Electrocatalytic Activity of Cobalt Doped Ceria Nanoparticles

doi:10.15541/jim20170516

Abstract

Abstract:

It is very difficult for single ceria to be used as an electrocatalyst because of its relatively poor electron conductivity and rare number of oxygen vacancy. Recently, it has been studied in the field of CO catalysis by doping transition metallic or non-metallic elements to improve the catalytic ability of ceria, while recent research has demonstrated that many oxides containing cobalt display better electrocatalytic activity. In this study cobalt doped ceria nanoparticles were prepared by homogeneous precipitation method. The electrochemical tests show that the optimum doping molar ratio is 20mol% for ORR and OER catalytic effect. After 10 hours of catalysis, the current density of ORR and OER decrease by about 20% and 5%, respectively, far below the corresponding values when noble metal and undoped cerium oxide nanoparticles were used as catalysts, and it indicated that the prepared catalyst owns good catalytic stability. In addition, XPS and other tests show that the decrease of charge transfer impedance (the improvement of electronic conductivity), the increase of active oxygen species, and the increased oxygen vacancies after doping are main reasons for improved catalytic performance. Therefore, doping cobalt greatly enhanced electrocatalytic properties of ceria nanoparticles are greatly enhanced by doping cobalt, providing guidence for other ionic conductors employed as bifunctional electrocatalysts.

Key words: ceria oxide, doping, electrocatalyst

CLC Number:

TQ174

YANG Zhi-Bin, YUE Tong-Lian, YU Xiang-Nan, WU Miao-Miao. Electrocatalytic Activity of Cobalt Doped Ceria Nanoparticles[J]. Journal of Inorganic Materials, 2018, 33(8): 845-853.

Figures/Tables 11

Fig. 1 XRD patterns of ceria nanoparticles with different doping ratio of cobalt(a) Whole range patterns; (b) Magnified patterns of the highest peak (111)

Fig. 2 (a) N2 adsorption-desorption isotherm of ceria nanoparticles and (b) BJH pore size distribution curve of ceria nanoparticles

Fig. 3 Polarization curves at 1600 r/min of different of ceria nanoparticles with different doping ratio(a) (ORR) and (b) (OER)

Fig. 4 Polarization curves at 1600 r/min of (a) ceria nanoparticles and Pt/C (ORR) and (b) ceria nanoparticles and RuO2 (OER)

Fig. 5 (a) Corresponding transfer electron number of ceria nanoparticles with different doping amount in RRDE model, and (b) corresponding K-L plots of ceria nanoparticles with different doping ratio at 0.5 V

Fig. 6 Current-time(I-t) chronoamperometric responses for ceria nanoparticles (a) at two different doping ratio and Pt/C, and (b) at two different doping ratio and RuO2

Fig. 7 (a) Corresponding ORR(a) and OER (b) electrochemical impedance spectra of Ceria at two different doping ratio

Fig. 8 Corresponding Raman spectra of Ceria at two different doping ratio of Co

Fig. 9 Corresponding TEM and HRTEM images of Ceria at two different doping ratio(a, b) 0; (c, d) 20mol%

Fig. 10 (a) XPS survey spectra and (b) high-resolution XPS spectra of Co2p of CeO2 doping with 20mol% Co; High-resolution XPS spectra of Ce3d (c) and O1s (d) of CeO2 with different doping ratio

Table 1 Corresponding XPS results of different doping ratio

Sample	Content
Sample	O_α/at%	O_β/at%	O_δ/at%	O_γ/at%	O_β/O_α	[Ce³⁺/(Ce⁴⁺+Ce³⁺)]/%
0	48.5	29.2	10.4	11.8	0.60	20.1
20mol%	27.2	53.1	10.5	9.2	1.95	24.1

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