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  Differences in perchlorate adsorption to azobenzene monolayers on gold formed from thioacetate and thiol precursors

Pang, B., Iqbal, D., Sarfraz, A., Biedermann, P. U., & Erbe, A. (2022). Differences in perchlorate adsorption to azobenzene monolayers on gold formed from thioacetate and thiol precursors. Zeitschrift fur Physikalische Chemie-International Journal of Research in Physical Chemistry & Chemical Physics. doi:10.1515/zpch-2021-3143.

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 Creators:
Pang, Beibei1, Author           
Iqbal, Danish2, Author           
Sarfraz, Adnan2, Author           
Biedermann, P. Ulrich3, Author           
Erbe, Andreas4, Author           
Affiliations:
1Interface Chemistry and Surface Engineering, Max-Planck-Institut für Eisenforschung GmbH, Max Planck Society, ou_1863348              
2Interface Spectroscopy, Interface Chemistry and Surface Engineering, Max-Planck-Institut für Eisenforschung GmbH, Max Planck Society, ou_1863358              
3Atomistic Modelling, Interface Chemistry and Surface Engineering, Max-Planck-Institut für Eisenforschung GmbH, Max Planck Society, ou_1863350              
4Department of Materials Science and Engineering, NTNU - Norwegian University of Science and Technology, 7491 Trondheim, Norway, ou_persistent22              

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 Abstract: Modification of metal surfaces with complex molecules opens interesting opportunities to build additional functionality into these surfaces. In this work, self assembled monolayers (SAMs) based on the same photoswitchable azobenzene motif but with different head groups have been synthesized and their SAMs on Au(111)/Si substrates have been characterized. 3-[(4-phenylazo)phenoxy]propyl thiol (PAPT) and its acetyl group protected analog, 3-[(4-phenylazo)phenoxy]propyl thioacetate (PAPA), have been synthesized. SAMs from PAPT and PAPA have been characterized by infrared (IR) spectroscopy, X-ray photoelectron spectroscopy (XPS), ellipsometry and cyclic voltammetry (CV). The SAM-forming units of both SAMs are the same, as confirmed by IR and XPS, and the SAMs have similar surface coverage, as evidenced by analysis of the reductive desorption peaks in CVs. The tilt angle of the azobenzene moiety was ca. 75 degrees with respect to the surface normal as determined by IR spectroscopy, i.e., the molecules are lying quite flat on the gold surface. Despite similar surface coverages, the CVs for PAPT in aqueous perchlorate solution show a typical perchlorate adsorption peak to gold, whereas the corresponding experiments with PAPA show no perchlorate adsorption at all. In conclusion, SAM formation can lead to an increase in the number of electrochemically accessible surface sites on the final, SAM covered surface. Whether the amount of such sites increases or decreases, depends on the precursor. The precursor most likely affects the adsorption mechanism and thus the atomic surface structure of the metal at the metal/SAM interface. Thus, details of the SAM formation mechanism, which is affected by the precursor used, can have quite strong effects on the electrochemical properties, and likely also electrocatalytic properties, of the resulting modified surface.

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Language(s): eng - English
 Dates: 2022-07-042022
 Publication Status: Published in print
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 Identifiers: DOI: 10.1515/zpch-2021-3143
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Project name : We acknowledge support from IMPRS Surmat and the Cluster of Excellence RESOLV (EXC 1069) funded by the Deutsche Forschungsgemeinschaft.
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Title: Zeitschrift fur Physikalische Chemie-International Journal of Research in Physical Chemistry & Chemical Physics
Source Genre: Journal
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Publ. Info: Frankfurt am Main : Akademische Verlagsgesellschaft
Pages: - Volume / Issue: - Sequence Number: - Start / End Page: - Identifier: ISSN: 0942-9352
CoNE: https://pure.mpg.de/cone/journals/resource/954925572905_2