J.Cent.South Univ.(2025) 32: 882－893
Graphic abstract:
1 Introduction
Humanity has been continuously exploring the uncharted territories of the oceans, which has resulted in unavoidable losses due to natural phenomena such as metal corrosion and fouling by marine organisms. According to the American Society of Corrosion Engineers, direct corrosion caused global losses of approximately 2.5 trillion dollars in 2016 [1]. However, recent estimates suggest that this value has increased to several trillion dollars per year [2]. The annual economic cost of fouling is estimated to be $15 billion [3]. Addressing marine corrosion and biofouling has significant economic benefits. Among the many methods of preventing corrosion on metal surfaces, in addition to changing the microstructure of the steel itself to enhance its corrosion resistance [4], applying an organic coating on its surface to protect the steel is the simplest, most efficient, and most cost-effective corrosion prevention method [5]. Marine biofouling is the negative impact caused by the colonization or proliferation of organisms on metal surfaces in water [6, 7]. To address this issue, various removal methods have been developed, including traditional mechanical removal, ultrasonic cleaning, electrochemical methods, and antifouling coatings. Among these methods, antifouling coatings are widely regarded as one of the most effective and economical options in the industry [8]. The combination with corrosion protection to form dual-action composites has been explored to address the drawbacks of using them alone, with significant economic benefits [9].
Epoxy resin (EP) is a thermosetting resin that widely used in marine corrosion protection and anti-biofouling substrates due to its excellent chemical resistance, mechanical strength, high strength, and stiffness, as well as very strong adhesion to the substrate [10-12]. Among these, bisphenol A-based epoxy resin (E44) coatings have excellent scratch-resistant hardness, adhesion, and other properties, making them a promising choice as coating substrates. However, it is important to note that many single-component epoxy resins have poor crack resistance [13] and tend to produce air bubbles during the curing process due to solvent evaporation. This can result in the formation of micropores and microcracks of varying sizes [14-16], which can allow corrosive media such as oxygen and chloride ions to come into contact with the metal substrate through the pores, leading to coating failure and removal [17, 18], One effective solution to this issue is the addition of biocides. In 2008, the International Maritime Organization (IMO) banned the use of tributyltin (TBT) as an additive due to its harmful effects on marine organisms’ reproduction and its tendency to accumulate in their bodies [19]. Therefore, there is an urgent need to find low-toxicity and environmentally friendly alternatives. Incorporating inorganic nanoparticles, two-dimensional materials, and metal-organic frameworks into organic coatings has been shown to create composite coatings with antimicrobial and anticorrosive properties. Examples of inorganic nanoparticles used include TiO2, ZnO, and Ag [20], while graphene and its derivatives, and covalent organic frameworks (COFs) [21, 22] are examples of two-dimensional materials. Copper 1,3,5-benzenetricarboxylate acid (Cu-BTC) and 2-methylimidazole zine salt (ZIF-8) [23, 24] are examples of metal-organic frameworks.
Metal-organic frameworks (MOFs) are periodic crystalline porous inorganic-organic hybrid materials formed through the self-assembly of organic linkers and transition metal ions as secondary building blocks [25-27]. MOFs offer several advantages, including high porosity, low density, large specific surface area, regular pore channels, and tunable pore size, as well as topological diversity and adjustability [28]. Furthermore, Cu-BTC has good thermal stability and corrosion resistance [29]. In addition, the copper ions released from its hydrolysis possess antibacterial properties, prevent bio-adhesion, and did not cause environmental problems due to high concentrations. Titanium dioxide, on the other hand, acts as a photocatalyst to generate large amounts of reactive oxygen species to kill bacteria and prevent contaminants from adhering to the coating surface under UV or visible light [30], and is used as an important self-cleaning coating [31], and the effect of the addition of nanoparticles on the enhancement of corrosion protection has been investigated [16]. SUNADA et al [32] found that titanium dioxide photocatalysis enhances the efficiency of copper ions in entering the cell. In order to combine the antimicrobial properties of both, it is essential to reduce the amount of copper used and apply it to the widely marketed marine metal surface coatings.
For the first time, we loaded titanium dioxide nanoparticles onto the surface of Cu-BTC to form inorganic metal-organic framework hybrids (TiO2/Cu-BTC). We used hydrothermal, mechanically stirred, and in-situ grown methods to create these hybrids. Subsequently, we added them to bisphenol A-based epoxy resin E44 to obtain a composite coating (TiO2/Cu-BTC@EP). We compared the effects of different synthesis methods and ratios on the antimicrobial and impedance values of the coatings. The study results indicate that titanium dioxide’s antimicrobial rate increased by 35.77% under light conditions. Additionally, Cu-BTC@EP exhibited excellent antimicrobial performance, with an antimicrobial rate of over 90% regardless of light exposure. The addition of fillers significantly improved the coatings’ anti-corrosion performance. The impedance values of the coatings with three different loading modes reached 1×1010 Ω. This provides a new approach to preparing integrated antimicrobial and anti-corrosion epoxy coatings.
2 Experimental
2.1 Materials and reagents
1,3,5-benzenetricarboxylic acid (98%) and copper (II) nitrate trihydrate (99%), were purchased from Shanghai Maclin Biochemical Technology Co., Ltd. Luria-Bertani (LB) broth culture medium, butyl titanate, and agar powder, anhydrous ethanol (98%) and glacial acetic acid (98%) were procured from Shanghai Aladdin Biochemical Technology Co., Ltd. Additionally, Phoenix brand epoxy resin (E44) was sourced from Nantong Xingchen Synthetic Materials Co., Ltd., while polyimide resin was obtained from Danyang Danbao Resin Co., Ltd. Q235 steel blocks, microscopy slides (Sail brand), deionized water, and Escherichia coli (E. coli) were provided by the local laboratory. No further treatment was applied to the materials.
2.2 Synthesis of Cu-BTC
The synthesis method used was the classical hydrothermal synthesis method with slight modifications based on our previous work [33]. In a 100 mL beaker, 0.96 g (4.0 mmol) of copper (II) nitrate trihydrate, 0.84 g (4.0 mmol) of 1,3,5-benzenetricarboxylic acid (BTC), 40 mL of deionized water, and 40 mL of ethanol were combined. The mixture was then ultrasonicated for 15 min and stirred until a homogeneous solution was formed. The solution was then transferred to a 100 mL Teflon-lined stainless steel autoclave and the reaction was conducted at 120 ℃ for 24 h. Afterward, the resulting product was suction-filtered, washed three times with anhydrous ethanol through centrifugation, and then vacuum-dried at 60 ℃ for 24 h.
2.3 Synthesis of TiO2
Titanium dioxide nanoparticles were synthesized using a modified hydrolysis method [34]. Anhydrous ethanol and deionized water (25 mL each) were mixed in a beaker and the pH was adjusted to 4 with glacial acetic acid. Butyl titanate (1 mL) was added dropwise to the beaker while stirring continuously. After stirring for 30 min, the obtained colloidal solution was filtered, washed three times with ethanol and deionized water, and then vacuum-dried at 80 ℃ for 10 h. Finally, the dried product was ground into a white solid powder.
2.4 Synthesis of TiO2/Cu-BTC
Firstly, take 20 mg of Cu-BTC and 100 mg of TiO2 in a beaker, and add 20 mL of methanol as a solvent. Place it in vigorous stirring for 7 d to obtain the mechanically stirred complexes (M-TiO2/Cu-BTC). With the same proportions as before, transfer the solution to a Teflon-lined stainless steel reactor after 5 min of ultrasonication, set the temperature to 120 ℃, and react for 24 h to obtain the hydrothermally synthesized complexes (W-TiO2/Cu-BTC). Building on Section 2.3, add 20 mg of Cu-BTC to the solution with the pH adjusted to 4 and ultrasonicate for 5 min. Then, add 400 mL of butyl titanate. The subsequent steps remain the same, resulting in the in-situ grown complexes (Y-TiO2/Cu-BTC). All three different complexes were centrifugally filtered, washed three times with ethanol, vacuum-dried at 80 ℃ for 10 h, and finally ground into a powdery form to obtain the end product (Figure 1).
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2.5 Preparation of antimicrobial coatings
Our epoxy resin employs the E44 series. Take 0.6 g of E44 in a container, and heat it to 60 ℃ to transform its state from a viscous material to a fluid substance. Then, add 500 mL of ethanol as a solvent and continuously stir to ensure even dispersion. Next, take 0.4 g of polyimide resin curing agent in the container, stir again to achieve uniformity, and evacuate the container to remove any residual air bubbles. Finally, using a 200 mm thickness film applicator, evenly coat the epoxy resin onto the surface of Q235 steel, naming it EP for antibacterial and anticorrosive testing. Take 10 mg of titanium dioxide, Cu-BTC and the three obtained complexes from Section 2.4, and disperse them in 800 μL of anhydrous ethanol. Heat the epoxy resin and polyimide resin mixture to 60 ℃ for 5 min, maintaining the same proportions, and mix thoroughly. The subsequent steps for making TiO2@EP, Cu-BTC@EP, W-TiO2/Cu-BTC@EP, M-TiO2/Cu-BTC@EP, and S-TiO2/Cu-BTC@EP remain unchanged.
2.6 Structural characterization
The sample surface morphology was examined using a field emission scanning electron microscope (FESEM, Zeiss/Bruker Gemini-500) equipped with an Edax Octane Elect EDS system (Edax/Ametek Inc.). The SEM utilized Cu Kα radiation (λ=1.5418 nm) as the radiation source, operating at 40 kV and 20 mA, with a scanning speed of 8°/min. Powder X-ray diffraction (PXRD) analysis was conducted using a Rigaku D/MAX-2200 instrument, with a diffraction angle range of 20°-80°.Fourier-transform infrared spectroscopy (FTIR) was performed on a PerkinElmer Spectrum 100 series spectrometer using KBr particles as a background, recording spectra in the range of 4000-400 cm⁻¹. UV-visible diffuse reflectance spectroscopy (UV-vis DRS) of solid samples was measured in the range of 200-800 nm using a Shimadzu UV-2700 spectrophotometer on a Perkin Elmer Lambda 650S spectrophotometer. Barium sulfate (BaSO4) served as the standard with a reflectance of 100%. A laser micro-focused Raman spectrometer (Raman, Renishaw, inVia reflex) with an excitation wavelength of 532 nm, a power range of 400- 2000 cm⁻¹, and a spectral resolution of 1 cm⁻¹ was used to collect Raman spectra from the material surface. The laser source was a frequency-doubled Nd-YAG laser with a power of 66 mW.
2.7 Antimicrobial testing
In the antibacterial experiments, E. coli was used as the test strains. First, E. coli inoculum was cultured in 40 mL of LB broth at 37 ℃ and 180 r/min for 12 h. Subsequently, the bacterial suspension was centrifuged, washed with a 0.9% NaCl solution, and finally resuspended in 10 mL of 0.9% NaCl solution. The optical density (OD) was measured using a UV spectrophotometer, and the concentration was determined to be between 108 and 109 CFU/mL. Next, 40 μL of the bacterial solution was added to a sterile tube and diluted to 40 mL with a 0.9% NaCl solution to a final concentration of 105-106 CFU/mL. The coatings prepared in Section 2.5 were then placed into the tubes and shaken for 3 h in a shaking incubator (37 ℃, 180 r/min) under both dark and light conditions. Afterward, 100 μL of the suspension was taken and spread on solid culture plates. It is important to note that for each sample, the average of three dilution gradients was calculated to reduce experimental error. Additionally, blank control experiments were set up. The plates were then incubated at 37 ℃ for 24 h, and the surviving colony count of E. coli was determined using the plate counting method. Finally, the survival rate (A) was calculated as follows:
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where C0 and C1 represent the bacterial concentrations on the LB agar plates for the blank control group and the experimental group, respectively.
2.8 Corrosion protection test
At standard room temperature, coatings prepared using the method mentioned in the Section 2.5 were uniformly applied to the polished surface of Q235 carbon steel plates (70 mm× 35 mm×1 mm). After waiting for 5 d for complete curing, the coated plates were immersed in a glass tube (inner diameter = 3.5 cm) containing 38 mL of 3.5% artificial seawater (ASW). Electrochemical testing was then performed. Electrochemical impedance spectroscopy (EIS) measurements were conducted using a Gamry-2 electrochemical workstation (Reference 3000, USA) with a voltage range of -1.2 to 0.2 V, a scan rate of 1 mV/s, and a sampling interval of 50 s. The obtained impedance and Bode data were analyzed and fitted using Z-SimpWin software.
3 Discussion of results
3.1 Morphological characterization
A high-resolution field emission scanning electron microscope was used to observe the surface morphology of TiO2, Cu-BTC, and TiO2/Cu-BTC synthesized by the three different loading methods. Nanoscale anatase-type titanium dioxide was successfully synthesized with an average size of around 150 nm, as shown in Figure 2(a). The Cu-BTC synthesized (Figure 2(b)) exhibits octahedral crystals with a size of approximately 15 μm, indicating the experiment’s success. Figures 1(c) and (d) show that nano-sized particles, attributed to titanium dioxide particles, are present on the smooth surface of Cu-BTC. The hybrids obtained through hydrothermal and mechanical stirring methods effectively retained their respective characteristics effectively. However, in-situ growth method resulted in titanium dioxide synthesized that covered the surface of Cu-BTC with a colloidal substance, possibly due to incomplete hydrolysis of titanium butoxide during the process.
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3.2 Structural characterization
Powder X-ray diffraction (PXRD), Raman spectroscopy, ultraviolet-visible (UV-vis) spectroscopy, and Fourier-transform infrared (FTIR) spectroscopy were used to analyze the crystal structure and functional groups of the synthesized materials. The PXRD results in Figure 3(a) show prominent diffraction peaks at 2θ=25.4°, 37.9°, 48.2°, 53.9°, 55.2° and 62.9°, which correspond to the (101), (004), (200), (105), (211) and (204) planes of anatase-type titanium dioxide [35]. The peaks at 2θ=25.32°, 29.34°, 35.24° and 37.8° correspond to the (731), (751), (773) and (882) crystal faces of the octahedral Cu-BTC [36]. A comparison shows that the hydrothermal synthesis of the loaded material predominantly exhibits the crystal structure of Cu-BTC, while M-TiO2/Cu-BTC obtained through mechanical stirring displays the main characteristic peaks of both TiO2 and Cu-BTC. The S-TiO2/Cu-BTC grown in-situ exhibits inconspicuous characteristic diffraction peaks, which can be attributed to the coverage effect of butyl titanate. This effect significantly weakens the diffraction results, consistent with the morphology observed in Figure 2(e). The Fourier transform infrared spectra presented in Figure 3(b) show O—H bonds from water in the wavelnumber range of 3100-3700 cm-1. The characteristic peaks of Cu-BTC at 1647, 1448, 1372 and 728 cm-1, corresponding to C=O, O—H, C—O and Cu—O bonds, respectively, are clearly observable in S-TiO2/Cu-BTC, M-TiO2/Cu-BTC and W-TiO2/Cu-BTC [37]. In the range of 450-900 cm⁻¹, Ti—O—Ti and O—Ti—O bonds belonging to TiO2 are observed [38]. UV-vis spectroscopy and Raman spectroscopy were used for validation. In the UV region (Figure 3(c)), their peak values match well. Figure 3(d) shows Raman testing at a wavelength of 532 nm. The Cu-BTC spectrum exhibits Cu—O stretching at 622 cm-1 and the C—C stretching mode originating from the BTC aromatic ring at 1131 cm-1. The Raman spectrum at 852 cm-1 shows the out-of-plane stretching mode of C—H. Asymmetric and symmetric C=O stretching occurs at 1416 and 1437 cm-1, respectively. The Raman shift at 1601 cm-1 in the Cu-BTC indicates the symmetric stretching mode of C=C [39].
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3.3 Antimicrobial testing
Survival of E. coli was counted using the plate count method. The results show that, compared to dark conditions, all antibacterial coatings exhibited excellent antibacterial effects under light conditions. Particularly, the epoxy coating containing titanium dioxide showed a significant antibacterial difference of 35.77% (Figure 4). This is mainly attributed to the reactive oxygen species (ROS) generated by TiO2 under light conditions, such as •OH, O2- •, and H2O2 [40]. The main active substances responsible for antibacterial action are •OH and h+ [41]. Subsequent, low concentrations of titanium dioxide (NPs) had a hindering effect on E. coli biofilm formation and inhibited its growth [42]. On the other hand, the antibacterial effect of the coating containing Cu-BTC was not significantly affected by light conditions, mainly due to the toxicity of Cu2+ generated by the hydrolysis of Cu-BTC to bacteria [43].
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Additionally, Cu2+ attached to bacterial membrane proteins and nucleic acids, causing damage to the bacterial membrane and cell wall, leading to bacterial injury and death [44]. When exposed to light, copper ions can be reduced to copper metal by photogenerated electrons (Eq. (1)) and copper metal can be oxidized to ions by photogenerated holes (Eq. (2)) [45-48]:
Loading titanium dioxide onto Cu-BTC has a dual effect on antibacterial activity. Specifically, under light conditions, electrons from Cu-BTC transfer to the titanium dioxide conduction band. On the surface of titanium dioxide, they react with dissolved oxygen molecules, inducing the formation of superoxide radicals (O2-•) [49].
The antibacterial effects of the coatings, prepared using three different doping methods are similar, with differences within 5%, regardless of light or dark conditions (Figure 4).
Commercial titanium dioxide or modified titanium dioxide are rarely used in epoxy resin applications. Excellent antimicrobial properties were demonstrated for both Gram-positive and Gram-negative bacteria under light conditions (Table 1). The materials that achieved the 100% antimicrobial rate were all exposed to UV light for 60-100 min. This is consistent with the trend of our coating experimental results.
To visually observe the changes in bacterial quantity, we used the plate counting method for observation (Figure 5). All variables were controlled consistently, except for differences in light conditions. The initial bacterial count in Group A (Figures 5(a)-(f)) was 1.45×105 CFU/mL, and the conclusions align with the results from Figure 4. Under dark conditions, the Cu-BTC@EP reduced the bacterial count to 4.35×103 CFU/mL, while Group B (Figures 5(a1)-(f1)) in light maintained a count of 1.26×103 CFU/mL. When exposed to strong sunlight, the outer side of the biofilm suffers damage from the titanium dioxide photocatalytic reaction products, which leads to the death of the bacteria [57-59]. In addition to the above antimicrobial mechanisms, for TiO2-Cu-BTC/EP there is also a second category, namely, the death phenomenon caused by the entry of copper ions into the cytoplasmic membrane (Figure 6) [32]. In this case, the photocatalytic reaction mainly assists the diffusion of copper ions, which effectively kills the bacteria even under weak light conditions.
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3.4 Anticorrosion test
The electrochemical impedance of the coatings was determined using a Coster electrochemical workstation. The Nyquist plot (Figure 7(a)) shows that the coatings with three different loading methods, W-TiO2/Cu-BTC@EP, M-TiO2/Cu-BTC@EP, and S-TiO2/Cu-BTC@EP, have the larger impedance arc radius. In contrast, the pure epoxy coating (EP) and the Cu-BTC added coating have much smaller impedance arc radii. The hydrophilicity and hydrolysis characteristics of Cu-BTC [24] may be responsible for this. However, its effect on impeding bubble formation during the epoxy resin curing process appears to be only partial. Nanoparticles of titanium dioxide can effectively diffuse into the micro-pores of the coating, providing protective effects [60]. This conclusion is supported by the Bode plot. The impedance value of the E44 epoxy coating is only 1×109 Ω. However, the coatings doped with titanium dioxide show a significant increase of one order of magnitude, reaching up to 1.2×1010 Ω (Figure 7(b)). This significant enhancement in corrosion performance is a crucial role in protecting metal facility equipment.
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4 Conclusions
This work, we employed three different loading methods, namely hydrothermal synthesis, mechanical stirring, and in-situ growth, to combine nano titanium dioxide particles with copper-based metal-organic frameworks (W-TiO2/Cu-BTC, M-TiO2/Cu-BTC, S-TiO2/Cu-BTC). These various hybrids were then added to the epoxy resin E44, which is known for its excellent corrosion resistance. The hybrids mixed well with the epoxy resin, leading to a significant enhancement in the antibacterial capability of the epoxy coating. The experimental strain chosen for this study was E. coli. The antibacterial effectiveness of Cu-BTC/EP was found to exceed 90%, regardless of light conditions. In contrast, the antibacterial effectiveness of titanium dioxide was more affected by light, showing a difference of up to 35.77%. These results suggest that copper-based metal-organic frameworks are more stable in bacterial toxicity than titanium dioxide, which exhibits larger fluctuations due to its photocatalytic ability. The antibacterial capabilities of the three loading methods exhibited similar antibacterial capabilities achieving approximately 50% antibacterial effectiveness. This confirms the synergistic antibacterial capabilities of titanium dioxide and Cu-BTC. Additionally, the impedance radius of the coating increased several times after the addition of hybrids, and the impedance value increased by one order of magnitude. The loading of titanium dioxide nanoparticles further increased the impedance value. Our epoxy coatings applied to the surfaces of marine structural metals provide excellent corrosion and biofouling protection, significantly reducing production protection costs and achieving substantial economic benefits.
Recent advances in corrosion protective composite coatings based on conducting polymers and natural resource derived polymers
[J]. Progress in Organic Coatings, 2014, 77(4): 743-756. DOI: 10.1016/j.porgcoat.2014.01.004.Bioinspired marine antifouling coatings: Status, prospects, and future
[J]. Progress in Materials Science, 2022, 124: 100889. DOI: 10.1016/j.pmatsci.2021.100889.Enhanced mechanical and anticorrosion properties in cryogenic friction stir processed duplex stainless steel
[J]. Materials & Design, 2023, 225: 111492. DOI: 10.1016/j.matdes.2022.111492.Fabrication and characterization of self-assembled graphene oxide/silane coatings for corrosion resistance
[J]. Surface and Coatings Technology, 2016, 304: 76-84. DOI: 10.1016/j.surfcoat.2016.07.002.Polymer-based marine antifouling and fouling release surfaces: Strategies for synthesis and modification
[J]. Annual Review of Chemical and Biomolecular Engineering, 2019, 10: 241-264. DOI: 10.1146/annurev-chembioeng-060718-030401.Recent progress in marine foul-release polymeric nanocomposite coatings
[J]. Progress in Materials Science, 2017, 87: 1-32. DOI: 10.1016/j.pmatsci.2017.02.001.Non-toxic antifouling strategies
[J]. Materials Today, 2010, 13(4): 36-44. DOI: 10.1016/S1369-7021(10)70058-4.Environmentally benign smart self-healing silicone-based coating with dual antifouling and anti-corrosion properties
[J]. Applied Materials Today, 2022, 28: 101551. DOI: 10. 1016/j.apmt.2022.101551.Facile preparation of epoxy based elastomers with tunable Tgs and mechanical properties
[J]. RSC Advances, 2018, 24: 13474-13481. DOI: 10.1039/C8RA00894A.Zinc-rich primers: Test performance and electrochemical properties
[J]. Progress in Organic Coatings, 2005, 54(3): 224-229. DOI: 10.1016/j.porgcoat.2005.06.009.Simultaneously enhanced tensile strength and fracture toughness of epoxy resins by a poly(ethylene oxide)-block-carboxyl terminated butadiene-acrylonitrile rubber dilock copolymer
[J]. RSC Advances, 2015, 53: 42362-42368. DOI: 10.1039/c5ra05124j.Effect of structure on glass transition temperature of amine crosslinked epoxies
[J]. Journal of Polymer Science Part B: Polymer Physics, 1987, 25(6): 1219-1234. DOI: 10.1002/polb.1987.09025 0604.Anti-corrosion coating within a polymer network: Enabling photothermal repairing underwater
[J]. Chemical Engineering Journal, 2021, 412: 128640. DOI:10.1016/j.cej. 2021.128640.Preparation of Ce-MOF@TEOS to enhance the anti-corrosion properties of epoxy coatings
[J]. Progress in Organic Coatings, 2019, 135: 613-621. DOI:10.1016/j.porgcoat.2019.06.015.Preparation of graphene oxide modified by titanium dioxide to enhance the anti-corrosion performance of epoxy coatings
[J]. Surface and Coatings Technology, 2015, 276: 471-478. DOI:10.1016/j.surfcoat.2015.06.027.The effect of microstructure on corrosion behavior of a novel AlCrTiSiN ceramic coating
[J]. Ceramics International, 2020, 46(8): 12584-12592. DOI: 10.1016/j.ceramint.2020. 02.022.A novel waterborne epoxy coating with anti-corrosion performance under harsh oxygen environment
[J]. Chemical Engineering Journal, 2022, 430: 133156. DOI: 10.1016/j.cej.2021.133156.Advanced nanostructures for the control of biofouling: The FP6 EU integrated project AMBIO
[J]. Biointerphases, 2008, 3(1): IR1-IR5. DOI: 10.1116/1.2844718.Surface topography effects on the wettability and antifouling performance of nano-ZnO epoxy composite coatings
[J]. Surface and Coatings Technology, 2022, 433: 128145. DOI: 10.1016/j.surfcoat.2022.128145.Epoxy-matrix polyaniline/p-phenylenediamine-functionalised graphene oxide coatings with dual anti-corrosion and anti-fouling performance
[J]. RSC Advances, 2021, 11(19): 11627-11641. DOI: 10.1039/d0ra10665h.Synergistic antibacterial and anti-inflammatory effects of a drug-loaded self-standing porphyrin-COF membrane for efficient skin wound healing
[J]. Advanced Healthcare Materials, 2021, 10(8):Influence of active nanofiller ZIF-8 metal-organic framework (MOF) by microemulsion method on anticorrosion of epoxy coatings
[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2021, 624: 126836. DOI: 10.1016/j.colsurfa.2021.126836.Water- and acid-sensitive Cu2O@Cu-MOF nano sustained-release capsules with superior antifouling behaviors
[J]. ACS Applied Materials & Interfaces, 2022, 14(1): 1910-1920. DOI: 10.1021/acsami.1c18288.Metal-organic frameworks: A new class of porous materials
[J]. Microporous and Mesoporous Materials, 2004, 73(1, 2): 3-14. DOI: 10.1016/j.micromeso.2004.03.034.A review on metal-organic frameworks: Synthesis and applications
[J]. TrAC Trends in Analytical Chemistry, 2019, 118: 401-425. DOI: 10.1016/j.trac.2019.06.007.Two-dimensional metal-organic framework materials: Synthesis, structures, properties and applications
[J]. Chemical Reviews, 2021, 121(7): 3751-3891. DOI: 10.1021/acs.chemrev.0c01049.Antimicrobial MOFs
[J]. Coordination Chemistry Reviews, 2021, 446: 214121. DOI: 10.1016/j.ccr.2021.214121.Enhanced stability of Cu-BTC MOF via perfluorohexane plasma-enhanced chemical vapor deposition
[J]. Journal of the American Chemical Society, 2012, 134(3): 1486-1489. DOI: 10.1021/ja211182m.Double-doped TiO2 nanoparticles as an efficient visible-light-active photocatalyst and antibacterial agent under solar simulated light
[J]. Applied Surface Science, 2014, 301: 338-345. DOI: 10.1016/j.apsusc.2014.02.074.Visible-light-induced photocatalytic inactivation of bacteria by composite photocatalysts of palladium oxide and nitrogen-doped titanium oxide
[J]. Applied Catalysis B: Environmental, 2009, 88(3, 4): 576-581. DOI: 10.1016/j.apcatb.2008.12.019.Bactericidal activity of copper-deposited TiO2 thin film under weak UV light illumination
[J]. Environmental Science & Technology, 2003, 37(20): 4785-4789. DOI: 10.1021/es034106g.Microstructure and bactericidal properties of Cu-MOF, Zr-MOF and Fe-MOF
[J]. Journal of Central South University, 2023, 30(10): 3237-3247. DOI: 10.1007/s11771-023-5471-9.Particle formation mechanism of TiCl4 hydrolysis to prepare nano TiO2
[J]. Applied Sciences, 2023, 13(22): 12213. DOI: 10. 3390/app132212213.Electrosorption and photocatalytic one-stage combined process using a new type of nanosized TiO2/activated charcoal plate electrode
[J]. Environmental Science and Pollution Research International, 2014, 21(14): 8555-8564. DOI: 10.1007/s11356-014-2777-z.Rational designed Cu-MOF@1D carbon nanofibers as free-standing and flexible electrode for robust electrochemical energy storage
[J]. Journal of Energy Storage, 2023, 67: 107617. DOI: 10.1016/j.est.2023.107617.Synthesis and analytical characterization of Ca-BTC metal organic framework
[J]. Heliyon, 2023, 9(11):Structural, optical and photoluminescence properties of TiO2 and TiO2: Tm3+ nanopowders
[J]. Optik, 2021, 227: 166083. DOI: 10.1016/j.ijleo.2020.166083.Cu-MOF/N-doped GO nanocomposites modified screen-printed carbon electrode towards detection of 4-nitrophenol
[J]. Journal of Electroanalytical Chemistry, 2022, 919: 116542. DOI: 10.1016/j.jelechem.2022.116542.Enhanced photocatalytic and antimicrobial performance of cuprous oxide/titania: The effect of titania matrix
[J]. Materials, 2018, 11(11): 2069. DOI: 10.3390/ma11112069.Research on the preparation of graphene quantum dots/SBS composite-modified asphalt and its application performance
[J]. Coatings, 2022, 12(4): 515. DOI: 10.3390/coatings12040515.Antibacterial characteristics of TiO2 nano-objects and their interaction with biofilm
[J]. Materials Technology, 2017, 32(6): 385-390. DOI: 10.1080/10667857.2016.1236515.Copper stress induces a global stress response in Staphylococcus aureus and represses sae and agr expression and biofilm formation
[J]. Applied and Environmental Microbiology, 2010, 76(1): 150-160. DOI: 10.1128/AEM.02268-09.Antibacterial mechanisms and applications of metal-organic frameworks and their derived nanomaterials
[J]. Trends in Food Science & Technology, 2021, 109: 413-434. DOI: 10.1016/j.tifs. 2021.01.012.Heterogeneous photocatalysis Transition metal ions in photocatalytic systems
[J]. Applied Catalysis B: Environmental, 1999, 23(2, 3): 89-114. DOI: 10.1016/S0926-3373(99)00069-7.Photocurrent enhancement via trapping of photogenerated electrons of titanium dioxide particles
[J]. The Journal of Physical Chemistry, 1982, 86(18): 3599-3605. DOI: 10.1021/j100215a021.Photocatalytic oxidation of phenol in the presence of hydrogen peroxide and titanium dioxide powders
[J]. Journal of Photochemistry and Photobiology A: Chemistry, 1990, 55(1): 115-126. DOI: 10.1016/1010-6030(90)80024-R.Photochemistry of semiconductor particles. Part 4. Effects of surface condition on the photodegradation of 2, 4-dichlorophenol catalysed by TiO2 suspensions
[J]. Journal of the Chemical Society, Faraday Transactions, 1995, 91(5): 917-923. DOI: 10.1039/ft9959100917.Photocatalytic activity of Cu2O/TiO2, Bi2O3/TiO2 and ZnMn2O4/TiO2 heterojunctions
[J]. Catalysis Today, 2005, 101(3, 4): 315-321. DOI: 10.1016/j.cattod.2005.03.038.Antimicrobial activity and cytotoxicity of cotton-polyester fabric coated with a metal-organic framework and metal oxide nanoparticle
[J]. Applied Nanoscience, 2023, 13(8): 5765-5776. DOI: 10.1007/s13204-023-02823-4.Gallium-carbenicillin framework coated defect-rich hollow TiO2 as a photocatalyzed oxidative stress amplifier against complex infections
[J]. Advanced Functional Materials, 2020, 30(43): 2004861. DOI: 10.1002/adfm.202004861.Highly efficient multifunctional Ag/TiO2 nanotubes/Ti plate coated with MIL-88B(Fe) as a photocatalyst, adsorbent, and disinfectant in water treatment
[J]. Applied Physics A, 2018, 125(1): 25. DOI: 10.1007/s00339-018-2324-8.Antibacterial effect of TiO2 nanoparticles modified with APTES
[J]. Catalysis Communications, 2020, 134: 105862. DOI: 10.1016/j.catcom.2019.105862.Preparation and characterization of copper-doped anatase TiO2 nanoparticles with visible light photocatalytic antibacterial activity
[J]. Journal of Photochemistry and Photobiology A: Chemistry, 2014, 280: 32-38. DOI: 10.1016/j.jphotochem.2014.02.006.Antibacterial properties of TiO2 modified with reduced graphene oxide
[J]. Ecotoxicology and Environmental Safety, 2018, 147: 788-793. DOI: 10.1016/j.ecoenv.2017.09.039.Enhanced photocathodic antifouling/antibacterial properties of polyaniline-Ag-N-doped TiO2 coatings
[J]. Journal of Materials Science, 2020, 55(34): 16255-16272. DOI:10. 1007/s10853-020-05170-9.Bactericidal and detoxification effects of TiO2 thin film photocatalysts
[J]. Environmental Science & Technology, 1998, 32(5): 726-728. DOI:10.1021/es970860o.Photocatalytic bactericidal effect of TiO2 thin films: Dynamic view of the active oxygen species responsible for the effect
[J]. Journal of Photochemistry and Photobiology A: Chemistry, 1997, 106(1-3): 51-56. DOI: 10.1016/S1010-6030(97)00038-5.Studies on photokilling of bacteria on TiO2 thin film
[J]. Journal of Photochemistry and Photobiology A: Chemistry, 2003, 156(1-3): 227-233. DOI: 10.1016/S1010-6030(02)00434-3.Anticorrosion reinforcement of waterborne polyacrylate coating with nano-TiO2 loaded graphene
[J]. Journal of Applied Polymer Science, 2020, 137(21): 48733. DOI:10. 1002/app.48733.SU Juan, KANG Fu-yan, ZHAO Zi-long and LIU Fa-qian declare that they have no conflict of interest.
SU Juan, KANG Fu-yan, ZHAO Zi-long, LIU Fa-qian. Antimicrobial and corrosion protection of coatings by copper metal organic frameworks loaded with titanium dioxide nanoparticles [J]. Journal of Central South University, 2025, 32(3): 882-893. DOI: https://doi.org/10.1007/s11771-025-5888-4.
苏娟,康福炎,赵子龙等.Cu-MOF负载TiO2纳米颗粒以提升涂层抗菌防腐能力[J].中南大学学报（英文版）,2025,32(3):882-893.