Zhu Jiawei, Li Wenqiang, Li Shuaihu, Zhang Jian, Zhou Huang, Zhang Chengtian, Zhang Jianan, Mu Shichun
State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan, 430070, P. R. China.
School of Science, Lanzhou University of Technology, Lanzhou, 730050, P. R. China.
Small. 2018 May;14(21):e1800563. doi: 10.1002/smll.201800563. Epub 2018 Apr 18.
Developing a facile and cost-efficient method to synthesize carbon-based nanomaterials possessing excellent structural and functional properties has become one of the most attractive topics in energy conversion and storage fields. In this study, density functional theory calculation results reveal the origin of high oxygen reduction reaction (ORR) activity predominantly derived from the synergistic effect of intrinsic defects and heteroatom dopants (e.g., N, S) that modulate the bandgap and charge density distribution of carbon matrix. Under the guidance of the first-principle prediction, by using ultralight biomass waste as precursor of C, N, and S elements, a defect-rich and N/S dual-doped cheese-like porous carbon nanomaterial is successfully designed and constructed. Herein, the intrinsic defects are artfully generated in terms of alkaline and ammonia activation. The electrochemical measurements display that such a material owns a comparable ORR activity (E = 0.835 V) to the commercial Pt/C catalyst, along with splendid durability and methanol tolerance in alkali media. Furthermore, as cathode catalyst, it displays a high Zn-air battery performance. The excellent ORR activity of the catalyst can be attributed to its unique 3D porous architecture, abundant intrinsic defects, and high-content active heteroatom dopants in the carbon matrix.
开发一种简便且经济高效的方法来合成具有优异结构和功能特性的碳基纳米材料，已成为能量转换和存储领域最具吸引力的课题之一。在本研究中，密度泛函理论计算结果揭示了高氧还原反应（ORR）活性的起源，其主要源于本征缺陷和杂原子掺杂剂（如N、S）的协同效应，这些效应调节了碳基体的带隙和电荷密度分布。在第一性原理预测的指导下，以超轻生物质废弃物作为C、N和S元素的前驱体，成功设计并构建了一种富含缺陷且N/S双掺杂的奶酪状多孔碳纳米材料。在此，通过碱和氨活化巧妙地产生了本征缺陷。电化学测量表明，这种材料具有与商业Pt/C催化剂相当的ORR活性（E = 0.835 V），在碱性介质中具有出色的耐久性和甲醇耐受性。此外，作为阴极催化剂，它展现出高的锌空气电池性能。该催化剂优异的ORR活性可归因于其独特的三维多孔结构、丰富的本征缺陷以及碳基体中高含量的活性杂原子掺杂剂。
