Selective Hydrodeoxygenation of Guaiacol to Phenolics by Ni/Anatase TiO 2 Catalyst Formed by Cross-Surface Migration of Ni and TiO 2

Xiaoqiang Zhang, Peifang Yan, Bin Zhao, Kairui Liu, Mayfair C. Kung, Harold H Kung, Shanyong Chen, Z. Conrad Zhang

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

The catalytic properties of physical mixtures of Ni particles (100-200 nm) with nanoparticles of anatase TiO 2 (TiO 2 -A), ZrO 2 , Al 2 O 3 , rutile TiO 2 (TiO 2 -R), and CeO 2 were investigated for the hydrodeoxygenation (HDO) of guaiacol. High selectivities to phenolics were obtained only for Ni mixed with anatase TiO 2 (Ni and TiO 2 -A), while saturated hydrocarbons were the main products for the mixtures with other supports. By thermal treatment in hydrogen gas only at 300 °C or higher and subsequently separating the large Ni particles from the TiO 2 -A particles with a magnet, it was further discovered that there was migration of TiO 2 from TiO 2 -A onto the large Ni particles, resulting in an amorphous TiO 2 overlayer on the Ni particles as evidenced by high-resolution TEM, and vice versa, migration of Ni onto TiO 2 -A. The TiO 2 overlayer rendered the Ni particles completely inactive as a hydrogenation/hydrodeoxygenation catalyst. Conversely, the small amounts of Ni (<1.5 wt %) migrated onto TiO 2 -A formed highly dispersed Ni, undetectable by high-resolution TEM (<2 nm), that were remarkably highly active for HDO of guaiacol, producing selectively phenolics. Such highly selective HDO catalysts could also be formed by incipient wetness impregnation of Ni in loadings above 2 wt % onto the TiO 2 -A, but it was essential to pretreat the sample in H 2 at 300 °C or higher. Pretreatment in H 2 at 200 °C generated catalysts that produced saturated ring products. The activity of the impregnated catalysts, as measured by guaiacol conversion, increased linearly with Ni loading below 0.5 wt %. The activity continued to increase with Ni loading but more slowly up to 2 wt %, beyond which there was little further change. The results suggested that two types of Ni species existed on the TiO 2 -A surface. One type consisted of a cluster of Ni atoms that were dominant on larger Ni particles that were active in aromatic ring hydrogenation and hydrodeoxygenation. They were readily covered by reducible TiO 2 -A at 300 °C or higher due to the traditional strong metal support interaction (SMSI) effect and became inactive. Another type was clusters of a very small number of Ni atoms, perhaps one atom, that were present as highly dispersed Ni clusters interacting strongly with the defect sites of TiO 2 -A. The strong interaction of this type of Ni with the TiO 2 defect deterred TiO x migration allowing surface exposed Ni atoms to catalyze the HDO of guaiacol with very high selectivities that were not characteristic of typical Ni particles.

Original languageEnglish
Pages (from-to)3551-3563
Number of pages13
JournalACS Catalysis
DOIs
Publication statusPublished - Jan 1 2019

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Guaiacol
Titanium dioxide
Atoms
Catalysts
Hydrogenation
Transmission electron microscopy
Defects
Hydrocarbons
Impregnation
Magnets
Hydrogen
Catalyst activity
Gases
Metals
Heat treatment
Nanoparticles
titanium dioxide

Keywords

  • guaiacol hydrodeoxygenation
  • lignin
  • phenol
  • SMSI or strong metal-support interaction
  • titania and nickel

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

Cite this

Selective Hydrodeoxygenation of Guaiacol to Phenolics by Ni/Anatase TiO 2 Catalyst Formed by Cross-Surface Migration of Ni and TiO 2 . / Zhang, Xiaoqiang; Yan, Peifang; Zhao, Bin; Liu, Kairui; Kung, Mayfair C.; Kung, Harold H; Chen, Shanyong; Zhang, Z. Conrad.

In: ACS Catalysis, 01.01.2019, p. 3551-3563.

Research output: Contribution to journalArticle

Zhang, Xiaoqiang ; Yan, Peifang ; Zhao, Bin ; Liu, Kairui ; Kung, Mayfair C. ; Kung, Harold H ; Chen, Shanyong ; Zhang, Z. Conrad. / Selective Hydrodeoxygenation of Guaiacol to Phenolics by Ni/Anatase TiO 2 Catalyst Formed by Cross-Surface Migration of Ni and TiO 2 In: ACS Catalysis. 2019 ; pp. 3551-3563.
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abstract = "The catalytic properties of physical mixtures of Ni particles (100-200 nm) with nanoparticles of anatase TiO 2 (TiO 2 -A), ZrO 2 , Al 2 O 3 , rutile TiO 2 (TiO 2 -R), and CeO 2 were investigated for the hydrodeoxygenation (HDO) of guaiacol. High selectivities to phenolics were obtained only for Ni mixed with anatase TiO 2 (Ni and TiO 2 -A), while saturated hydrocarbons were the main products for the mixtures with other supports. By thermal treatment in hydrogen gas only at 300 °C or higher and subsequently separating the large Ni particles from the TiO 2 -A particles with a magnet, it was further discovered that there was migration of TiO 2 from TiO 2 -A onto the large Ni particles, resulting in an amorphous TiO 2 overlayer on the Ni particles as evidenced by high-resolution TEM, and vice versa, migration of Ni onto TiO 2 -A. The TiO 2 overlayer rendered the Ni particles completely inactive as a hydrogenation/hydrodeoxygenation catalyst. Conversely, the small amounts of Ni (<1.5 wt {\%}) migrated onto TiO 2 -A formed highly dispersed Ni, undetectable by high-resolution TEM (<2 nm), that were remarkably highly active for HDO of guaiacol, producing selectively phenolics. Such highly selective HDO catalysts could also be formed by incipient wetness impregnation of Ni in loadings above 2 wt {\%} onto the TiO 2 -A, but it was essential to pretreat the sample in H 2 at 300 °C or higher. Pretreatment in H 2 at 200 °C generated catalysts that produced saturated ring products. The activity of the impregnated catalysts, as measured by guaiacol conversion, increased linearly with Ni loading below 0.5 wt {\%}. The activity continued to increase with Ni loading but more slowly up to 2 wt {\%}, beyond which there was little further change. The results suggested that two types of Ni species existed on the TiO 2 -A surface. One type consisted of a cluster of Ni atoms that were dominant on larger Ni particles that were active in aromatic ring hydrogenation and hydrodeoxygenation. They were readily covered by reducible TiO 2 -A at 300 °C or higher due to the traditional strong metal support interaction (SMSI) effect and became inactive. Another type was clusters of a very small number of Ni atoms, perhaps one atom, that were present as highly dispersed Ni clusters interacting strongly with the defect sites of TiO 2 -A. The strong interaction of this type of Ni with the TiO 2 defect deterred TiO x migration allowing surface exposed Ni atoms to catalyze the HDO of guaiacol with very high selectivities that were not characteristic of typical Ni particles.",
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AU - Zhao, Bin

AU - Liu, Kairui

AU - Kung, Mayfair C.

AU - Kung, Harold H

AU - Chen, Shanyong

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N2 - The catalytic properties of physical mixtures of Ni particles (100-200 nm) with nanoparticles of anatase TiO 2 (TiO 2 -A), ZrO 2 , Al 2 O 3 , rutile TiO 2 (TiO 2 -R), and CeO 2 were investigated for the hydrodeoxygenation (HDO) of guaiacol. High selectivities to phenolics were obtained only for Ni mixed with anatase TiO 2 (Ni and TiO 2 -A), while saturated hydrocarbons were the main products for the mixtures with other supports. By thermal treatment in hydrogen gas only at 300 °C or higher and subsequently separating the large Ni particles from the TiO 2 -A particles with a magnet, it was further discovered that there was migration of TiO 2 from TiO 2 -A onto the large Ni particles, resulting in an amorphous TiO 2 overlayer on the Ni particles as evidenced by high-resolution TEM, and vice versa, migration of Ni onto TiO 2 -A. The TiO 2 overlayer rendered the Ni particles completely inactive as a hydrogenation/hydrodeoxygenation catalyst. Conversely, the small amounts of Ni (<1.5 wt %) migrated onto TiO 2 -A formed highly dispersed Ni, undetectable by high-resolution TEM (<2 nm), that were remarkably highly active for HDO of guaiacol, producing selectively phenolics. Such highly selective HDO catalysts could also be formed by incipient wetness impregnation of Ni in loadings above 2 wt % onto the TiO 2 -A, but it was essential to pretreat the sample in H 2 at 300 °C or higher. Pretreatment in H 2 at 200 °C generated catalysts that produced saturated ring products. The activity of the impregnated catalysts, as measured by guaiacol conversion, increased linearly with Ni loading below 0.5 wt %. The activity continued to increase with Ni loading but more slowly up to 2 wt %, beyond which there was little further change. The results suggested that two types of Ni species existed on the TiO 2 -A surface. One type consisted of a cluster of Ni atoms that were dominant on larger Ni particles that were active in aromatic ring hydrogenation and hydrodeoxygenation. They were readily covered by reducible TiO 2 -A at 300 °C or higher due to the traditional strong metal support interaction (SMSI) effect and became inactive. Another type was clusters of a very small number of Ni atoms, perhaps one atom, that were present as highly dispersed Ni clusters interacting strongly with the defect sites of TiO 2 -A. The strong interaction of this type of Ni with the TiO 2 defect deterred TiO x migration allowing surface exposed Ni atoms to catalyze the HDO of guaiacol with very high selectivities that were not characteristic of typical Ni particles.

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