Cycloaddition of Metal Porphines on Metal-Supported Graphene: A Computational Study
Cycloaddition of Metal Porphines on Metal-Supported Graphene: A Computational Study
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DOI：
10.1021/jp512247n
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发表时间：
2015-04
影响因子：
3.7
通讯作者：
M. Lattelais;M. Bocquet
中科院分区：
文献类型：
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作者：
M. Lattelais;M. Bocquet
采用色散校正密度泛函理论（DFT）方法研究了铁卟啉与石墨烯在一系列晶格匹配和晶格失配金属表面上的环加成反应.我们的计算证明了在特定的中空C-顶部C -中空C注册区域上石墨烯与3π单元的非经典环加成。最有利的环加合物的结果从一个放热的[3 + 2]过程与C2边缘的卟吩分子。我们还表明，环加成的可行性取决于石墨烯下面的金属的性质：Ir是最具反应性的金属，而Re的反应性较低，Cu几乎不活泼。外延石墨烯的各种反应性可以追溯到功能化之前石墨烯的金属杂化π态的能量定位和功能化之后石墨烯-金属相互作用的加强。我们的工作预测了一个意想不到的方式控制共价官能化的…
The cycloaddition reactions of iron porphine with graphene epitaxed to a series of lattice-matched and lattice-mismatched metal surfaces have been investigated by using dispersion-corrected density functional theory (DFT) calculations. Our calculations evidence the nonclassic cycloaddition with 3π units from graphene on specific hollow C– top C – hollow C registry areas. The most favorable cycloadduct results from an exothermic [3 + 2] process with a C2 edge of the porphine molecule. We also show that the feasibility of the cycloaddition depends on the nature of the metal below graphene: Ir is the most reactive metal, while Re is less reactive and Cu is almost inactive. The various reactivities of epitaxial graphene can be traced back to both the energy positioning of the metal-hybridized π states of graphene prior to the functionalization and the strengthening of the graphene–metal interaction after the functionalization. Our work predicts an unanticipated way for controlled covalent functionalization of...