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Acta Physico-Chimica Sinca  2017, Vol. 33 Issue (5): 984-992    DOI: 10.3866/PKU.WHXB201702084
ARTICLE     
Catalytic Properties of Platinum Nanoclusters Supported on Iron Oxides for the Solvent-Free Hydrogenation of Halonitrobenzene
Chao LIAN1,2,Kai ZHANG2,Yuan WANG2,*()
1 Department of Chemistry, School of Science, Beijing Jiaotong University, Beijing 100044, P. R. China
2 Beijing National Laboratory for Molecular Sciences, State Key Laboratory for Structural Chemistry of Unstable and Stable Species, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, P. R. China
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Abstract  

It is of significance to investigate the support effect in heterogeneous metal catalysts. Pt/Fe3O4, Pt/ γ-Fe2O3, and Pt/α-Fe2O3 nanocomposites with the same Pt nanoclusters were prepared by adsorbing Pt colloidal particles stabilized with simple ions and solvent molecules on different iron oxide supports. The catalytic performances over the as-prepared catalysts for the selective hydrogenation of o-chloronitrobenzene (o-CNB) in the absence of solvent were evaluated. It was found that the catalytic activity and selectivity over the prepared iron oxide-supported Pt nanocluster catalysts were higher than those of a commercial Pt/C catalyst. The selectivity towards o-chloroaniline over Pt/γ-Fe2O3 or Pt/α-Fe2O3 was higher than that over Pt/Fe3O4, while the catalytic activity over Pt/Fe3O4 was 50% higher than that over Pt/α-Fe2O3. The Pt/iron oxide catalysts also exhibited excellent catalytic properties for the solvent-free selective hydrogenation of other tested halonitrobenzenes, with the selectivity to corresponding haloanilines being > 99%. In addition, the influences of temperature and hydrogen pressure on the solvent-free selective hydrogenation of o-CNB over Pt/Fe3O4 were studied. This work is helpful in understanding the superior properties of iron oxide-supported metal nanocluster catalysts and provides a foundation for further developing highly efficient catalytic systems based on metal nanoclusters.



Key wordsPlatinum      Metal nanocluster      Iron oxide      Halonitrobenzene      Haloaniline      Selective hydrogenation     
Received: 28 November 2016      Published: 08 February 2017
MSC2000:  O643  
Fund:  the National Natural Science Foundation of China(21573010);MOST, China(2016YFE0118700);and Fundamental Research Funds for the Central Universities, China(2015RC070)
Corresponding Authors: Yuan WANG     E-mail: wangy@pku.edu.cn
Cite this article:

Chao LIAN,Kai ZHANG,Yuan WANG. Catalytic Properties of Platinum Nanoclusters Supported on Iron Oxides for the Solvent-Free Hydrogenation of Halonitrobenzene. Acta Physico-Chimica Sinca, 2017, 33(5): 984-992.

URL:

http://www.whxb.pku.edu.cn/10.3866/PKU.WHXB201702084     OR     http://www.whxb.pku.edu.cn/Y2017/V33/I5/984

Fig 1 XRD patterns of the Pt/Fe3O4 (a), Pt/γ-Fe2O3 (b) and Pt/α-Fe2O3 (c) catalysts XRD: X-ray diffraction
Fig 2 TEM images (a-c) of the catalysts and the Pt particle size distributions (d-f) TEM: transmission electron microscopy. (a, d) Pt/Fe3O4, (b, e) Pt/γ-Fe2O3, (c, f) Pt/α-Fe2O3
Fig示意图1 Reaction pathways for the solvent-free hydrogenation of halonitrobenzene
CatalystReaction time/minReaction ratebConversionc/%dSelectivity/%d
o-CANANothers
Pt/Fe3O41121.510099.40.5trace
Pt/γ-Fe2O31371.210099.80.2trace
Pt/α-Fe2O31691.010099.70.2trace
Pt/C (Acros)e3350.510085.14.310.6f
Table 1 Catalytic properties of platinum supported on iron oxides for the solvent-free hydrogenation of o-CNBa
PVP-PtPt/Fe3O4Pt/α-Fe2O3Pt/γ-Fe2O3
Binding energy/eV70.871.371.171.1
Table 2 Binding energy of the Pt 4f7/2 core-level in the Pt/iron oxides catalystsa
Temperature/℃ Pressure/MPa Reaction time/min Reaction rateb Conversionc/% Selectivity/%
o-CANANothersd
502.01121.510099.40.5trace
702.01001.710099.20.8trace
902.0672.510099.01.0trace
1102.0523.210098.91.1trace
501.02920.610099.60.4trace
503.0991.710099.40.6trace
504.0702.410098.80.50.7
505.0453.710095.30.44.3
Table 3 Influences of temperature and hydrogen pressure on the solvent-free hydrogenation of o-CNB over Pt/Fe3O4a
SubstrateTemperature/℃Reaction time/minConversionb/%Yieldc/%
608010099.5
1004510099
906110099.2
608510099.1
Table 4 Solvent-free selective hydrogenation of other halonitrobenzenes over Pt/Fe3O4a
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