Yao Qilu, Lu Zhang-Hui, Zhang Zhujun, Chen Xiangshu, Lan Yaqian
Jiangxi Inorganic Membrane Materials Engineering Research Centre, College of Chemistry and Chemical Engineering, Jiangxi Normal University, Nanchang 330022, China.
Jiangsu Key Laboratory of Biofunctional Materials, College of Chemistry and Materials Science, Nanjing Normal University, Nanjing 210023, China.
Sci Rep. 2014 Dec 23;4:7597. doi: 10.1038/srep07597.
Ultrafine copper nanoparticles (Cu NPs) within porous silica nanospheres (Cu@SiO2) were prepared via a simple one-pot synthetic route in a reverse micelle system and characterized by SEM, TEM, EDX, XRD, N2 adsorption-desorption, CO-TPD, XPS, and ICP methods. The characterized results show that ultrafine Cu NPs with diameter of around 2 nm are effectively embedded in the center of well-proportioned spherical SiO2 NPs of about 25 nm in diameter. Compared to commercial SiO2 supported Cu NPs, SiO2 nanospheres supported Cu NPs, and free Cu NPs, the synthesized core-shell nanospheres Cu@SiO2 exhibit a superior catalytic activity for the hydrolytic dehydrogenation of ammonia borane (AB, NH3BH3) and hydrazine borane (HB, N2H4BH3) under ambient atmosphere at room temperature. The turnover frequencies (TOF) for the hydrolysis of AB and HB in the presence of Cu@SiO2 nanospheres were measured to be 3.24 and 7.58 mol H2 (mol Cu min)(-1), respectively, relatively high values for Cu nanocatalysts in the same reaction. In addition, the recycle tests show that the Cu@SiO2 nanospheres are still highly active in the hydrolysis of AB and HB, preserving 90 and 85% of their initial catalytic activity even after ten recycles, respectively.
通过反向胶束体系中的简单一锅合成路线制备了多孔二氧化硅纳米球(Cu@SiO2)内的超细铜纳米颗粒(Cu NPs),并通过扫描电子显微镜(SEM)、透射电子显微镜(TEM)、能谱仪(EDX)、X射线衍射仪(XRD)、N2吸附-脱附、程序升温脱附(CO-TPD)、X射线光电子能谱(XPS)和电感耦合等离子体质谱(ICP)方法对其进行了表征。表征结果表明,直径约2 nm的超细Cu NPs有效地嵌入了直径约25 nm的比例均匀的球形SiO2 NPs的中心。与商业SiO2负载的Cu NPs、SiO2纳米球负载的Cu NPs和游离Cu NPs相比,合成的核壳纳米球Cu@SiO2在室温环境气氛下对氨硼烷(AB,NH3BH3)和硼烷肼(HB,N2H4BH3)的水解脱氢表现出优异的催化活性。在Cu@SiO2纳米球存在下,AB和HB水解的周转频率(TOF)分别测定为3.24和7.58 mol H2(mol Cu min)-1,这在相同反应中对于Cu纳米催化剂来说是相对较高的值。此外,循环测试表明,Cu@SiO2纳米球在AB和HB的水解中仍然具有高活性,即使经过十次循环后,分别仍保留其初始催化活性的90%和85%。