Effect of van der Waals interactions in the DFT description of self-assembled monolayers of thiols on gold

Fajín, José L. C.; Teixeira, Filipe; Gomes, José R. B.; Cordeiro, M. Natália D. S.

doi:10.1007/s00214-015-1666-y

Cited by 21 publications

(13 citation statements)

References 99 publications

(128 reference statements)

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“…156 This approach has been shown to reproduce a wide range of properties for sulfur monolayers bound to Au(111) at FCC sites. 158 For situations in which a system of interest interacts with its surroundings, we have also found useful methods that treat the environmental dispersion interaction using dielectric continuum models. In this case, it is critical to verify that such implicit treatment of dispersion match well to the explicit treatment used for the represented atoms.…”

Section: Appropriate Modern Computational Methodsmentioning

confidence: 99%

Competition of van der Waals and chemical forces on gold–sulfur surfaces and nanoparticles

et al. 2017

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Section: Appropriate Modern Computational Methodsmentioning

confidence: 99%

Competition of van der Waals and chemical forces on gold–sulfur surfaces and nanoparticles

et al. 2017

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“…The slight discrepancy with the experimental value along the c direction is due to the limitation of our computation method to predict the weak interactions between layers. [44][45][46] From the schematic crystal structure, we can see that each imide unit forms eight H-bonds with its four nearest neighbors, including four N-H•••O hydrogen bonds (1.91 Å) and four N-H•••N hydrogen bonds (1.97 Å). All these hydrogen bonds are enabled by the DAT linkers.…”

Section: Resultsmentioning

confidence: 99%

2D Molecular Sheets of Hydrogen‐Bonded Organic Frameworks for Ultrastable Sodium‐Ion Storage

Mao

Zhang

et al. 2021

Advanced Materials

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little volume change during cycling. [15,16] It should be noted that albeit with high theoretic capacities, small organic molecules are often subjected to dissolution in the electrolyte at their charged or discharged states, and thereby suffer from very poor cyclability. [16] Poly merization through covalent bonding represents an effective strategy to suppress their dissolution. [17][18][19] A number of conjugated polymers (such as covalent organic frameworks or COFs) with different building units and topologies have been accordingly explored. [20][21][22][23][24][25] They often have low structural crystallinity and unsatisfactory cycling stability limited to a few hundreds of cycles.In addition to covalent bonding, some organic building blocks (such as those containing carboxylic acid or amine functionalities) may also self-assemble through weak hydrogen bonding to form ordered two-dimensional (2D) or three-dimensional (3D) frameworks known as hydrogen bonded organic frameworks (HOFs). [26][27][28][29] They generally have great structural crystallinity, large surface areas and porosity, and have been widely investigated for gas separation, sensing, proton conduction and so on. [26,27,30] Unfortunately, their potentials in electrochemical energy storage are elusive since the weak hydrogen bonds would be disrupted in common organic electrolytes, eventually leading to the collapse of ordered frameworks. [27,30] The construction of chemically stable HOFs remains a challenging task, and necessitates the design of novel linker units capable of forming multi-site hydrogen bonds.To this end, we here introduce diaminotriazole (DAT) as the linker unit for the first time in the construction of chemically stable HOFs. DAT is a nitrogen-rich heterocycle that can potentially forms multiple hydrogen bonds. Its reaction with dianhydride gives rise to imide building blocks that further selfassemble in solution to form 2D HOF molecular sheets. Owing to the multi-site hydrogen bond interactions (eight H-bonds per building blocks), the resultant product is highly robust in spite of its ultrathin thickness of ∼1 nm, and has diminished solubility in most polar or non-polar organic solvents. When evaluated as the cathode material of SIBs, HOF molecular sheets deliver a large capacity, and most surprisingly, outstanding cycling performance of >10,000 cycles at 1 A g −1 that is far from attainable with conventional organic electrode materials in our best knowledge. This impressive electrochemical performance is afforded by the high chemical stability and fast Na + diffusion There has been growing research interest in hydrogen bonded organic frameworks (HOFs) by virtue of their great structural crystallinity, large surface areas and porosity. Their potential in electrochemical applications, unfortunately, remains elusive because weak hydrogen bonds would dissociate in solution that eventually compromises the structural integrity. Herein, it is demonstrated that this issue may be overcome by designing and introducing multisite hydrogen bo...

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“…According to the QCM measurements the formation of the lipid coating is very fast. In contrast, the self-assembly of monolayers such as thiols on gold is generally a very slow process (41)(42)(43)(44), where longer time produces better monolayer packing. However, DMPA is delivered to the surface in bilayer vesicles where the packing is already at energy minimum following the Israelachvili-Mitchell-Ninham model of surfactant selfassembly (45,46).…”

Section: Discussionmentioning

confidence: 99%

“…The formation of phosphate-based self-assembled monolayers on transition metal oxide surfaces is based on a condensation reaction between the phosphate moiety and hydroxyl groups on the surface (32,42). It can be assumed that a hydrated metal oxide surface contains hydroxyl moieties; to gain more certainty the surface of an iron coated sensor was characterized by XPS.…”

Section: Xps Measurementsmentioning

confidence: 99%

Corrosion inhibition of iron surfaces with phosphatidic acid

Al-Badran

Mechler

2019

The EuroBiotech Journal

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Preventing the corrosion of iron in inaccessible structures requires a coating method that reaches all surface areas and creates a uniform protective layer. An ages old practice to protect iron artefacts is to coat them with animal fat, that is, a mixture of lipids. This “method” is accidentally ingenious: some natural phospholipids found in animal fat have the potential to form a tightly packed self-assembled monolayer on metal oxide surfaces, similar to the surfactant monolayers that have attracted increasing attention lately. Thus, the most primitive corrosion prevention method may point at a way to coat complex iron structures in an industrial environment. Here the ability of phosphatidic acid, a natural lipid, to coat and protect iron surfaces was examined. Iron coated quartz crystal microbalance (QCM) sensors were used for the experiments, to monitor the deposition of the lipid as well as the acidic corrosion (dissolution) of iron in situ, in real time. The sensors were coated by self-assembled monolayers of di-myristoyl phosphatidic acid using the liposome deposition method. In this process, 50-100 nm vesicles formed by the lipid are delivered in an aqueous solution and spontaneously coat the iron surfaces upon contact. QCM and ellipsometry measurements confirmed that continuous bilayer and monolayer surface coatings can be achieved by this method. QCM measurements also confirmed that the layers were corrosion resistant in 0.01M acetic acid solution that would dissolve the thin iron layer in minutes in the absence of the protective coating. XPS results suggested a chemisorption-based mechanism of phosphatidic acid attachment to the iron surface. Hence, liposome deposition of phosphatidic acid offers a suitable solution to coat iron surfaces in inaccessible structures in situ.

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Effect of van der Waals interactions in the DFT description of self-assembled monolayers of thiols on gold

Cited by 21 publications

References 99 publications

Competition of van der Waals and chemical forces on gold–sulfur surfaces and nanoparticles

Competition of van der Waals and chemical forces on gold–sulfur surfaces and nanoparticles

2D Molecular Sheets of Hydrogen‐Bonded Organic Frameworks for Ultrastable Sodium‐Ion Storage

Corrosion inhibition of iron surfaces with phosphatidic acid

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