Translucency of Graphene to van der Waals Forces Applies to Atoms/Molecules with Different Polar Character

Presel, Francesco; Gijón, Alfonso; Hernández, Eduardo; Lacovig, Paolo; Lizzit, Silvano; Baraldi, Alessandro

doi:10.1021/acsnano.9b07277

Cited by 11 publications

(7 citation statements)

References 67 publications

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“…In addition to wetting transparency, other surface-related properties might also be transparent to 2D materials. Adsorption transparency, which has implications in catalysis, was recently reported and warrants additional attention. …”

Section: Discussionmentioning

confidence: 90%

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Effect of Environmental Contaminants on the Interfacial Properties of Two-Dimensional Materials

et al. 2022

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Metrics & MoreArticle Recommendations CONSPECTUS:The surface of 2D materials can spontaneously adsorb and react with molecules in the environment during their processing and storage. This effect, while having a significant impact on many properties of 2D materials, is not always recognized and accounted for in the research involving them. This Account summarizes our recent work in understanding how the ambient environment impacts the properties of 2D materials and its mitigation strategies. We highlight graphene and hydrocarbons in our discussion and complement it with selected studies involving other 2D materials as well as water and oxygen.When graphene and graphite are exposed to air and water, their surfaces adsorb the residue hydrocarbons, typically at part-pertrillion to part-per-billion levels, in the environment. The adsorption of hydrocarbons reduces the surface energy of graphene and graphite and creates a barrier between them and the electrolyte. As a result, the wettability and electrochemical properties of graphene and graphite can be significantly altered by mere exposure to the ambient environment. These changes can be very significant yet highly variable depending on the local environment: several hours of air exposure can increase the water contact angle of graphene by up to 40°and reduce the double-layer capacitance of graphite by up to 50%! The high hydrophobicity and poor electrochemical performance of pristine graphitic carbons, once believed to be intrinsic properties of these materials, are largely due to unintentional surface contamination. The same type of hydrocarbon adsorption was reported for many other 2D materials, such as MoS 2 , hexagonal BN, and mica. In the case of mica, which is highly ionic in nature, the adsorption of hydrocarbons disrupts its interaction with ionic liquid and alters the self-assembly structure of ionic liquid at the mica surface. Similarly, water also impacts the surface properties of graphene in several ways. Water vapor can compete with hydrocarbons for adsorption onto the surface of graphene, thus reducing the rate of hydrocarbon contamination. Water can intercalate between graphene and some of its supporting substrate, altering their interactions. Finally, water enhances the doping of 2D materials by O 2 by promoting an electrochemical doping mechanism involving the O 2 /H 2 O redox couple.Reducing and reversing the surface contamination of 2D materials can greatly enhance material and device performances. While completely stopping the contamination is still challenging, a high-humidity environment is shown to reduce the rate of contamination, as mentioned above. For samples already contaminated by airborne hydrocarbons, their surface properties can be partially restored by treatment in high-vacuum, high-temperature, or mildly oxidative environments.

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Section: Discussionmentioning

confidence: 90%

“…Adsorption transparency, which has implications in catalysis, was recently reported and warrants additional attention. 50…”

Section: Discussionmentioning

confidence: 99%

Effect of Environmental Contaminants on the Interfacial Properties of Two-Dimensional Materials

et al. 2022

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“…Recently, x-ray techniques including x-ray photoelectron spectroscopy (XPS) and x-ray photon correlation spectroscopy (XPCS) have been utilized to understand how the addition of graphene on an underlying substrate influences adsorption. [18][19][20] Presel et al employed combined experimental XPS and theoretical approach to study adsorption of carbon monoxide (CO) and argon (Ar) and concluded 50% transmission of vdW interactions. 18 In another study, adsorption of water was found to be fully dominated by water-substrate interactions.…”

Section: Introductionmentioning

confidence: 99%

“…[18][19][20] Presel et al employed combined experimental XPS and theoretical approach to study adsorption of carbon monoxide (CO) and argon (Ar) and concluded 50% transmission of vdW interactions. 18 In another study, adsorption of water was found to be fully dominated by water-substrate interactions. 19 Additionally, surfacesensitive non-linear spectroscopies, second harmonic generation (SHG) and sum frequency generation (SFG), have been employed to provide insights into graphene's ability to screen or transmit interactions.…”

Section: Introductionmentioning

confidence: 99%

Screening of hydrogen bonding interactions by a single layer graphene

2021

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“…In this paper, we report on a successful on-surface metalation of 5,5′-dibromosalophene with Co, Fe, and Cr on Co-intercalated graphene on Ir(111) (Gr/Co) . The graphene layer is known to prevent strong hybridization of molecules with the substrate, ,− while the intercalation, in the valleys of the moiré pattern, provides sufficient interaction with the molecules to limit the desorption of molecules at elevated temperatures. , The successful realization of the metalation reaction was ensured by X-ray photoelectron spectroscopy (XPS) measurements and by comparison of the electronic structure of ex situ and in situ metalated 5,5′-dibromosalophenato–cobalt(II). Scanning tunneling spectroscopy (STS) and density functional theory (DFT) calculations of the obtained products reveal the differences in the electronic structures of different metal–organic complexes.…”

Section: Introductionmentioning

confidence: 99%

In Situ Synthesis of Metal–Salophene Complexes on Intercalated Graphene

et al. 2020

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On-surface metalation provides a tool to vary magnetic and electronic properties of metal−organic complexes and produces clean samples of the desired product. We used this technique to metalate 5,5′-dibromosalophene with the 3d transition metals Co, Fe, and Cr on Co-intercalated graphene grown on Ir(111). The metalation process was investigated by X-ray photoelectron spectroscopy (XPS). The electronic structure of the obtained salophene complexes was investigated using a combination of scanning tunneling microscopy and spectroscopy with density functional theory calculations. XPS data show that deposition of the transition metals at 398 K causes the metal atoms to interact with the molecules, while higher temperatures are needed to complete the reaction. Furthermore, we are able to distinguish the three different metal−organic complexes by their electronic structure.

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Translucency of Graphene to van der Waals Forces Applies to Atoms/Molecules with Different Polar Character

Cited by 11 publications

References 67 publications

Effect of Environmental Contaminants on the Interfacial Properties of Two-Dimensional Materials

Effect of Environmental Contaminants on the Interfacial Properties of Two-Dimensional Materials

Screening of hydrogen bonding interactions by a single layer graphene

In Situ Synthesis of Metal–Salophene Complexes on Intercalated Graphene

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