Direct Access to Metal or Metal Oxide Nanocrystals Integrated with One-Dimensional Nanoporous Carbons for Electrochemical Energy Storage
Direct Access to Metal or Metal Oxide Nanocrystals Integrated with One-Dimensional Nanoporous Carbons for Electrochemical Energy Storage
复制标题
直接获取与一维纳米多孔碳集成的金属或金属氧化物纳米晶体用于电化学储能
DOI：
10.1021/ja106612d
复制
发表时间：
2010-10-27
影响因子：
15
通讯作者：
Muellen, Klaus
中科院分区：
文献类型：
--
作者：
Liang, Yanyu;Schwab, Matthias Georg;Muellen, Klaus
金属和金属氧化物纳米晶体由于其优异的催化、磁性和电子性能而引起了人们的极大兴趣。特别是，金属纳米晶体和一维（1D）导电碳的集成形成金属-碳杂化物可以提高物理和化学性能，甚至可以创造出与单组分材料相比的新性能。然而，直接获得热稳定且结构有序的一维金属-碳杂化材料仍然是一个主要挑战。我们报道了通过有机金属前驱体控制的热裂解方法，将Co3O4或Pt纳米晶体结合到一维纳米孔碳（npc）中。首先将AB(2)型（一二烯和二亲二烯）3,4-二（4-十二烷基苯基）取代环戊二烯酮及其相关的钴或铂配合物浸渍在AAO（阳极氧化氧化铝）膜的纳米通道中。这些前体分子的分子间Diels-Alder反应提供了钴或铂功能化聚苯骨架的形成。随后的热裂解将聚苯骨架转化为一维纳米多孔碳质框架，而金属部分分别还原为Co3O4或Pt纳米晶体。去除AAO模板后，得到1D NPCs/Co3O4或NPCs/Pt，其结构表征表明，高质量的Co3O4或Pt纳米晶体均匀分布在碳框架内。这些独特的一维金属碳杂化物在电化学储能方面表现出很好的潜力。NPCs/Co3O4被评估为超级电容器中的电极材料，其中Co3O4纳米晶体贡献了1066 F g（-1）的极高重量电容值。与商用E-TEK （Pt/C）催化剂相比，NPCs/Pt作为电催化剂对甲醇氧化表现出优异的催化效率。
Metal and metal oxide nanocrystals have sparked great interest due to their excellent catalytic, magnetic, and electronic properties. Particularly, the integration of metallic nanocrystals and one-dimensional (1D) electronically conducting carbons to form metal-carbon hybrids can lead to enhanced physical and chemical properties or even the creation of new properties with respect to single component materials. However, direct access to thermally stable and structurally ordered 1D metal-carbon hybrids remains a primary challenge. We report an in situ fabrication of Co3O4 or Pt nanocrystals incorporated into 1D nanoporous carbons (NPCs) via an organometallic precursor-controlled thermolysis approach. The AB(2)-type (one diene and two dienophile) 3,4-bis(4-dodecynylphenyl)-substituted cyclopentadienone and its relevant cobalt or platinum complex are first impregnated into the nanochannels of AAO (anodic alumina oxide) membranes. The intermolecular Diels-Alder reaction of these precursor molecules affords the formation of cobalt or platinum functionalized polyphenylene skeletons. Subsequent thermolysis transforms the polyphenylene backbones into 1D nanoporous carbonaceous frameworks, while the metallic moieties are reduced into Co3O4 or Pt nanocrystals, respectively. After removal of the AAO template, 1D NPCs/Co3O4 or NPCs/Pt are obtained, for which structural characterizations reveal that high-quality Co3O4 or Pt nanocrystals are distributed homogeneously within carbon frameworks. These unique 1D metal-carbon hybrids exhibit a promising potential in electrochemical energy storage. NPCs/Co3O4 is evaluated as an electrode material in a supercapacitor, for which Co3O4 nanocrystals contribute an exceptionally high gravimetric capacitance value of 1066 F g(-1). NPCs/Pt is applied as an electrocatalyst showing excellent catalytic efficiency toward methanol oxidation in comparison to commercial E-TEK (Pt/C) catalyst.