@article{c9a76016c7da4594ae3e19ee76232638,
title = "Self‐Induced and Progressive Photo‐Oxidation of Organophosphonic Acid Grafted Titanium Dioxide",
abstract = "While synthesis-properties-performance correlations are being studied for organophosphonic acid grafted TiO2 , their stability and the impact of the exposure conditions on possible changes in the interfacial surface chemistry remain unexplored. Here, the impact of different ageing conditions on the evolution of the surface properties of propyl- and 3-aminopropylphosphonic acid grafted mesoporous TiO2 over a period of 2 years is reported, using solid-state 31 P and 13 C NMR, ToF-SIMS and EPR as main techniques. In humid conditions under ambient light exposure, PA grafted TiO2 surfaces initiate and facilitate photo-induced oxidative reactions, resulting in the formation of phosphate species and degradation of the grafted organic group with a loss of carbon content ranging from 40 to 60 wt %. By revealing its mechanism, solutions were provided to prevent degradation. This work provides valuable insights for the broad community in choosing optimal exposure/storage conditions that extend the lifetime and improve the materials' performance, positively impacting sustainability.",
keywords = "ageing, organophosphonic acids, photo-oxidation, surface chemistry, titanium dioxide",
author = "Nick Gys and Bram Pawlak and Kristof Marcoen and Gunter Reekmans and Velasco, {Leticia F.} and Rui An and Kenny Wyns and Kitty Baert and Kaimin Zhang and Lufungula, {Leon Luntadila} and Alessandra Piras and Laurens Siemons and Bart Michielsen and {Van Doorslaer}, Sabine and Frank Blockhuys and Tom Hauffman and Peter Adriaensens and Steven Mullens and Vera MEYNEN",
note = "Funding Information: This work is supported by the Research Foundation Flanders (FWO) and Hasselt University via the Hercules project AUHL/15/2‐GOH3816N. K. Zhang is supported by the EASiCHEM project funded by the Flemish Strategic Basic Research Program of the Catalisti cluster and Flanders Innovation & Entrepreneurship (HBC.2018.0484). B. Pawlak acknowledges the FWO project G. 0121.17N and Rui An is grateful for the DOCPRO4 bonus project of the University of Antwerp. V. Meynen acknowledges the Research Foundation‐Flanders (FWO) for project K801621N. EPR measurements were performed in the UAntwerp EPR facility funded by FWO (grant I004920N to S. Van Doorslaer and V. Meynen). All calculations were performed using the Hopper HPC infrastructure at the CalcUA core facility of the University of Antwerp, a division of the Flemish Supercomputer Center VSC, funded by the Hercules Foundation, the Flemish Government (department EWI) and the University of Antwerp. The authors would like to acknowledge Jef De Wit for the CHNS analysis, Wilfried Brusten and Filip Beutels for the ICP measurements, Saskia Defoss{\'e} and Karen Leyssens for the N sorption measurements, Raymond Kemps for the SEM measurements, Y.H. Vincent Ching for help with the EPR measurements and Myrjam Mertens for the XRD measurements. 2 Funding Information: This work is supported by the Research Foundation Flanders (FWO) and Hasselt University via the Hercules project AUHL/15/2-GOH3816N. K. Zhang is supported by the EASiCHEM project funded by the Flemish Strategic Basic Research Program of the Catalisti cluster and Flanders Innovation & Entrepreneurship (HBC.2018.0484). B. Pawlak acknowledges the FWO project G. 0121.17N and Rui An is grateful for the DOCPRO4 bonus project of the University of Antwerp. V. Meynen acknowledges the Research Foundation-Flanders (FWO) for project K801621N. EPR measurements were performed in the UAntwerp EPR facility funded by FWO (grant I004920N to S. Van Doorslaer and V. Meynen). All calculations were performed using the Hopper HPC infrastructure at the CalcUA core facility of the University of Antwerp, a division of the Flemish Supercomputer Center VSC, funded by the Hercules Foundation, the Flemish Government (department EWI) and the University of Antwerp. The authors would like to acknowledge Jef De Wit for the CHNS analysis, Wilfried Brusten and Filip Beutels for the ICP measurements, Saskia Defoss{\'e} and Karen Leyssens for the N2 sorption measurements, Raymond Kemps for the SEM measurements, Y.H. Vincent Ching for help with the EPR measurements and Myrjam Mertens for the XRD measurements. Publisher Copyright: {\textcopyright} 2023 The Authors. ChemPlusChem published by Wiley-VCH GmbH.",
year = "2023",
month = mar,
day = "10",
doi = "10.1002/cplu.202200441",
language = "English",
volume = "88",
journal = "ChemPlusChem",
issn = "2192-6506",
publisher = "Wiley-VCH Verlag",
number = "3",
}