CO2气氛中La掺杂BaCo0.88Nb0.12O3-δ膜的透氧性能及结构稳定性

doi:10.7503/cjcu20141082

摘要/Abstract

摘要：

利用固相合成法制备了A位La掺杂BaCo_0.88Nb_0.12O_3-_δ[BLCN-x, x为La的掺杂量(摩尔分数)]钙钛矿透氧膜材料, 采用X射线衍射(XRD)、扫描电子显微镜(SEM)、热重分析(TG)及程序升温脱附-质谱(TPD-MS)等方法研究了CO₂气氛静态处理及动态透氧条件BLCN-x系列材料的结构稳定性. 研究结果表明, 随着La掺杂量的增加, BLCN-x膜片材料抗CO₂腐蚀的性能明显提高. 当La含量高于0.5时, 在850 ℃纯CO₂气氛静态处理或透氧条件下均未观察到碳酸盐衍射峰. 尽管La掺杂会降低BLCN-x膜片的初始透氧量, 但在CO₂气氛吹扫时透氧量的降低速率明显减慢, 其中BLCN-0.5膜片在纯CO₂气氛下10 h后的透氧量仍可达到0.46 mL·cm^-2·min^-1. 通过容差因子和平均金属-氧键能计算可知, 良好的结构稳定性和增强的金属-氧键能是导致La掺杂样品抗CO₂腐蚀的主要因素.

关键词: 钙钛矿, 透氧膜, 二氧化碳, 掺杂, 结构稳定性

Abstract:

La-doped BaCo_0.88Nb_0.12O_3-_δ(BLCN-x, x represents the molar ratio of La) perovskite membranes were prepared by solid phase reaction. The structrural stability of membranes was analyzed by X-ray diffraction(XRD), scanning electron microscopy(SEM), thermogravimetric(TG) analysis and temperature programmed desorption-mass spectrography(TPD-MS) methods. The results indicated that the CO₂ tolerance properties of BLCN-x membranes were improved markedly with the increase of La content. Specially, the diffraction peaks of witherite can’t be observed for the membranes with a La content higher than 0.5, whatever the membranes were calcined or conducted the oxygen permeation measurement with pure CO₂ sweeping. The initial oxygen permeation flux of BLCN-x membranes would be reduced with the doping of La, however, the oxygen flux of BLCN-x membranes swept by CO₂was more stable with the increase of La content. Particularly, the oxygen flux of BLCN-0.5 membrane is about 0.46 mL·cm^-2·min^-1 after pure CO₂ sweeping for 10 h. The better structural stability and CO₂ tolerance properties of BLCN-x membranes with higher La content are due to more appropriate Goldschmidt tolerance factor and the enhanced average metal-oxygen bond energy.

Key words: Perovskite, Oxygen permeation membrane, CO2, Doping, Structural stability

中图分类号:

O613
O643

TrendMD:

张星星, 吴成章, 周建芳, 杨恭辉, 刘银河, 张玉文, 丁伟中. CO₂气氛中La掺杂BaCo_0.88Nb_0.12O_3-_δ膜的透氧性能及结构稳定性. 高等学校化学学报, 2015, 36(7): 1246.

ZHANG Xingxing, WU Chengzhang, ZHOU Jianfang, YANG Gonghui, LIU Yinhe, ZHANG Yuwen, DING Weizhong. Oxygen Permeation Property and Structural Stabiltiy of La-doped BaCo_0.88Nb_0.12O_3-_δ Membranes in CO₂ Atmosphere^†. Chem. J. Chinese Universities, 2015, 36(7): 1246.

图/表 10

Fig.1 XRD patterns(A) and (110) reflection peaks(B) of as-synthesized BLCN-x powdersa. BCN; b. BLCN-0.1; c. BLCN-0.2;d. BLCN-0.3; e. BLCN-0.5; f. LCN.

Table 1 Calculated lattice parameters, tolerance factor, activation energy of the oxygen permeability, and average metal-oxygen bond energy(ABE) for BLCN-x membranes

Membrane	Lattice parameter/nm	ABE/(kJ·mol^-1)	Tolerance factor(Co⁴⁺/Co³⁺)	Activation energy/(kJ·mol^-1)
BCN	0.408	-279.1	1.084/1.091	35.8, 132.7
BCLN-0.1	0.404	-285.2	1.076/1.083	65.1
BLCN-0.2	0.401	-291.2	1.067/1.074	67.0
BLCN-0.3	0.396	-297.3	1.058/1.065	70.1
BLCN-0.5	0.391	-309.3	1.041/1.048	56.5
LCN	0.382	-339.2	0.998/1.004	36.2

Fig.2 SEM images of the fresh BLCN-x membranes(A) BCN; (B) BLCN-0.1; (C) BLCN-0.2; (D) BLCN-0.3; (E) BLCN-0.5; (F) LCN.

Fig.3 XRD patterns of BLCN-x powders calcined at 850 ℃ for 5 h under pure CO2 atmospherea. BCN; b. BLCN-0.1; c. BLCN-0.2;d. BLCN-0.3; e. BLCN-0.5.

Fig.4 SEM images of BLCN-x membranes after calcining at 850 ℃ for 5 h under pure CO2 atmosphere(A) BCN; (B) BLCN-0.1; (C) BLCN-0.2; (D) BLCN-0.3; (E) BLCN-0.5; (F) LCN.

Fig.5 Mass change of BLCN-x powders under the atmosphere of N2 or CO2a. BCN; b. BLCN-0.1; c. BLCN-0.2;d. BLCN-0.3; e. BLCN-0.5.

Fig.6 CO2 TPD-MS spectra of BLCN-x powders calcined at 850 ℃ for 5 h under pure CO2 atmospherea. BCN; b. BLCN-0.1; c. BLCN-0.2; d. BLCN-0.3; e. BLCN-0.5. Inset is the magnified TPD-MS spectra of BLCN-0.3 and BLCN-0.5.

Fig.7 Temperature dependence of oxygen permeable flues through BLCN-x membranes(A) and related Arrhenius plots(B)a. BCN; b. BLCN-0.1; c. BLCN-0.2; d. BLCN-0.3; e. BLCN-0.5; f. LCN.

Fig.8 Oxygen permeation flues of BLCN-x membrane swept by pure CO2 at 850 ℃Thickness of membrane: 0.5 mm;air flow rate: 110 mL/min;CO2 flow rate: 80 mL/min.

Fig.9 XRD patterns of BLCN-x membranes after oxygen permeation for 10 h at 850 ℃ under pure CO2 atmospherea. BCN; b. BLCN-0.1; c. BLCN-0.2;d. BLCN-0.3; e. BLCN-0.5; f. LCN.

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CO₂气氛中La掺杂BaCo_0.88Nb_0.12O_3-_δ膜的透氧性能及结构稳定性

Oxygen Permeation Property and Structural Stabiltiy of La-doped BaCo_0.88Nb_0.12O_3-_δ Membranes in CO₂ Atmosphere^†

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