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Catalysts 2015, 5(2), 759-773; doi:10.3390/catal5020759

Effect of Phosphine Doping and the Surface Metal State of Ni on the Catalytic Performance of Ni/Al2O3 Catalyst

1,2,3
,
1,2,* , 1,2
,
1,2
,
1,2
,
1,2
and
1,2,*
1
State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China
2
Laboratory of Green Chemistry and Process, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China
3
University of Chinese Academy of Sciences, Beijing 100049, China
*
Authors to whom correspondence should be addressed.
Academic Editor: Masahiko Arai
Received: 12 February 2015 / Revised: 6 April 2015 / Accepted: 15 April 2015 / Published: 23 April 2015
(This article belongs to the Special Issue Metal Catalysts Recycling and Heterogeneous/Homogeneous Catalysis)
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Abstract

Ni-based catalysts as replacement for noble metal catalysts are of particular interest in the catalytic conversion of biomass due to their cheap and satisfactory catalytic activity. The Ni/SiO2 catalyst has been studied for the hydrogenolysis of glycerol, and doping with phosphorus (P) found to improve the catalytic performance significantly because of the formation of Ni2P alloys. However, in the present work we disclose a different catalytic phenomenon for the P-doped Ni/Al2O3 catalyst. We found that doping with P has a significant effect on the state of the active Ni species, and thus improves the selectivity to 1,2-propanediol (1,2-PDO) significantly in the hydrogenolysis of glycerol, although Ni-P alloys were not observed in our catalytic system. The structure and selectivity correlations were determined from the experimental data, combining the results of X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), hydrogen temperature-programmed reduction (H2-TPR) and ammonia temperature-programmed desorption (NH3-TPD). The presence of NiO species, formed from P-doped Ni/Al2O3 catalyst, was shown to benefit the formation of 1,2-PDO. This was supported by the results of the Ni/Al2O3 catalyst containing NiO species with incomplete reduction. Furthermore, the role the NiO species played in the reaction and the potential reaction mechanism over the P-doped Ni/Al2O3 catalyst is discussed. The new findings in the present work open a new vision for Ni catalysis and will benefit researchers in designing Ni-based catalysts. View Full-Text
Keywords: glycerol; hydrogenolysis; Ni/Al2O3; phosphorus-doping; metal state glycerol; hydrogenolysis; Ni/Al2O3; phosphorus-doping; metal state
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

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Li, X.; Cheng, H.; Liang, G.; He, L.; Lin, W.; Yu, Y.; Zhao, F. Effect of Phosphine Doping and the Surface Metal State of Ni on the Catalytic Performance of Ni/Al2O3 Catalyst. Catalysts 2015, 5, 759-773.

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