Zhang Yuelan, Li Liping, Li Qi, Fan Jianming, Zheng Jing, Li Guangshe
States Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun, 130012, P.R. China.
Key Laboratory of Design and Assembly of Functional Nanostructures, Fujian Institute of Research on the Structure of Matter, Fuzhou, 350002, P.R. China.
Chemistry. 2016 Sep 26;22(40):14196-204. doi: 10.1002/chem.201601681. Epub 2016 Jul 19.
Developing new methods to synthesize intermetallics is one of the most critical issues for the discovery and application of multifunctional metal materials; however, the synthesis of Sn-containing intermetallics is challenging. In this work, we demonstrated for the first time that a self-disproportionation-induced in situ process produces cavernous Sn-Cu intermetallics (Cu3 Sn and Cu6 Sn5 ). The successful synthesis is realized by introducing inorganic metal salts (SnCl2 ⋅2 H2 O) to NaOH aqueous solution to form an intermediate product of reductant (Na2 SnO2 ) and by employing steam pressures that enhance the reduction ability. Distinct from the traditional in situ reduction, the current reduction process avoided the uncontrolled phase composition and excessive use of organic regents. An insight into the mechanism was revealed for the Sn-Cu case. Moreover, this method could be extended to other Sn-containing materials (Sn-Co, Sn-Ni). All these intermetallics were attempted in the catalytic effect on thermal decompositions of ammonium perchlorate. It is demonstrated that Cu3 Sn showed an outstanding catalytic performance. The superior property might be primarily originated from the intrinsic chemical compositions and cavernous morphology as well. We supposed that this smart solution reduction methodology reported here would provide a new recognition for the reduction reaction, and its modified strategy may be applied to the synthesis of other metals, intermetallics as well as some unknown materials.
开发合成金属间化合物的新方法是多功能金属材料发现与应用的关键问题之一；然而，含锡金属间化合物的合成具有挑战性。在这项工作中，我们首次证明了自歧化诱导原位过程可生成海绵状锡 - 铜金属间化合物（Cu3Sn和Cu6Sn5）。通过将无机金属盐（SnCl2·2H2O）引入氢氧化钠水溶液中形成还原剂中间产物（Na2SnO2），并利用蒸汽压力增强还原能力，实现了成功合成。与传统的原位还原不同，当前的还原过程避免了相组成失控和有机试剂的过度使用。揭示了锡 - 铜体系的反应机理。此外，该方法可扩展到其他含锡材料（Sn - Co、Sn - Ni）。对所有这些金属间化合物进行了高氯酸铵热分解催化效果的尝试。结果表明，Cu3Sn表现出优异的催化性能。这种优异性能可能主要源于其内在化学成分和海绵状形态。我们认为，本文报道的这种智能溶液还原方法将为还原反应提供新的认识，其改进策略可能应用于其他金属、金属间化合物以及一些未知材料的合成。
