Physical & Materials Chemistry Division, National Chemical Laboratory, Dr Homi Bhabha Road, Pune, 411008.
Nanoscale. 2012 Jan 21;4(2):591-9. doi: 10.1039/c1nr10944h. Epub 2011 Dec 6.
Herein, for the first time, we report a generalized strategy for the successful synthesis of highly crystalline metal and metal oxide nanoparticles embedded in a carbon matrix by the controlled thermolysis of metal organic frameworks (MOFs). The rationalized synthesis strategy of a broad range of metal and metal oxides nanoparticles, such as Cu/CuO, Co/Co(3)O(4), ZnO, Mn(2)O(3), MgO and CdS/CdO, by thermolysis of MOFs demonstrates for the first time that metal ions with a reduction potential of -0.27 volts or higher present in MOFs always form pure metal nanoparticles during thermolysis in N(2), whereas metal ions with a reduction potential lower than -0.27 volts form metal oxide nanoparticles during thermolysis in N(2). Another point of interest is the fact that we have found a unique relationship between the nanoparticle size and the distance between the secondary building units inside the MOF precursors. Interestingly, the crystallinity of the carbon matrix was also found to be greatly influenced by the environment (N(2) and air) during thermolysis. Moreover, these nanoparticles dispersed in a carbon matrix showed promising H(2) and CO(2) adsorption properties depending on the environment used for the thermolysis of MOFs.
在此，我们首次报道了一种通过金属有机框架（MOFs）的可控热解成功合成高度结晶的金属和金属氧化物纳米粒子嵌入碳基质中的通用策略。通过 MOFs 的热解，合理地合成了广泛范围的金属和金属氧化物纳米粒子，如 Cu/CuO、Co/Co(3)O(4)、ZnO、Mn(2)O(3)、MgO 和 CdS/CdO，这首次证明了在 MOFs 中具有-0.27 伏或更高还原电位的金属离子在 N(2)中热解时总是形成纯金属纳米粒子，而还原电位低于-0.27 伏的金属离子在 N(2)中热解时形成金属氧化物纳米粒子。另一个有趣的观点是，我们发现纳米粒子尺寸与 MOF 前体中次级结构单元之间的距离之间存在独特的关系。有趣的是，还发现碳基质的结晶度也受到热解过程中环境（N(2)和空气）的极大影响。此外，这些分散在碳基质中的纳米粒子根据用于 MOF 热解的环境表现出有前途的 H(2)和 CO(2)吸附性能。
