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Title: Solution Deposition of Phenylphosphinic Acid Leads to Highly Ordered, Covalently Bound Monolayers on TiO 2 (110) Without Annealing

Abstract

Solution-deposited phosphonic acids, O=P(OH)2R, have been used to impart new functionality to a variety of metal oxide surfaces for applications ranging from organic field-effect transistors to biocompatible coatings on implants. Interestingly, the as-deposited monolayers are easily rinsed off, becoming robust and strongly adherent only after a long, low-temperature thermal anneal (e.g., 18 h at 120 °C). The need for this thermal treatment has raised questions about the nature of the bonding of the as-deposited monolayer. Is it merely physisorbed, requiring heat treatment for covalent bonding? To understand the first stages of monolayer formation, we have studied the reactivity and molecular bonding geometry of a prototypical, solution-deposited phosphinic acid, O=PH(OH)R, on the prototypical metal oxide surface rutile (110). We show that solution deposition produces near ideal, dense phenylphosphinate monolayers covalently bound in a bridged bidentate geometry. Three nearly orthogonal molecular vibrations—the P–H stretch vibration and the symmetric and antisymmetric OPO stretch vibrations—provided an unambiguous signature of the three-dimensional structure and binding of the adsorbed monolayer; scanning tunneling microscopy provided information on long-range order and intermolecular conformation; and X-ray photoemission spectroscopy provided coverage quantification. Despite their covalent bidentate attachment and significantly higher binding energy than the corresponding carboxylic acid, a H2O rinsemore » removed most of the phosphinate monolayer, demonstrating that hydrolytic stability does not result from covalent attachment alone. The H2O rinse also oxidized ~25% of the phosphinate monolayer to the corresponding phosphonate, producing a species that was somewhat more resistant to H2O rinsing.« less

Authors:
 [1];  [1]; ORCiD logo [1]
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  1. Cornell Univ., Ithaca, NY (United States). Dept. of Chemistry and Chemical Biology
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1480487
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 121; Journal Issue: 26; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Skibinski, Erik S., DeBenedetti, William J. I., and Hines, Melissa A. Solution Deposition of Phenylphosphinic Acid Leads to Highly Ordered, Covalently Bound Monolayers on TiO 2 (110) Without Annealing. United States: N. p., 2017. Web. doi:10.1021/acs.jpcc.7b04167.
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Skibinski, Erik S., DeBenedetti, William J. I., & Hines, Melissa A. Solution Deposition of Phenylphosphinic Acid Leads to Highly Ordered, Covalently Bound Monolayers on TiO 2 (110) Without Annealing. United States. https://doi.org/10.1021/acs.jpcc.7b04167
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Skibinski, Erik S., DeBenedetti, William J. I., and Hines, Melissa A. Thu . "Solution Deposition of Phenylphosphinic Acid Leads to Highly Ordered, Covalently Bound Monolayers on TiO 2 (110) Without Annealing". United States. https://doi.org/10.1021/acs.jpcc.7b04167. https://www.osti.gov/servlets/purl/1480487.
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@article{osti_1480487,
title = {Solution Deposition of Phenylphosphinic Acid Leads to Highly Ordered, Covalently Bound Monolayers on TiO 2 (110) Without Annealing},
author = {Skibinski, Erik S. and DeBenedetti, William J. I. and Hines, Melissa A.},
abstractNote = {Solution-deposited phosphonic acids, O=P(OH)2R, have been used to impart new functionality to a variety of metal oxide surfaces for applications ranging from organic field-effect transistors to biocompatible coatings on implants. Interestingly, the as-deposited monolayers are easily rinsed off, becoming robust and strongly adherent only after a long, low-temperature thermal anneal (e.g., 18 h at 120 °C). The need for this thermal treatment has raised questions about the nature of the bonding of the as-deposited monolayer. Is it merely physisorbed, requiring heat treatment for covalent bonding? To understand the first stages of monolayer formation, we have studied the reactivity and molecular bonding geometry of a prototypical, solution-deposited phosphinic acid, O=PH(OH)R, on the prototypical metal oxide surface rutile (110). We show that solution deposition produces near ideal, dense phenylphosphinate monolayers covalently bound in a bridged bidentate geometry. Three nearly orthogonal molecular vibrations—the P–H stretch vibration and the symmetric and antisymmetric OPO stretch vibrations—provided an unambiguous signature of the three-dimensional structure and binding of the adsorbed monolayer; scanning tunneling microscopy provided information on long-range order and intermolecular conformation; and X-ray photoemission spectroscopy provided coverage quantification. Despite their covalent bidentate attachment and significantly higher binding energy than the corresponding carboxylic acid, a H2O rinse removed most of the phosphinate monolayer, demonstrating that hydrolytic stability does not result from covalent attachment alone. The H2O rinse also oxidized ~25% of the phosphinate monolayer to the corresponding phosphonate, producing a species that was somewhat more resistant to H2O rinsing.},
doi = {10.1021/acs.jpcc.7b04167},
journal = {Journal of Physical Chemistry. C},
number = 26,
volume = 121,
place = {United States},
year = {Thu Jun 22 00:00:00 EDT 2017},
month = {Thu Jun 22 00:00:00 EDT 2017}
}
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Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acs.jpcc.7b04167
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Cited by: 13 works
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Figures / Tables:

Figure 1 Figure 1: Rutile (110) surface. (a) STM image of chemically etched, bicarbonate-terminated TiO2 (110) showing the production of near ideal, atomically flat terraces (+1.7 V, 500 pA). (b) STM image of UHV-prepared TiO2 (110) showing rows of undersaturated Ti atoms, which image as elliptical protrusions, separated by bridging O rows,more » which image as depressions (+1.3 V, 100 pA). (c) Molecular model of the rutile (110) surface in which Ti and O atoms are represented by blue and red spheres, respectively.« less
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