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Frontiers of Chemical Science and Engineering

Front. Chem. Sci. Eng.    2019, Vol. 13 Issue (3) : 501-510     https://doi.org/10.1007/s11705-019-1810-7
RESEARCH ARTICLE
Plasma-electrochemical synthesis of europium doped cerium oxide nanoparticles
Liangliang Lin1(), Xintong Ma2, Sirui Li2(), Marly Wouters2, Volker Hessel3
1. School of Chemical and Material Engineering, Jiangnan University, Wuxi 214122, China
2. Micro Flow Chemistry and Process Technology, Chemical Engineering and Chemistry Department, Eindhoven University of Technology, 5600 MB Eindhoven, the Netherlands
3. School of Chemical Engineering, The University of Adelaide, South Australia 5005, Australia
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Abstract

In the present study, a plasma-electrochemical method was demonstrated for the synthesis of europium doped ceria nanoparticles. Ce(NO3)3·6H2O and Eu(NO3)3·5H2O were used as the starting materials and being dissolved in the distilled water as the electrolyte solution. The plasma-liquid interaction process was in-situ investigated by an optical emission spectroscopy, and the obtained products were characterized by complementary analytical methods. Results showed that crystalline cubic CeO2:Eu3+ nanoparticles were successfully obtained, with a particle size in the range from 30 to 60 nm. The crystal structure didn’t change during the calcination at a temperature from 400°C to 1000°C, with the average crystallite size being estimated to be 52 nm at 1000°C. Eu3+ ions were shown to be effectively and uniformly doped into the CeO2 lattices. As a result, the obtained nanophosphors emit apparent red color under the UV irradiation, which can be easily observed by naked eye. The photoluminescence spectrum further proves the downshift behavior of the obtained products, where characteristic 5D07F1,2,3 transitions of Eu3+ ions had been detected. Due to the simple, flexible and environmental friendly process, this plasma-electrochemical method should have great potential for the synthesis of a series of nanophosphors, especially for bio-application purpose.

Keywords plasma-electrochemical method      europium doped ceria      rare earth nanoparticles      photoluminescence     
Corresponding Authors: Liangliang Lin,Sirui Li   
Just Accepted Date: 20 March 2019   Online First Date: 05 May 2019    Issue Date: 22 August 2019
 Cite this article:   
Liangliang Lin,Xintong Ma,Sirui Li, et al. Plasma-electrochemical synthesis of europium doped cerium oxide nanoparticles[J]. Front. Chem. Sci. Eng., 2019, 13(3): 501-510.
 URL:  
http://journal.hep.com.cn/fcse/EN/10.1007/s11705-019-1810-7
http://journal.hep.com.cn/fcse/EN/Y2019/V13/I3/501
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Liangliang Lin
Xintong Ma
Sirui Li
Marly Wouters
Volker Hessel
Fig.1  The schematic diagram of the microplasma reactor used in this study
Fig.2  The images of the electrolyte solution treated by plasma for (a) 0 h, (b) 1 h, (c) 2 h, (d) 3 h and (e) 4 h
Fig.3  Emission spectra of pure argon plasma as well as argon plasma interacting with the electrolyte solution
Fig.4  (a) Element mapping area, (b) Ce, (c) O, (d) Eu and (e) EDX spectrum of the obtained samples
Fig.5  (a) XRD patterns of CeO2:Eu3+ (2 mol%?10 mol%) annealed at 1000°C; (b) XRD patterns of CeO2:Eu3+ annealed at different temperatures
Fig.6  (a,b) Representative TEM images, (c) HRTEM image and (d) SAED image of 10% Eu-doped CeO2 nanoparticles obtained at 1000°C
Fig.7  Raman spectra of CeO2 nanoparticles with and without Eu3+ doping
Fig.8  (a) Full XPS spectra of CeO2 nanoparticles with and without Eu3+ doping; (b) XPS spectrum of Ce3d; (c) XPS spectrum of Eu3d; (d) XPS spectrum and the associated spectral decomposition of O1s
Fig.9  Representative photoluminescent emission spectra (a) CeO2 and (b) CeO2:4%Eu under UV excitation. Inset shows a typical photograph of the obtained nanophosphors under the UV irradiation of 360 nm
Methods Step Extra toxic chemicals Temperature/°C Size/nm Pre/post treatment Remark Ref.
Plasma-assisted 2 None 400?1000 20?60 Centrifugation
Coprecipitation- calcination 4 HNO3
NH4OH
C2H5OH
1300 Micro-powder Centrifugation Washing Eu2O3 as the raw material [29]
Hydrothermal
method
4 Na3PO4·12H2O
C2H5OH
180?450 300?400 Stirring
Centrifugation Washing
[23]
Ultrasonic spray pyrolysis 5 C2H6O2
NaHCO3
HNO3
1000 40?80 Dissolution
Centrifugation Washing
Filtering
Need to prepare solution droplets [30]
Micro-emulsion reaction method 6 C6H8O7
C12H26O7
C6H14
CHCl3
NH4OH
1000 30?55 (surfactant needed) Milling
Washing
Stirring
Evaporation
CeO2 as the raw material [31]
Sol-gel method 4 C6H8O7·H2OEthylene glycol 400?900 15?55 Milling
Pre-fire
Stirring
Complex procedures [32]
Solvothermal process 3 C2H5OH
NH4OH
500?900 5?27 Pre-heating
Stirring
Washing
Centrifugation
Long reaction time [33]
Tab.1  Summary of main parameters for the synthesis of CeO2:Eu nanoparticles by various methods
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