Attachment Chemistry of 4-Fluorophenylboronic Acid on TiO2 and Al2O3 Nanoparticles

Abstract
Surface modification of nanoparticulate TiO2 and Al2O3 materials with 4-fluorophenylboronic acid is investigated in order to both evaluate the novel surface modification schemes and develop spectroscopic labels for surface characterization. The chemistry of the modification is followed on all these surfaces using X-ray photoelectron spectroscopy, multinuclear (11B, 19F, and 13C) solid-state and solution NMR, and infrared spectroscopy to determine the binding modes of this compound using boron and fluorine as probe atoms. Density functional theory model calculations are utilized to visualize predicted surface species and to interpret the results of spectroscopic measurements. A comparison is made among TiO2 rutile, TiO2 anatase, and γ-Al2O3. On all three materials, the modification proceeds via the boronic functional groups, with metal oxide-controlled surface chemistry. The bonding configuration depends on the material and is dominated by a monodentate species for titania and by bidentate species for alumina. The surface structures determined to form on all the oxide semiconductors investigated suggest that sensitization or monolayer doping approaches with a well-defined chemical interaction via a boronic functionality can be developed.
Description
This document is the Accepted Manuscript version of a Published Work that appeared in final form in Chemistry of Materials, copyright © 2022 American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.chemmater.2c02789. This article will be embargoed until 12-13-2023
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Citation
Byron, Carly, Dhamelyz Silva-Quinones, Sucharita Sarkar, Scott C. Brown, Shi Bai, Caitlin M. Quinn, Zachary Grzenda, Mitchell S. Chinn, and Andrew V. Teplyakov. “Attachment Chemistry of 4-Fluorophenylboronic Acid on TiO2 and Al2O3 Nanoparticles.” Chemistry of Materials 34, no. 23 (December 13, 2022): 10659–69. https://doi.org/10.1021/acs.chemmater.2c02789.