Electropolymerization of Polydopamine at Electrode-Supported Insulating Mesoporous Films

H Samet Varol; Tilmann Herberger; Marius Kirsch; Joanna Mikolei; Lothar Veith; Venkataprasanna Kannan-Sampathkumar; Raoul D Brand; Christopher V Synatschke; Tanja Weil; Annette Andrieu-Brunsen

doi:10.1021/acs.chemmater.3c01890

Electropolymerization of Polydopamine at Electrode-Supported Insulating Mesoporous Films

Chem Mater. 2023 Nov 2;35(21):9192-9207. doi: 10.1021/acs.chemmater.3c01890. eCollection 2023 Nov 14.

Affiliations

¹ Ernst-Berl Institut für Technische und Makromolekulare Chemie, Technische Universität Darmstadt, 64287 Darmstadt, Germany.
² Department of Chemistry "Giacomo Ciamician″, Università degli Studi di Bologna, Via Selmi 2, 40126 Bologna, Italy.
³ Max Planck Institute for Polymer Research, Ackermannweg 10, 55128 Mainz, Germany.
⁴ Institute of Physical Chemistry, Justus-Liebig University, 35392 Giessen, Germany.

Abstract

Bioinspired, stimuli-responsive, polymer-functionalized mesoporous films are promising platforms for precisely regulating nanopore transport toward applications in water management, iontronics, catalysis, sensing, drug delivery, or energy conversion. Nanopore technologies still require new, facile, and effective nanopore functionalization with multi- and stimuli-responsive polymers to reach these complicated application targets. In recent years, zwitterionic and multifunctional polydopamine (PDA) films deposited on planar surfaces by electropolymerization have helped surfaces respond to various external stimuli such as light, temperature, moisture, and pH. However, PDA has not been used to functionalize nanoporous films, where the PDA-coating could locally regulate the ionic nanopore transport. This study investigates the electropolymerization of homogeneous thin PDA films to functionalize nanopores of mesoporous silica films. We investigate the effect of different mesoporous film structures and the number of electropolymerization cycles on the presence of PDA at mesopores and mesoporous film surfaces. Our spectroscopic, microscopic, and electrochemical analysis reveals that the amount and location (pores and surface) of deposited PDA at mesoporous films is related to the combination of the number of electropolymerization cycles and the mesoporous film thickness and pore size. In view of the application of the proposed PDA-functionalized mesoporous films in areas requiring ion transport control, we studied the ion nanopore transport of the films by cyclic voltammetry. We realized that the amount of PDA in the nanopores helps to limit the overall ionic transport, while the pH-dependent transport mechanism of pristine silica films remains unchanged. It was found that (i) the pH-dependent deprotonation of PDA and silica walls and (ii) the insulation of the indium-tin oxide (ITO) surface by increasing the amount of PDA within the mesoporous silica film affect the ionic nanopore transport.