Surface plasma Ag-decorated Bi5O7I microspheres uniformly distributed on a zwitterionic fluorinated polymer with superfunctional antifouling property
Graphical abstract
Introduction
Biofouling or fouling is a naturally occurring phenomenon caused by accumulation, settlement, and rapid colonization of marine organisms (e.g., bacteria, algae, and mollusks) on submerged surfaces, including ship hulls, pipelines, oil platforms, and ocean sensors, in marine environments [[1], [2], [3]]. This causes serious problems, particularly for marine industries, because of deterioration of surfaces, increased roughness, higher fuel usage, and loss of vessel speed [4,5]. Historically, toxic release has been used to combat marine biofouling, but it causes severe ecological damage. Thus, there is an urgent need for new antifouling strategies that are more environmental friendly but effective controlling adhesion of fouling communities [6,7].
Recently, the photocatalytic antifouling technique, an economical, effective, and environmentally photooxidation process, has attracted much attention because it uses solar energy and has low toxicity [8,9]. This approach is considered to be a promising technique for marine engineering materials [10,11]. When semiconductor materials are irradiated by visible light, reactive oxygen species (ROS), such as e−, h+, OH, and O2−, are produced, and they play important roles in photocatalytic systems [12,13]. Many types of semiconductor materials, such as TiO2, C3N4, and ZnO, are considered to be suitable photocatalysts for widespread application because of their high activity, stability, and low cost [[14], [15], [16], [17]]. TiO2 is the most widely used photocatalyst because of its low cost, good stability, and environmental friendly characteristics. However, its band-gap energy of 3.2 eV means that TiO2 can only absorb a small fraction of solar energy (<4%) [18,19]. To achieve sufficient utilization of solar energy, novel photocatalysts driven by visible light have attracted considerable attention. Bismuth oxyhalides (BiOX, X = Cl, Br, and I) are a group of V–VI–VII ternary compound semiconductors with layered configurations composed of [Bi2O2] layers, and they have recently shown low recombination rate of electron–hole pairs and remarkable photocatalytic activity [[20], [21], [22]]. Among the bismuth oxyhalides, BiOI has been extensively investigated because of its visible light absorption range and suitable band-gap energy, and it has attracted extensive research interest in the field of photocatalysis [23,24]. Unfortunately, because of some deficiencies, such as unsatisfactory charge separation and utilization efficiency, the low light absorption efficiency of BiOI greatly limits its further applications. A series of optimized strategies have been explored to overcome these intrinsic deficiencies, such as crystal face exposure, ion doping, and heterojunction construction [[25], [26], [27]]. Recently, a bismuth-rich strategy has been reported to be effective for improving the photocatalytic efficiency of bismuth oxyhalides, and Bi5O7I possesses a more positively positioned valence band edge and generates more photoholes than other bismuth oxyhalides (such as BiOI, Bi4O5I2 and Bi2O3) [28,29].
It has been reported that some metals (including Ag and Pt) deposited on the surface of photocatalysts act as an electron mediator and also exhibit plasmon-enhanced light harvesting and charge separation [29,30]. Ag nanoparticles are commonly used as an effective co-catalyst and active sites on the surface of semiconductors, because Ag has low cost and excellent ability for absorbing visible light owing to surface plasmon resonance [31,32]. However, released Ag ions can change the permeability of the cytomembrane and denature proteins in biofouling organisms, which cause the fouling organisms to lose their bioactivity [33,34].
Photoexcitation of semiconductors can also generate heat, which have higher initial carrier temperature than the lattice temperature. Some nanoparticles containing Au, Ag, and Bi have been reported as photothermal materials based on their light absorption to exhibit a photothermal response [[35], [36], [37]]. Therefore, the Ag plasmon-enhanced Bi5O7I composite can act as a photothermal agent for antifouling applications.
Zwitterionic polymers have also attracted considerable attention as promising antifouling materials owing to their high hydrophilicity and environmental stability. They contain equal numbers of opposite charges within each repeat unit, resulting in a net medium charge but a high density of local charge [38,39]. This locally highly charged feature causes a significant hydration layer on the surface of the zwitterionic polymer by electrostatic interactions. Although zwitterionic polymers exhibit effective antifouling properties, many defects still exist [40]. Modification of zwitterionic polymer surfaces with nanoparticles is a common strategy to improve the resistance to adhesion [41].
In this study, we prepared Bi5O7I/Ag/zwitterionic fluorinated polymer (ZFP) (ABZFP) composite films consisting of a flower-like Bi5O7I structure, plasma-enhanced Ag co-catalyst, and ZFP for the first time. Their crystal structures, chemical compositions, chemical valences, and morphologies were then investigated. Their antifouling activities and photocatalytic activities under visible light irradiation were also investigated. In addition to the individual function of each component, the combination of Ag, Bi5O7I, and ZFP realized synergistic ion release, photothermal catalysis, and the hydration effect to improve the antifouling activity. These results may open a new route for marine antifouling.
Section snippets
Preparation of the Bi5O7I/Ag composite
Bi(NO3)3·5H2O (2 mmol) was dissolved in ethanol (20 mL) under 1 h magnetic stirring at room temperature to form white suspension A. KI (2 mmol) was added to deionized water (20 mL) to obtain solution B. Solution B was then added to suspension A drop by drop under magnetic stirring, and the pH of the mixed solution was adjusted to 7 with NaOH solution (1 M) to obtain brick-red suspension C. Subsequently, suspension C was heated for 5 h at 80 °C in an oil bath. The product was collected by
Structure and characteristics of the Bi5O7I/Ag flower-like microspheres
Successful synthesis of the Bi5O7I and Bi5O7I/Ag micro/nanostructures was confirmed by SEM and TEM (Fig. 1a, b, e, S3 and S5). Bi5O7I/Ag had a uniform hierarchical flower-like morphology with diameters of 2–3 μm composed of thin platelets with an average size of 800 nm where the Ag particles grew. The XRD pattern and Raman spectra of the Bi5O7I/Ag sample (Fig. 1c and S6) was indexed to orthorhombic Bi5O7I (JCPDS No. 00-40-0548). There were no diffraction peaks related to Ag, which is attributed
Conclusions
In summary, a ABZFP superfunctional composite film consisting of flower-like structure Bi5O7I with plasma-enhanced co-catalysts Ag and ZFP have been reported as a new-generation efficient marine antifouling film. Specifically, ABZFP-1 reduces diatom adhesion by 99.70 % and disinfects 99.62 % of E. coil and 99.78 % of S. aureus in 12 h. The mechanisms driving antifouling were systematically investigated. ROS, including OH and O2−, play significant roles, while the heat produced by
Author contributions
Linlin Zhang synthesized Bi5O7I/Ag particles, analyzed the photocatalytic mechanism of the materials and writing - original draft.
Jianang Sha synthesized the zwitterionic fluorinated polymer (ZFP) and analyzed the performance of ZFPs.
Rongrong Chen performed the formal analysis.
Qi Liu performed the data curation.
Jing yuan Liu performed the data curation.
Jing Yu performed the investigation.
Hongsen Zhang performed the analysis of XPS and SEM of the composite coating.
Cunguo Lin contributed the
Declaration of Competing Interest
The authors declare that they have no know competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
Acknowledgments
This work was supported by National Natural Science Foundation of China (NSFC) 21871078 and 51672073, Domain Foundation of Equipment Advance Research of 13th Five-year Plan (No. 61409220419), Postdoctoral Science Foundation of China (2019M663416), Open Fund of Shandong Key Laboratory of Corrosion Science (No. KLCS201902), National Key Research and Development Project (2019YFC0312102) and Defense Industrial Technology Development Program (JCKY2018604C011).
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