Zhang Yuelan, Li Liping, Ao Saren, Wang Jianghao, 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, Chinese Academy of Sciences, Fuzhou 350002, P. R. China.
ACS Omega. 2018 Jun 27;3(6):6988-6997. doi: 10.1021/acsomega.8b00725. eCollection 2018 Jun 30.
The design and synthesis of heteroatom-doping porous materials with unique surface/interfaces are of great significance for enhancing the sensitive surface performance in the fields of catalytic energy, especially gas sensor, CO oxidation, and ammonium perchlorate decomposition. Usually, the template method followed by a high-temperature calcination process is considered as the routes of choice in preparing ion-doped porous materials, but it requires extra templates and will undergo complicated steps. Here, we present a simple fusion/diffusion-controlled intermetallics-transformation method to synthesize various heteroatom-doping porous SnO only by changing the species of intermetallics. By this new method, Ni-doped popcornlike SnO with plenty of ∼30 nm pores and two kinds of Cu-doped SnO nanocages was successfully constructed. Phase-evolution investigations demonstrated that growth kinetics, diffusion, and solubility of the intermediates are highly related to the architecture of final products. Moreover, low-solid-solution limit of MO (M: Ni, Cu) in SnO made the ion dope close to the surface to form a special surface/interfaces structure, and selective removal of MO produce abundant pores to increase the surface area. As a consequence, Ni-doped composite exhibits higher sensitivity in formaldehyde detection with a relative low-operating temperature in a short response time (i.e., 23.7-50 ppm formaldehyde, 170 °C, and 5 s) and Cu-doped composites show excellent activity in decreasing the catalytic temperature of CO oxidation and ammonium perchlorate decomposition. The fusion/diffusion-controlled intermetallics-transformation method reported in this work could be readily adopted for the synthesis of other active heteroatom-doping porous materials for multipurpose uses.
设计与合成具有独特表面/界面的杂原子掺杂多孔材料对于提高催化能源领域（尤其是气体传感器、CO氧化和高氯酸铵分解）的敏感表面性能具有重要意义。通常，采用模板法并结合高温煅烧工艺被认为是制备离子掺杂多孔材料的首选途径，但它需要额外的模板且步骤复杂。在此，我们提出一种简单的融合/扩散控制金属间化合物转化方法，仅通过改变金属间化合物的种类就可以合成各种杂原子掺杂的多孔SnO。通过这种新方法，成功构建了具有大量约30 nm孔隙的Ni掺杂爆米花状SnO和两种Cu掺杂的SnO纳米笼。相演变研究表明，中间体的生长动力学、扩散和溶解度与最终产物的结构高度相关。此外，MO（M：Ni、Cu）在SnO中的低固溶极限使离子掺杂靠近表面形成特殊的表面/界面结构，选择性去除MO会产生大量孔隙以增加表面积。因此，Ni掺杂复合材料在甲醛检测中表现出更高的灵敏度，在相对较低的操作温度下具有较短的响应时间（即23.7 - 50 ppm甲醛，170 °C，5 s），而Cu掺杂复合材料在降低CO氧化和高氯酸铵分解的催化温度方面表现出优异的活性。本文报道的融合/扩散控制金属间化合物转化方法可很容易地用于合成其他用于多种用途的活性杂原子掺杂多孔材料。
