基于TM-N-C配位关系调控选择性吸附O2/N2的机理研究
江西理工大学, 材料冶金化学学部, 江西赣州 341000
| 摘 要： | 化石燃料的大量燃烧，造成环境污染日益严重。燃料电池作为新型能量转化装置，涉及氧电催化反应，但这些反应过程复杂，过电位高，需要寻找合适的催化剂，促进反应顺利进行。氧还原反应（ORR）和氮还原反应（NRR）的反应物O2、N2都来自空气，生成物H2O、NH3是重要的化学资源。本文通过计算研究石墨烯分别锚定13种非贵过渡金属（TM）在不同N浓度掺杂情况下，对O2/N2的选择性吸附，得出结论：单空位和双空位结构中，N含量越高，基底稳定性越好，且双空位的稳定性比单空位好。重点研究了稳定性最好的ZrN4催化基底，通过穆丽肯电荷分布以及分波态密度（PDOS），发现其电荷对称分布，电子转移明显。进一步分析基底吸附O2和H2O的变形态密度，得出该催化基底吸附与脱附能力优良。除CuN0C4、ZnN0C4、CdN4C0、CdN2C2-o、ZnN2C1基底外，其余结构具有适度的反应物O2吸附能力及产物H2O脱附能力，是酸性环境ORR催化剂的潜在来源。 |
| 关 键 词： | 石墨烯; 氧还原反应; 氮还原反应; 密度泛函理论; 单原子掺杂 |
| DOI： | 10.57237/j.mater.2022.02.004 |
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收稿日期: 2022-11-11
接受日期: 2022-12-29
在线出版日期: 2023-01-05
Mechanism of Selective Adsorption of O2 / N2 Based on TM-N-C Coordination Relationship
Faculty of Materials Metallurgy and Chemistry, Jiangxi University of Science and Technology, Ganzhou 341000, China
| Abstract: | The burning of fossil fuels has caused increasingly serious environmental pollution. As a new energy conversion device, fuel cell involves oxygen electrocatalytic reaction, but these reaction processes are complicated and high overpotential, so it is necessary to find suitable catalyst to promote the smooth reaction. The reactants O2 and N2 of oxygen reduction reaction (ORR) and nitrogen reduction reaction (NRR) all come from air, while the products H2O and NH3 are important chemical resources. In this paper, the selective adsorption of O2/N2 by 13 kinds of non-expensive transition metals (TM) anchored by graphene under different N concentration doping conditions was studied by calculation. It was concluded that the higher the content of N in single-vacancy and double-vacancy structures, the better the stability of the substrate, and the stability of the double-vacancy structure is better than that of the single vacancy. The ZrN4 catalytic substrate with the best stability was mainly studied. Through the Mulliken charge distribution and partial wave density of state (PDOS), it was found that its charge distribution was symmetrical and the electron transfer was obvious. Further analysis of the deformed state density of the substrate adsorbing O2 and H2O shows that the catalytic substrate has excellent adsorption and desorption capacity. Except CuN0C4, ZnN0C4, CdN4C0, CdN2C2-o and ZnN2C1 substrates, the other structures have moderate adsorption capacity of reactant O2 and desorption capacity of product H2O, which are potential sources of ORR catalysts in acidic environment. |
| Keywords: | Graphene; Oxygen Reduction Reaction; Nitrogen Reduction Reaction; Density Functional Theory; Single-Atom Doping |
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