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中国物理学会期刊

Ag, Cu掺杂氧化石墨烯吸附NH3的第一性原理研究

CSTR: 32037.14.aps.74.20241737

First-principles study of NH3 adsorption on Ag- and Cu doped graphene oxide

CSTR: 32037.14.aps.74.20241737
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  • 基于第一性原理的密度泛函理论, 系统地研究了氧化石墨烯及其Ag与Cu掺杂对NH3分子的吸附特性. 通过计算电荷分布、态密度、能带结构和吸附能, 研究了含氧基团及金属掺杂对氧化石墨烯气敏性能的调控效应. 通过对掺杂Ag原子的氧化石墨烯的态密度进行分析, 发现Ag原子与NH3中的N原子的s, p和d轨道之间存在共振, 表明Ag原子和N原子之间形成了化学键. 这种化学键导致Ag对NH3的吸附作用明显强于含氧基团, 从而使得掺杂后的氧化石墨烯的吸附能提升了数倍. 此外, Cu掺杂氧化石墨烯同样能够显著地提升其对NH3的吸附性能. 在掺杂浓度均为3.13%的条件下, Cu掺杂的氧化石墨烯对NH3表现出更强的吸附能力. 同时, Ag或Cu掺杂的氧化石墨烯中, 羧基和环氧基对NH3的吸附模式由物理吸附转变为化学吸附; 而羟基则在掺杂前后始终显示出化学吸附特性. 综上所述, 金属掺杂的氧化石墨烯的吸附能会受到含氧基团和金属原子共同作用影响, 且Ag或Cu原子掺杂能显著提高氧化石墨烯对NH3的吸附性能.

     

    Graphene has attracted great attention due to its large specific surface area, high charge carrier mobility, and excellent electrical conductivity. However, the inherent structural integrity and zero bandgap characteristics of graphene limit its gas sensing properties. Consequently, researchers have embarked on exploring avenues such as doping graphene or using graphene oxide as a gas-sensitive material to design gas sensors that respond optimally to ammonia. This work, based on first-principle density functional theory, focuses on the field of ammonia gas sensors, investigating in detail the adsorption characteristics of ammonia molecules on graphene oxide (GO) and graphene oxide doped with Ag and Cu (AgGO, CuGO). By calculating parameters including charge distribution, density of states, band structures, and adsorption energy, this work delves into the influences of diverse oxygen-containing groups and metal doping on the gas sensing properties of graphene oxide. The research results show that there is a substantial charge density overlap between the density of states of hydroxyl groups in graphene oxide and NH3 molecules, indicating a clear tendency towards chemical adsorption. It is particularly noteworthy that after NH3 adsorption, the graphene oxide containing hydroxyl shows the highest charge transfer (0.078e) and adsorption energy (0.60 eV), which indicates that the adsorption efficacy of NH3 is higher, followed by carboxyl groups and epoxy groups, which mainly participate in physical adsorption. Furthermore, this work delves into the influence of metal doping on graphene oxide, demonstrating that the adsorption capability of doped graphene oxide hinges upon the synergistic influence of oxygen-containing groups and metal atoms, with Ag-doped graphene oxide showing a several-fold increase in adsorption energy. Through the analysis of density of states, it is found that Ag atoms resonate with s, p, and d orbitals of the N atom in NH3, proving the formation of a chemical bond between Ag atom and N atom. Moreover, a comparative analysis shows that Cu-doped graphene oxide (CuGO) has an increased charge transfer of about 0.020e and slightly higher adsorption energy than Ag-doped graphene oxide (AgGO) when adsorbing NH3. Intriguingly, under the same doping concentration, CuGO exhibits superior adsorption performance to NH3. It is worth noting that in graphene oxide doped with Ag or Cu, the adsorption mechanism of carboxyl and epoxy groups transforms from physical adsorption into chemical adsorption, while the hydroxyl groups maintain consistent chemical adsorption properties before and after doping. This indicates that doping with Ag or Cu atoms can significantly enhance the adsorption capability of graphene oxide to NH3.

     

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