Laser-Induced Graphitization of Polydopamine on Titania Nanotubes

Adrian Olejnik; Krzysztof Polaczek; Marek Szkodo; Alicja Stanisławska; Jacek Ryl; Katarzyna Siuzdak

doi:10.1021/acsami.3c11580

Laser-Induced Graphitization of Polydopamine on Titania Nanotubes

ACS Appl Mater Interfaces. 2023 Nov 1;15(45):52921-52938. doi: 10.1021/acsami.3c11580. Online ahead of print.

Authors

Adrian Olejnik^{1

2}, Krzysztof Polaczek^{2

3}, Marek Szkodo⁴, Alicja Stanisławska⁴, Jacek Ryl⁵, Katarzyna Siuzdak²

Affiliations

¹ Department of Metrology and Optoelectronics, Faculty of Electronics, Telecommunications and Informatics, Gdańsk University of Technology, Narutowicza 11/12 St., Gdańsk 80-233, Poland.
² Centre for Plasma and Laser Engineering, The Szewalski Institute of Fluid-Flow Machinery, Polish Academy of Sciences, Fiszera 14 St., Gdańsk 80-231, Poland.
³ Department of Biomedical Chemistry, Faculty of Chemistry University of Gdansk, Wita Stwosza 63 St, Gdańsk 80-308, Poland.
⁴ Institute of Manufacturing and Materials Technology, Faculty of Mechanical Engineering and Ship Technology, Gdańsk University of Technology, Narutowicza 11/12 St., Gdańsk 80-233, Poland.
⁵ Institute of Nanotechnology and Materials Engineering and Advanced Materials Center, Gdańsk University of Technology, Narutowicza 11/12, Gdańsk 80-233, Poland.

Abstract

Since the discovery of laser-induced graphite/graphene, there has been a notable surge of scientific interest in advancing diverse methodologies for their synthesis and applications. This study focuses on the utilization of a pulsed Nd:YAG laser to achieve graphitization of polydopamine (PDA) deposited on the surface of titania nanotubes. The partial graphitization is corroborated through Raman and XPS spectroscopies and supported by water contact angle, nanomechanical, and electrochemical measurements. Reactive molecular dynamics simulations confirm the possibility of graphitization in the nanosecond time scale with the evolution of NH₃, H₂O, and CO₂ gases. A thorough exploration of the lasing parameter space (wavelength, pulse energy, and number of pulses) was conducted with the aim of improving either electrochemical activity or photocurrent generation. Whereas the 532 nm laser pulses interacted mostly with the PDA coating, the 365 nm pulses were absorbed by both PDA and the substrate nanotubes, leading to a higher graphitization degree. The majority of the photocurrent and quantum efficiency enhancement is observed in the visible light between 400 and 550 nm. The proposed composite is applied as a photoelectrochemical (PEC) sensor of serotonin in nanomolar concentrations. Because of the suppressed recombination and facilitated charge transfer caused by the laser graphitization, the proposed composite exhibits significantly enhanced PEC performance. In the sensing application, it showed superior sensitivity and a limit of detection competitive with nonprecious metal materials.

Keywords: IPCE; graphitization; intensity-modulated photovoltage spectroscopy; laser-induced graphene; photoelectrochemistry; polydopamine; titania nanotubes.