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Mixed monolayers of alkane thiols with polar terminal group on gold: Investigation of structure dependent surface properties
KTH, School of Information and Communication Technology (ICT), Materials- and Nano Physics, Material Physics, MF. (surface physics and Surface Chemistry and corrosion)ORCID iD: 0000-0002-9828-7753
KTH, School of Chemical Science and Engineering (CHE), Chemistry.ORCID iD: 0000-0002-7114-1439
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Surface and Corrosion Science.
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Surface and Corrosion Science.ORCID iD: 0000-0003-2206-0082
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2016 (English)In: Journal of Colloid and Interface Science, ISSN 0021-9797, E-ISSN 1095-7103, Vol. 484, no 279, 279-290 p., j.jcis.2016.08.053Article in journal, Editorial material (Refereed) Published
Abstract [en]

Adsorption of thiols with cationic or anionic terminal group on gold has been studied from mixed solutions of 11-Amino-1-undecanethiol (AUT) and 3-Mercaptopropionic acid (MPA) using Quartz Crystal Microbalance with Dissipation (QCM-D), X-ray Photoelectron Spectroscopy (XPS), atomic force microscopy (AFM) and contact angles. The goal is to probe the nature of such layers, and the additivity or otherwise of the pH responsiveness, with a view to evaluate their suitability as smart materials. For each of the two pure (unmixed) cases, ordered molecular monolayers are formed with sulfur binding to gold and the alkane chain pointing out from the surface as expected. Adsorption from the thiol mixtures, however, leads to a more complex behaviour. The surface concentration of thiols from the mixtures, as determined by QCM-D, is considerably lower than for the pure cases and it reaches a minimum at a 3:1 MPA/AUT relative concentration in the solution. The XPS results confirm a reduction in adsorbed amount in mixtures with the lowest overall intensity for the 3:1 ratio. Monolayers formed from mixtures display a wettability which is much lower and less pH sensitive. Collectively these results confirm that for adsorption from mixed systems, the configuration is completely different. Complex formation in the mixed solutions leads to the adsorption of molecules parallel to the surface in an axially in-plane configuration. This parallel layer of thiols is mechanically relatively robust to nano-shaving based on AFM measurements. These results will have a significant impact on the design of biomimetic surface coatings particularly when mixtures of oppositely charged molecules are present on the surface, as is commonly the case in biological, proteinaceous surfaces (e.g. hair and skin).

Place, publisher, year, edition, pages
Academic Press, 2016. Vol. 484, no 279, 279-290 p., j.jcis.2016.08.053
Keyword [en]
Self-assembled monolayer (SAM), Thiols, Quartz Crystal Microbalance with Dissipation (QCM-D), Atomic force microscopy (AFM), X-ray Photoelectron Spectroscopy (XPS)
National Category
Composite Science and Engineering
Identifiers
URN: urn:nbn:se:kth:diva-195612DOI: 10.1016/j.jcis.2016.08.053ISI: 000385690200032ScopusID: 2-s2.0-84986258342OAI: oai:DiVA.org:kth-195612DiVA: diva2:1044674
Funder
Swedish Research Council
Note

QC 20161107

Available from: 2016-11-04 Created: 2016-11-04 Last updated: 2016-11-29Bibliographically approved
In thesis
1. Adsorption of molecular thin films on metal and metal oxide surfaces
Open this publication in new window or tab >>Adsorption of molecular thin films on metal and metal oxide surfaces
2016 (English)Doctoral thesis, comprehensive summary (Other academic) [Artistic work]
Abstract [en]

Metal and metal oxides are widely used in industry, and to optimize their performance their surfaces are commonly functionalized by the formation of thin films. Self-assembled monolayers (SAMs) are deposited on metals or metal oxides either from solution or by gas deposition. Thiols with polar terminal groups are utilized for creating the responsive surfaces which can interact electrostatically with other adsorbates. Surface charge effects wetting and adhesion, and many other surface properties. Polar terminal groups in thiols could be used to modify these factors. Mixed SAMs can provide more flexible surfaces, and could change the resulting surface properties under the influence of factors such as pH, temperature, and photo-illumination. Therefore, in order to control these phenomena by mixed polar-terminated thiols, it is necessary to understand the composition and conformation of the mixed SAMs and their response to these factors. In this work, mixtures of thiols with carboxylic and amino terminal groups were studied. Carboxylic and amino terminal groups of thiol interact with each other via hydrogen bonding in solution and form a complex. Complexes adsorb to the surface in non-conventional orientations. Unmixed SAMs from each type, either carboxylic terminated thiols or amino terminated thiols are in standing up orientation while SAMs from complexes are in an axially in-plane orientation. Selenol is an alternative to replace thiols for particular applications such as contact with biological matter which has a better compatibility with selenol than sulfur. However, the    Se-C bond is weaker than the S-C bond which limits the application of selenol. Understanding the selenol adsorption mechanism on gold surfaces could shed some light on Se-C cleavage and so is investigated in this work. Se-C cleavage happens in the low coverage areas on the step since atoms at steps have lower coordination making them more reactive than atoms on the terraces.  Another area where the self-assembly of molecules is of importance is for dye sensitized solar cells, which are based on the adsorption of the dye onto metal oxides surfaces such as TiO2.The interface between the SAM of dye and the substrate is an important factor to consider when designing dyes and surfaces in dye sensitized solar cells (DSSCs). The quality of the self-assembled monolayers of the dye on the TiO2 surface has a critical influence on the efficiency of the DSSCs.  Creation of just a monolayer of dye on the surface could lead to an efficient current of photo-excited electrons to the TiO2 and degeneration of the dye by redox. This work, T-PAC dye showed island growth with some ad-layer that is not in contact with the surface, whereas the MP13 dye adsorption is laminar growth.  Cuprite (Cu2O) is the initial and most common corrosion product for copper under atmospheric conditions. Copper could be a good replacement for noble metal as catalysts for methanol dehydrogenation. Knowledge about the structure of Cu2O(100) and Cu2O(111) surfaces could be used to obtain a deeper understanding of methanol dehydrogenation mechanisms with respect to adsorption sites on the surfaces. In this work, a detailed study was done of Cu2O(100) surface which revealed the possible surface structures as the result of different preparation conditions. Studies of the structure of Cu2O(100) and Cu2O(111) surfaces show that Cu2O(100) has a comparatively stable surface and reduces surface reactivity. As a consequence, dehydrogenation of methanol is more efficient on the Cu2O(111) surface. The hydrogen produced from methanol dehydrogenation is stored in oxygen adatom sites on both surfaces.

 

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2016. 85 p.
Series
TRITA-ICT, 2016:37
Keyword
Self assembled monolayer (SAM), dye synthesis solar cell (DSSC), thiol, selenol, Cu2O(100), Cu2O(111) and dehydrogenation
National Category
Physical Sciences
Research subject
Physics; Materials Science and Engineering
Identifiers
urn:nbn:se:kth:diva-195613 (URN)978-91-7729-178-7 (ISBN)
Public defence
2016-12-09, Sal C Electrum, Kistagången 16 16440 Kista,, stockholm, 10:00 (English)
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Supervisors
Note

QC 20161107

Available from: 2016-11-09 Created: 2016-11-04 Last updated: 2016-12-01Bibliographically approved

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