Selective gas phase hydrogenation of p-nitrobenzonitrile to p-aminobenzonitrile over zirconia supported gold

Xiaodong Wang, Yufen Hao, Mark A. Keane

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Abstract

The catalytic action of Au/ZrO2 in the gas phase hydrogenation of p-nitrobenzonitrile (p-NBN) to p-aminobenzonitrile (p-ABN) has been assessed against Au/Al2O3. Crystalline ZrO2 was prepared by precipitation of ZrOCl2 with aqueous NH3 and calcined to generate tetragonal and monoclinic phases. Catalyst and support were characterised by surface area/porosity, temperature-programmed reduction (TPR), H2 chemisorption/temperature programmed desorption (TPD), X-ray diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) measurements. Higher calcination temperatures (673–973 K) increased the monoclinic ZrO2 content with a decrease in surface area and pore volume. Introduction of Au by deposition–precipitation resulted in tetragonal → monoclinic transformation with post-TPR formation of Au particles in the 3–13 nm size range and electron transfer from ZrO2. Reaction over Au/ZrO2 delivered 100% p-ABN yield with higher turnover frequency (267 h−1) than Au/Al2O3 (109 h−1) attributed to greater H2 chemisorption capacity under reaction conditions and enhanced −NO2 activation. Au/ZrO2 outperformed benchmark Pd/Al2O3 and Ni/Al2O3, which generated p-aminotoluene via subsequent hydrogenation/hydrogenolysis.
Original languageEnglish
Pages (from-to)171–179
Number of pages9
JournalApplied Catalysis A: General
Volume510
Early online date19 Nov 2015
DOIs
Publication statusPublished - 25 Jan 2016

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Zirconia
Gold
Hydrogenation
Gases
Chemisorption
Toluidines
Hydrogenolysis
Temperature programmed desorption
Catalyst supports
Calcination
Temperature
X ray photoelectron spectroscopy
Porosity
Chemical activation
Crystalline materials
Transmission electron microscopy
X ray diffraction
Catalysts
Electrons
zirconium oxide

Keywords

  • selective hydrogenation
  • Au/ZrO2
  • Au/Al2O3
  • p-Nitrobenzonitrile
  • p-Aminobenzonitrile

Cite this

Selective gas phase hydrogenation of p-nitrobenzonitrile to p-aminobenzonitrile over zirconia supported gold. / Wang, Xiaodong; Hao, Yufen; Keane, Mark A.

In: Applied Catalysis A: General, Vol. 510, 25.01.2016, p. 171–179.

Research output: Contribution to journalArticle

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abstract = "The catalytic action of Au/ZrO2 in the gas phase hydrogenation of p-nitrobenzonitrile (p-NBN) to p-aminobenzonitrile (p-ABN) has been assessed against Au/Al2O3. Crystalline ZrO2 was prepared by precipitation of ZrOCl2 with aqueous NH3 and calcined to generate tetragonal and monoclinic phases. Catalyst and support were characterised by surface area/porosity, temperature-programmed reduction (TPR), H2 chemisorption/temperature programmed desorption (TPD), X-ray diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) measurements. Higher calcination temperatures (673–973 K) increased the monoclinic ZrO2 content with a decrease in surface area and pore volume. Introduction of Au by deposition–precipitation resulted in tetragonal → monoclinic transformation with post-TPR formation of Au particles in the 3–13 nm size range and electron transfer from ZrO2. Reaction over Au/ZrO2 delivered 100{\%} p-ABN yield with higher turnover frequency (267 h−1) than Au/Al2O3 (109 h−1) attributed to greater H2 chemisorption capacity under reaction conditions and enhanced −NO2 activation. Au/ZrO2 outperformed benchmark Pd/Al2O3 and Ni/Al2O3, which generated p-aminotoluene via subsequent hydrogenation/hydrogenolysis.",
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N1 - Acknowledgements We acknowledge the contribution of Dr. N. Perret to this work. EPSRC support for free access to the TEM/SEM facility at the University of St. Andrews and financial support to Dr. X. Wang and Y. Hao through the Overseas Research Students Award Scheme (ORSAS) are also acknowledged.

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N2 - The catalytic action of Au/ZrO2 in the gas phase hydrogenation of p-nitrobenzonitrile (p-NBN) to p-aminobenzonitrile (p-ABN) has been assessed against Au/Al2O3. Crystalline ZrO2 was prepared by precipitation of ZrOCl2 with aqueous NH3 and calcined to generate tetragonal and monoclinic phases. Catalyst and support were characterised by surface area/porosity, temperature-programmed reduction (TPR), H2 chemisorption/temperature programmed desorption (TPD), X-ray diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) measurements. Higher calcination temperatures (673–973 K) increased the monoclinic ZrO2 content with a decrease in surface area and pore volume. Introduction of Au by deposition–precipitation resulted in tetragonal → monoclinic transformation with post-TPR formation of Au particles in the 3–13 nm size range and electron transfer from ZrO2. Reaction over Au/ZrO2 delivered 100% p-ABN yield with higher turnover frequency (267 h−1) than Au/Al2O3 (109 h−1) attributed to greater H2 chemisorption capacity under reaction conditions and enhanced −NO2 activation. Au/ZrO2 outperformed benchmark Pd/Al2O3 and Ni/Al2O3, which generated p-aminotoluene via subsequent hydrogenation/hydrogenolysis.

AB - The catalytic action of Au/ZrO2 in the gas phase hydrogenation of p-nitrobenzonitrile (p-NBN) to p-aminobenzonitrile (p-ABN) has been assessed against Au/Al2O3. Crystalline ZrO2 was prepared by precipitation of ZrOCl2 with aqueous NH3 and calcined to generate tetragonal and monoclinic phases. Catalyst and support were characterised by surface area/porosity, temperature-programmed reduction (TPR), H2 chemisorption/temperature programmed desorption (TPD), X-ray diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) measurements. Higher calcination temperatures (673–973 K) increased the monoclinic ZrO2 content with a decrease in surface area and pore volume. Introduction of Au by deposition–precipitation resulted in tetragonal → monoclinic transformation with post-TPR formation of Au particles in the 3–13 nm size range and electron transfer from ZrO2. Reaction over Au/ZrO2 delivered 100% p-ABN yield with higher turnover frequency (267 h−1) than Au/Al2O3 (109 h−1) attributed to greater H2 chemisorption capacity under reaction conditions and enhanced −NO2 activation. Au/ZrO2 outperformed benchmark Pd/Al2O3 and Ni/Al2O3, which generated p-aminotoluene via subsequent hydrogenation/hydrogenolysis.

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KW - p-Aminobenzonitrile

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