Hierarchically Flower-like N-Doped Porous Carbon Materials Derived from an Explosive 3-Fold Interpenetrating Diamondoid Copper Metal-Organic Framework for a Supercapacitor.
Hierarchically Flower-like N-Doped Porous Carbon Materials Derived from an Explosive 3-Fold Interpenetrating Diamondoid Copper Metal-Organic Framework for a Supercapacitor.
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DOI：
10.1021/acs.inorgchem.6b00746
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发表时间：
2016-06
影响因子：
4.6
通讯作者：
Zuo-Xi Li;Kang-Yu Zou;Xue Zhang;Tongxin Han;Ying Yang
中科院分区：
文献类型：
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作者：
Zuo-Xi Li;Kang-Yu Zou;Xue Zhang;Tongxin Han;Ying Yang
采用自组装方法合成了一种特殊的铜金属有机骨架（Cu-MOF），它是以正方形平面Cu（II）节点为基础的三重互穿类金刚石网络。虽然它表现出高度的相互渗透，但Cu-MOF仍然表现出一维通道，这为通过“前体”策略构建多孔材料提供了模板。此外，通道中存在的爆炸性ClO 4（-）离子能促使有机组分快速分解并释放出大量气体，有利于后期材料的多孔性。值得注意的是，我们首次利用这种爆炸性的MOF通过在不同温度下的煅烧-热处理方法制备了一系列Cu@C复合材料，其包含具有各种形状和与碳基体结合的铜颗粒。考虑到Cu颗粒的成孔作用，采用HCl腐蚀Cu@C复合材料，得到一系列具有层次结构的花状N掺杂多孔碳材料（NPC），这些NPC保持了Cu-MOF的原始形貌。有趣的是，NPC-900，来自于在900 °C下煅烧的Cu-MOF，表现出更规则的花状形态，最大的比表面积，丰富的孔隙率和多个氮官能团。在6 M氢氧化钾水溶液中，NPC-900电极在5 mV·s（-1）和0.5A·g（-1）时的比电容分别为138 F·g（-1）和149 F·g（-1）。在1A g（-1）下，经过2000次循环，电容保持率为86.8%（125 F g（-1）），具有良好的化学稳定性。这些发现表明NPC-900可以用作超级电容器的合适电极。
A peculiar copper metal-organic framework (Cu-MOF) was synthesized by a self-assembly method, which presents a 3-fold interpenetrating diamondoid net based on the square-planar Cu(II) node. Although it exhibits a high degree of interpenetration, the Cu-MOF still exhibits a one-dimensional channel, which provides a template for constructing porous materials through the "precursor" strategy. Furthermore, the explosive ClO4(-) ion, which resided in the channel, could induce the quick decomposition of organic ingredients and release a huge amount of gas, which is beneficial for the porosity of postsynthetic materials. Significantly, we first utilize this explosive MOF to prepare a series of Cu@C composites through the calcination-thermolysis method at different temperatures, which contain copper particles exhibiting various shapes and combinations with the carbon substrate. Considering the hole-forming effect of copper particles, Cu@C composites were etched by HCl to afford a sequence of hierarchically flower-like N-doped porous carbon materials (NPCs), which retain the original morphology of the Cu-MOF. Interestingly, NPC-900, originating from the calcination of the Cu-MOF at 900 °C, exhibits a more regular flower-like morphology, the largest specific surface area, abundant porosities, and multiple nitrogen functionalities. The remarkable specific capacitances are 138 F g(-1) at 5 mV s(-1) and 149 F g(-1) at 0.5 A g(-1) for the NPC-900 electrode in a 6 M potassium hydroxide aqueous solution. Moreover, the retention of capacitance remains 86.8% (125 F g(-1)) at 1 A g(-1) over 2000 cycles, which displays good chemical stability. These findings suggest that NPC-900 can be applied as a suitable electrode for a supercapacitor.