3LiBH4/CeF3体系的放氢性能及机制

doi:10.7503/cjcu20150848

高等学校化学学报 ›› 2016, Vol. 37 ›› Issue (4): 688.doi: 10.7503/cjcu20150848

3LiBH₄/CeF₃体系的放氢性能及机制

顾润, 张明, 王春阳, 黄维军, 柳东明()

安徽工业大学材料科学与工程学院, 马鞍山 243002

收稿日期:2015-11-04 出版日期:2016-04-10 发布日期:2016-01-24
基金资助:
国家自然科学基金(批准号: 51371008)资助

Dehydrogenation Property and Mechanism of 3LiBH4/CeF3System

GU Run, ZHANG Ming, WANG Chunyang, HUANG Weijun, LIU Dongming^*()

School of Materials Science and Engineering Anhui University of Technology,Maanshan 243002, China

Received:2015-11-04 Online:2016-04-10 Published:2016-01-24
Contact: LIU Dongming E-mail:ldm_ahut@163.com
Supported by:
† Supported by the National Natural Science Foundation of China(No.51371008)

摘要/Abstract

摘要：

采用球磨法制备了3LiBH₄/CeF₃反应体系, 通过压力-组成-温度(PCT)测试仪、 X射线衍射仪(XRD)和傅里叶变换红外光谱仪(FTIR)研究了体系的放氢性能、反应机制及性能改善机理. 结果表明, 3LiBH₄/CeF₃体系在295 ℃左右快速放氢, 总放氢量为4.1%(质量分数). 放氢过程中CeF₃与LiBH₄直接发生反应: 3LiBH₄+CeF₃1/2CeB₆+1/2CeH₂+3LiF+11/2H₂. 与纯LiBH₄相比, 放氢热力学稳定性和表观活化能的降低是3LiBH₄/CeF₃体系放氢温度下降的主要原因.

关键词: 硼氢化锂, 氟化铈, 放氢性能, 放氢机制

Abstract:

The 3LiBH₄/CeF₃ reactive system was prepared by ball-milling treatment. Its dehydrogenation property and reaction as well as the property improvement mechanism were investigated by pressure-composition-temperature(PCT) analyser, X-ray diffractometer(XRD) and Fourier transform infrared spectrometer(FTIR). It was found that the 3LiBH₄/CeF₃ system fast released hydrogen at about 295 ℃ with about 4.1%(mass fraction) of hydrogen totally desorbed. During the dehydrogenation process, CeF₃ reacted directly with LiBH₄ according to the reaction 3LiBH₄+CeF₃ 1/2CeB₆+1/2CeH₂+3LiF+11/2H₂. In comparison with pristine LiBH₄, the decrease in dehydrogenation thermodynamic stability and apparent activation energy are the main reasons for the declined dehydrogenation temperature of the 3LiBH₄/CeF₃ system.

Key words: LiBH₄, CeF₃, Dehydrogenation property, Dehydrogenation mechanism

中图分类号:

O643

TrendMD:

顾润, 张明, 王春阳, 黄维军, 柳东明. 3LiBH₄/CeF₃体系的放氢性能及机制. 高等学校化学学报, 2016, 37(4): 688.

GU Run, ZHANG Ming, WANG Chunyang, HUANG Weijun, LIU Dongming. Dehydrogenation Property and Mechanism of 3LiBH4/CeF3System. Chem. J. Chinese Universities, 2016, 37(4): 688.

图/表 7

Fig.1 Hydrogen desorption curves of the 3LiBH4/CeF3 system ball-milled for different time

Fig.2 XRD patterns of the 3LiBH4/CeF3(BM-2 h) system dehydrogenated at 250(a), 350(b) and 450 ℃(c), respectively

Fig.3 FTIR spectra of the 3LiBH4/CeF3(BM-2 h) system before(a) and after(b—f) heating at different temperaturesHeating temperature/℃: b. 250; c. 300; d. 350; e. 400; f. 450.

Fig.4 Dehydrogenation p-c isotherm of the 3LiBH4/CeF3 system at 290 ℃

Fig.5 Isothermal dehydrogenation curves of the 3LiBH4/CeF3 system at different temperatures

Fig.6 Plots of [-ln(1-α)]1/2 vs. t for the 3LiBH4/CeF3 system dehydrogenated at different temperatures

Fig.7 Arrhenius curve for the dehydrogenation of the 3LiBH4/CeF3 system

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3LiBH₄/CeF₃体系的放氢性能及机制

Dehydrogenation Property and Mechanism of 3LiBH4/CeF3System

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