjers, Charles S.; Sim, Richard S.; Sturgis, Nicholas P.; Kabius, Bernd C.; Rioux, Jr., Robert Martin.

In: ACS Catalysis, Vol. 5, No. 6, 05.06.2015, p. 3304-3315.

Research output: Contribution to journalArticle

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T1 - In situ spectroscopic characterization of Ni1- xZnx/ZnO catalysts and their selectivity for acetylene semihydrogenation in excess ethylene

AU - Spanjers, Charles S.

AU - Sim, Richard S.

AU - Sturgis, Nicholas P.

AU - Kabius, Bernd C.

AU - Rioux, Jr., Robert Martin

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N2 - The structures of ZnO-supported Ni catalysts were explored with in situ X-ray absorption spectroscopy, temperature-programmed reduction, X-ray diffraction, high-resolution transmission electron microscopy (HRTEM), scanning transmission electron microscopy, and electron energy loss spectroscopy. Calcination of nickel nitrate on a nanoparticulate ZnO support at 450 °C results in the formation of Zn-doped NiO (ca. Ni0.85Zn0.15O) nanoparticles with the rock salt crystal structure. Subsequent in situ reduction monitored by X-ray absorption near-edge structure (XANES) at the Ni K edge reveals a direct transformation of the Zn-doped NiO nanoparticles to a face-centered cubic alloy, Ni1-xZnx, at ∼400 °C with x increasing with increasing temperature. Both in situ XANES and ex situ HRTEM provide evidence for intermetallic β1-NiZn formation at ∼550 °C. In comparison to a Ni/SiO2 catalyst, Ni/ZnO necessitates a higher temperature for the reduction of NiII to Ni0, which highlights the strong interaction between Ni and the ZnO support. The catalytic activity for acetylene removal from an ethylene feed stream is decreased by a factor of 20 on Ni/ZnO in comparison to Ni/SiO2. The decrease in catalytic activity of Ni/ZnO is accompanied by a reduced absolute selectivity to ethylene. H-D exchange measurements demonstrate a reduced ability of Ni/ZnO to dissociate hydrogen in comparison to Ni/SiO2. These results of the catalytic experiments suggest that the catalytic properties are controlled, in part, by the zinc oxide support and stress the importance of reporting absolute ethylene selectivity for the catalytic semihydrogenation of acetylene in excess ethylene.

AB - The structures of ZnO-supported Ni catalysts were explored with in situ X-ray absorption spectroscopy, temperature-programmed reduction, X-ray diffraction, high-resolution transmission electron microscopy (HRTEM), scanning transmission electron microscopy, and electron energy loss spectroscopy. Calcination of nickel nitrate on a nanoparticulate ZnO support at 450 °C results in the formation of Zn-doped NiO (ca. Ni0.85Zn0.15O) nanoparticles with the rock salt crystal structure. Subsequent in situ reduction monitored by X-ray absorption near-edge structure (XANES) at the Ni K edge reveals a direct transformation of the Zn-doped NiO nanoparticles to a face-centered cubic alloy, Ni1-xZnx, at ∼400 °C with x increasing with increasing temperature. Both in situ XANES and ex situ HRTEM provide evidence for intermetallic β1-NiZn formation at ∼550 °C. In comparison to a Ni/SiO2 catalyst, Ni/ZnO necessitates a higher temperature for the reduction of NiII to Ni0, which highlights the strong interaction between Ni and the ZnO support. The catalytic activity for acetylene removal from an ethylene feed stream is decreased by a factor of 20 on Ni/ZnO in comparison to Ni/SiO2. The decrease in catalytic activity of Ni/ZnO is accompanied by a reduced absolute selectivity to ethylene. H-D exchange measurements demonstrate a reduced ability of Ni/ZnO to dissociate hydrogen in comparison to Ni/SiO2. These results of the catalytic experiments suggest that the catalytic properties are controlled, in part, by the zinc oxide support and stress the importance of reporting absolute ethylene selectivity for the catalytic semihydrogenation of acetylene in excess ethylene.

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