Wu Qiao, Liang Jun, Yi Jun-Dong, Meng Dong-Li, Shi Peng-Chao, Huang Yuan-Biao, Cao Rong
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China.
Dalton Trans. 2019 Jun 7;48(21):7211-7217. doi: 10.1039/c8dt04941f. Epub 2019 Jan 23.
Metal-organic framework (MOF) derived carbon materials are promising for energy storage and conversion as they could inherit the advantages of MOF precursors, such as high porosity, large surface area and uniform heteroatom doping. Although the morphologies of MOF precursors have a significant effect on the properties of the resulting materials, up to now, there has been no systematic study on the relationship of the morphologies of MOFs and the properties of their pyrolized carbonaceous materials. Herein, three isomorphous imidazolate-based ZIF-7 materials with different morphologies (sphere, polyhedron and rod shape) have been selected as precursors and carbonized to obtain porous N-doped carbon materials with a tunable morphology, pore features and surface areas. The spherical precursor ZIF-7-S with an average size of 45 nm was cross-linked to form carbon networks during pyrolysis, while the rod shape of ZIF-7-R (0.6 μm in diameter and 3 μm in length) was well retained in the NC-R-800 material. NC-D-800 derived from polyhedral ZIF-7-D (125 nm) was constructed by partially interlinked particles and interparticle mesopores were formed. NC-D-800 has the highest Brunauer-Emmett-Teller (BET) surface area of 538 m g of the three carbon materials. Moreover, NC-D-800 shows superiority over NC-S-800 and NC-R-800 in the oxygen reduction reaction. This work discloses that the morphologies of MOF precursors could indeed affect the morphologies, and physical and catalytic properties of their corresponding carbon materials.
金属有机框架(MOF)衍生的碳材料因其能够继承MOF前驱体的优势,如高孔隙率、大表面积和均匀的杂原子掺杂,在能量存储和转换方面具有广阔前景。尽管MOF前驱体的形态对所得材料的性能有显著影响,但截至目前,尚未有关于MOF形态与其热解碳质材料性能之间关系的系统研究。在此,选择了三种具有不同形态(球形、多面体和棒状)的同构咪唑基ZIF-7材料作为前驱体,并进行碳化以获得具有可调节形态、孔特征和表面积的多孔氮掺杂碳材料。平均尺寸为45 nm的球形前驱体ZIF-7-S在热解过程中交联形成碳网络,而ZIF-7-R(直径0.6μm,长度3μm)的棒状形态在NC-R-800材料中得到了很好的保留。由多面体ZIF-7-D(125 nm)衍生的NC-D-800是由部分相互连接的颗粒构建而成,并形成了颗粒间介孔。在这三种碳材料中,NC-D-800具有最高的布鲁诺尔-埃米特-泰勒(BET)表面积,为538 m²/g。此外,在氧还原反应中,NC-D-800比NC-S-800和NC-R-800表现更优。这项工作表明,MOF前驱体的形态确实会影响其相应碳材料的形态、物理和催化性能。