【作者】 李志杰；

【导师】 王吉德； 刘瑞泉；

【作者基本信息】 新疆大学 ， 物理化学， 2005， 硕士

【摘要】 合成氨工业对于人类社会发展具有重要的意义,传统哈伯（Harber）氨合成法的基本原理局限了氨合成工业的进一步发展,所以各种合成氨新方法的探索在世界范围内展开,而利用高温质子导体作为电解质常压电化学方法合成氨的发展则是其中一个比较新颖合理的分支,高温质子导体（HTPC）自八十年代初期见诸报道以来,人们已经作了大量工作,包括:传导机制、结构测定、相关电性质、应用研究等。由于高温质子导体在高温条件下的含氢气氛中展现出质子传导性,故在传感器,燃料电池,气体分离等方面有很大的潜在应用价值。而George Marnellos 和Michael Stoukides 关于利用HTPC 在常压下合成氨的报道,使这种应用前景显得更加具体,从而更加具有吸引力。本文针对高温质子导体中的一种类型-钙钛矿型,用柠檬酸盐溶胶-凝胶法制备合成了三个系列的钙钛矿型高温质子导体: 简单钙钛矿型BaCe_0.90Y_0.10O3-δ BaCeO₃ 基: BaCe_0.8Gd_0.2O3-δ BaCe_0.90Sm_0.10O3-δ Ba_0.90La_0.10Ce_0.90Y_0.10O_3-δ BaCe_0.80Gd_0.10Sm_0.10O3-δ BaZrO₃基: BaCe_0.2Zr_0.7Y_0.1O3-δ BaZr_0.9Y_0.1O_3-δ更多还原

【Abstract】 The industry of synthesis ammonia is most important to the development of our society. The traditional method of ammonia synthesis is Harber way which limited its further development. So, many novelty methods of ammonia synthesis were explored in recent years. It is one reasonable way of the methods that synthesis ammonia using high-temperature proton conductors（HTPC）. A lot of research works have been done since the high temperature proton conductor was reported in 1980’s,such as: conduction mechanism, structure, related electrical characterization, application research, etc. The potential application value of HTPC in gas sensors, SOFCs（solid oxide fuel cells） and gas separators is attributed to its high proton conduction ranges at high temperature under atmosphere containing hydrogen. While, the synthesis of ammonia using HTPC under atmosphere reported by George Marnellos and Michael Stoukides makes its perspective of application more practical and even more charming. We synthesized three series perovskite-type compounds using citrate sol-gel method which are one style of HTPC in this paper. BaCe_0.90Y_0.10O3-δ BaCeO₃ 基: BaCe_0.8Gd_0.2O3-δ BaCe_0.90Sm_0.10O3-δ Ba_0.90La_0.10Ce_0.90Y_0.10O_3-δ BaCe_0.80Gd_0.10Sm_0.10O3-δ Simple perovskite-type BaZrO3 type: BaCe0.2Zr0.7Y0.1O3-δBaZr0.9Y0.1O3-δ Ba3CaZr0.5Nb1.5O9-δComplex perovskite-type BCN18 type: Ba3（Ca1.18Nb1.82）O9-δ Ba3Ca0.9Nd0.28Nb1.82O9-δ We use thermal analysis （TG-DTA） to obtain the optimum calcination temperature of thermal decomposition. A single perovskite-type phase was confirmed by powder X-ray diffraction （XRD）. The topography was characterized with transmission electron microscopy （TEM） and scanning electron microscopy （SEM）. Parameters such as working temperatures, different gas ambiences were changed to characterize the electrical properties of HTPC sinters prepared. All of the samples produce ammonia at different degrees, and the rates of ammonia formation are up to 10-9 mol.s-1.cm-2. And we also analyzed the effection of synthesing temperature and potential to the rate of ammonia formation. The result shows that we got larger specific surface of the samples using citrate sol-gel method comparison to the traditional solid reaction method, at the same time, the samples shoes the better sinter property and proton conduction property. During the experiment of synthesizing ammonia using different series HTPC, we found that the ability of synthesizing ammonia of each series HTPC were listed below: BaCeO3 type > BaZrO3 type > BCN18 type What is more, to the same series HTPC, double doped samples showed better更多还原