Chlorinated graphene and graphene nanoribbons: A density functional theory study

IF 5.9 3区 材料科学 Q2 CHEMISTRY, PHYSICAL FlatChem Pub Date : 2024-05-14 DOI:10.1016/j.flatc.2024.100670
Florentino López-Urías , Juan L. Fajardo-Díaz , Verónica L. Medina-Llamas , Armando D. Martínez-Iniesta , Morinobu Endo , Emilio Muñoz-Sandoval
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Abstract

Functional groups based on halides, such as fluorine (F), chlorine (Cl), bromine (Br), and iodine (I), are crucial for understanding the chemical reactivity of graphitic nanomaterials. Except for I, halogens exhibit electronegativity greater than carbon (C); therefore, charge transfer from carbon to halogen is expected. First-principles density functional theory calculations were performed to determine the role of different Cl-functional groups (methyl-trichloride, ethyl-trichloride, chloride, acyl-chloride, vinyl-chloride, acetyl hypochlorite, chloramines, sulfonyl chloride, and more) on the electronic properties of graphene and graphene nanoribbons (GNRs). GNRs with zigzag edges (ZGNRs) and armchair edges (AGNRs) were studied. We analyzed the optimized structures, band structure, density of states, cohesive energy, and band gap. Our results revealed that the based-Cl functional groups can provide an alternative route to activate the borders and surfaces of sp2 carbon materials. Methyl-trichloride and acyl-chloride can induce magnetism and metallicity. Chloride and acyl-chloride are the most energetically stable functional groups attached to the edges. Surprisingly, methyl-trichloride or acyl-chloride functionalizing the surface of the AGNRs showed a direct (indirect) band gap for states with spin-up (spin-down). The results of aromatic (chlorobenzene- and dichlorobenzene-like structures) functionalization considering F, Cl, Br, and I are also shown. Finally, –F2 and –ClF functionalization cases are discussed.

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氯化石墨烯和石墨烯纳米带:密度泛函理论研究
基于卤化物的官能团,如氟(F)、氯(Cl)、溴(Br)和碘(I),对于了解石墨纳米材料的化学反应活性至关重要。除 I 外,卤素的电负性均大于碳(C);因此,电荷有望从碳转移到卤素。第一原理密度泛函理论计算确定了不同 Cl 官能团(甲基三氯化物、乙基三氯化物、氯化物、酰基氯化物、乙烯基氯化物、乙酰次氯酸盐、氯胺、磺酰氯等)对石墨烯和石墨烯纳米带 (GNR) 电子特性的作用。我们研究了具有人字形边缘(ZGNRs)和扶手椅边缘(AGNRs)的 GNRs。我们分析了优化结构、带状结构、态密度、内聚能和带隙。我们的研究结果表明,基-Cl 官能团可以为活化 sp2 碳材料的边缘和表面提供另一种途径。甲基三氯和酰基氯可以诱导磁性和金属性。氯化物和酰基氯是附着在边缘上能量最稳定的官能团。令人惊讶的是,AGNR 表面官能化的甲基-三氯化物或酰基-氯显示出自旋上升(自旋下降)态的直接(间接)带隙。此外,还显示了考虑到 F、Cl、Br 和 I 的芳香族(氯苯和类二氯苯结构)官能化的结果。最后还讨论了 -F2 和 -ClF 功能化的情况。
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来源期刊
FlatChem
FlatChem Multiple-
CiteScore
8.40
自引率
6.50%
发文量
104
审稿时长
26 days
期刊介绍: FlatChem - Chemistry of Flat Materials, a new voice in the community, publishes original and significant, cutting-edge research related to the chemistry of graphene and related 2D & layered materials. The overall aim of the journal is to combine the chemistry and applications of these materials, where the submission of communications, full papers, and concepts should contain chemistry in a materials context, which can be both experimental and/or theoretical. In addition to original research articles, FlatChem also offers reviews, minireviews, highlights and perspectives on the future of this research area with the scientific leaders in fields related to Flat Materials. Topics of interest include, but are not limited to, the following: -Design, synthesis, applications and investigation of graphene, graphene related materials and other 2D & layered materials (for example Silicene, Germanene, Phosphorene, MXenes, Boron nitride, Transition metal dichalcogenides) -Characterization of these materials using all forms of spectroscopy and microscopy techniques -Chemical modification or functionalization and dispersion of these materials, as well as interactions with other materials -Exploring the surface chemistry of these materials for applications in: Sensors or detectors in electrochemical/Lab on a Chip devices, Composite materials, Membranes, Environment technology, Catalysis for energy storage and conversion (for example fuel cells, supercapacitors, batteries, hydrogen storage), Biomedical technology (drug delivery, biosensing, bioimaging)
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