Effect of Defect Tuning on the Catalytic Behavior of Perovskite Structure Lanthanum Manganite†

doi:10.7503/cjcu20170497

Abstract

Abstract:

In this paper, lanthanum manganite with perovskite structure was chosen as a model compound of which the valence of Mn and oxygen defects were tuned by introducing A-site defect. Electrochemical catalytic oxygen evolution reaction(OER) and catalytic oxidation of CO were performed to evaluate the relationship between the defects and catalytic properties. All the samples were prepared via a sol-gel method, and the composition was determined by ICP-OES. The valence of Mn was titrated by iodometric method. The oxygen defect(δ) was calculated according to the principle of neutrality. The chemical formulas of the samples were La_0.85MnO_2.85, La_0.80MnO_2.81 and La_0.75MnO_2.74, respectively. The structure, binding energy of Mn and morphology of the samples were characterized by X-ray diffraction(XRD), X-ray photoelectron spectroscopy(XPS) and scanning electron microscopy(SEM). The specific surface area of the samples was determined by physical adsorption. The OER results indicated a linear relationship between the concentration of defect and OER property, while the La_0.80MnO_2.81 sample showed the best CO catalytic property.

Key words: Oxygen defect, lanthanum manganite, Oxygen evolution reaction(OER), Catalytic oxidation of CO

CLC Number:

O611

TrendMD:

JIANG Yilan, YUAN Long, WANG Xiyang, HUANG Keke, FENG Shouhua. Effect of Defect Tuning on the Catalytic Behavior of Perovskite Structure Lanthanum Manganite^†[J]. Chem. J. Chinese Universities, 2018, 39(3): 416.

Figures/Tables 6

Fig.1 XRD patterns of La0.85MnO2.85(a), La0.80MnO2.81(b) and La0.75MnO2.74(c)

Fig.2 XPS spectra of La0.85MnO2.85(a), La0.80MnO2.81(b) and La0.75MnO2.74(c) (A) O1s; (B) Mn3s; (C) Mn2p.

Table 1 Valence of the surface Mn, surface La/Mn ratio, Oads/Olatt surface atomic ratio and BET surface area of the samples

Sample	Valence of surface Mn	Surface La/Mn ratio	Surface O_ads/ $O latt$ ratio	Surface area/(m²·g^-1)
La_0.85Mn $O 2.8 5$	3.22	1.20	0.75	21.9
La_0.80MnO_2.81	3.33	1.03	0.81	35.5
La_0.75MnO_2.74	3.44	0.95	0.90	34.2

Table 1 Valence of the surface Mn, surface La/Mn ratio, Oads/Olatt surface atomic ratio and BET surface area of the samples

Sample	Valence of surface Mn	Surface La/Mn ratio	Surface O_ads/ $O latt$ ratio	Surface area/(m²·g^-1)
La_0.85Mn $O 2.8 5$	3.22	1.20	0.75	21.9
La_0.80MnO_2.81	3.33	1.03	0.81	35.5
La_0.75MnO_2.74	3.44	0.95	0.90	34.2

Fig.3 SEM images(A—C) and EDS spectra(D—F) of LaxMnO3-δ(A), (D) La0.85MnO2.85; (B), (E) La0.80MnO2.81; (C), (F) La0.75MnO2.74.

Fig.4 OER electrocatalytic activities(A) and corresponding Tafel plots(B) of La0.85MnO2.85(a), La0.80MnO2.81(b) and La0.75MnO2.74(c)

Fig.5 CO conversion as a function of temperature over LaxMnO3-δ(A) and the T10 CO, T50 CO, T90 CO,T100 CO of LaxMnO3-δ(B)T10 CO, T50 CO, T90 CO, T100 CO are the temperature at CO conversion of 10%, 50%, 90% and 100%, respectively.

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