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Article

Direct In Situ Fabrication of Strong Bonding ZIF-8 Film on Zinc Substrate and Its Formation Mechanism

by
Haidong Wang
1,
Jie Liu
2,
Baosheng Liu
2,
Zhechao Zhang
2,
Xiaoxia Ren
2,
Xitao Wang
2,*,
Pengpeng Wu
2 and
Yuezhong Zhang
2,*
1
School of Applied Technology, Changchun Institute of Technology, Changchun 130012, China
2
School of Materials Science and Engineering, Taiyuan University of Science and Technology, Taiyuan 030024, China
*
Authors to whom correspondence should be addressed.
Metals 2024, 14(12), 1403; https://doi.org/10.3390/met14121403
Submission received: 10 October 2024 / Revised: 4 December 2024 / Accepted: 6 December 2024 / Published: 9 December 2024
(This article belongs to the Special Issue Manufacturing Processes of Metallic Materials)
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Abstract

:
There is much promise for creating metal organic framework (MOF) films on metal substrates in fields including sensing and electrical conduction. For these applications, direct production of MOF films with strong bonding on metal substrates is extremely desirable. In this study, a simple one-step method without the need for additives or pre-modification is used to directly create zeolitic imidazolate framework-8 (ZIF-8) films with strong bonding on zinc substrate. The formation mechanisms of ZIF-8 film are analyzed. The strong bonding ZIF-8 film can be attributed to an in-situ grown ZnO interlayer between the ZIF-8 and substrate. The growth process shows the formation time of zinc oxide on the substrate, which is subsequently covered by ZIF-8 crystals. The ZnO interlayer results from a combination of decomposition products of the solvent and the zinc ions. Furthermore, the ZnO interlayer serves as a sacrificial precursor for the in-situ nucleation and continuous growth of ZIF-8 film. It serves as an anchoring site between ZIF-8 film and substrate, resulting in strong adhesion. This paper describes a simple and straightforward production process that is expected to provide a theoretical basis for the laboratory preparation of ZIF films.

1. Introduction

A subclass of metal organic frameworks (MOFs) known as zeolitic imidazolate frameworks (ZIFs) combines the special qualities of both zeolites and MOFs, including large internal surface areas, high grades of crystallinity, permanent porosity, adjustable pore sizes, and chemical and thermal stability [1]. More recently, ZIFs have demonstrated their intriguing potential as novel functional materials by being used in energy storage [2], sensors [3], optoelectronics [4], membrane separations [5], and catalysis [6]. It is more advantageous to fabricate ZIF materials as films or membranes (rather than powders) for use in these applications, as the former can help with the direct fabrication of ZIFs into gas sensors [7,8,9], electronic devices [10], and other microelectronic devices, while the latter can be used for gas separations [11,12,13].
Various MOF films or membranes that correspond to thin layers have been created thus far using either in situ or secondary growth techniques on a variety of support materials [14], including aluminum oxide [15], titanium dioxide [16], glass [17], organic polymers, etc. [18,19,20]. Less research has been done on ZIF films or membranes synthesized directly on metal substrates [21,22], which could be employed as sensors or electrodes in electrochemical and electrical applications. Furthermore, it is still a challenge to directly fabricate strong-bonding MOF films on metal substrates. The main handicap for directly growing MOF films or membranes on metal substrates is weak interface adhesion and poor heterogeneous nucleation sites [23,24,25]. Therefore, modification of the support surface with suitable functional groups like organosilanes, imidazole derivatives, dopamine, and metal oxides became necessary to improve binding affinity or/and nucleation density. Compared with organic functional, the inorganic modification layer is more favored because it not only can enhance affinity and compatibility but also has strong thermal stability and environmental friendliness. To enhance the binding strength of the MOF layer with the substrate, modifying a metal substrate with metal oxide or hydroxide micro-nanostructures is employed to promote MOF crystal nucleation because these structures can act as both nucleation centers and anchor bars for film growth. For example, Falcaro and co-workers fabricated HKUST-1 (Cu3(BTC)2) film on Cu substrate by converting pre-prepared copper hydroxide coating into HKUST-1 [26]. This approach may be applied to four different MOF films (Cu-BTC, Cu-BDC, ZIF-8, and MOF-5) on either a Cu or Zn substrate, as Kim et al. found [27]. Li et al. also fabricated Co3(HCOO)6 membranes on a Co3O4-modified Ni foam substrate [28]. Nevertheless, these strategies always involved a preceding oxidation step of the metal substrate.
Recently, modified ZnO micro/nanostructures on substrates have been proven to be an effective method for promoting ZIF film or membrane growth and enhancing binding strength to the substrate. For example, a series of ZIFs (ZIF-8, ZIF-68, ZIF-71, and ZIF-78) membranes were fabricated on porous ZnO or ZnO-modified α-Al2O3 substrates [29,30,31,32,33,34,35,36]. In these cases, the ZnO layer acts as a multifunctional role, inducing the nucleation for ZIF crystals, providing the zinc source for Zn-based ZIFs films, and the anchorages between the film and substrate. However, in most of the previous research, ZnO layer deposition was completed via sol-gel and heating methods, resulting in an unstable ZnO layer and complicated operation. Furthermore, activation of the ZnO layer is a non-negligible step to create nucleated species for homogeneous nucleation and induce the growth of ZIF crystals on the ZnO layer surface [37,38]. Therefore, to develop a facile and direct method to fabricate strong-bonding ZIF films derived from ZnO layers on metal substrates is highly desirable.
Here, a one-step solvothermal method was used to directly create a dense zeolitic imidazolate framework-8 (ZIF-8) layer on a zinc substrate. In our strategy, DMF solution only containing zinc ions and 2-methyl imidazolate (mim) ligands were used to synthesize ZIF-8 film (schematically shown in Figure 1). During this one-step process, a hexagonal plate-like ZnO interlayer was in situ constructed between the ZIF-8 crystal layer and substrate, resulting in a separate ZnO preparation or/and activation process that was omitted in previous reports. For the ZIF-8 film to nucleate and grow continuously, the ZnO interlayer acted as a sacrificial precursor. It also acted as an anchoring site between the ZIF-8 film and substrate, strengthening the stability of the film.

2. Experimental

2.1. Materials and Methods

We bought 99.9% zinc foil with a thickness of 0.2 mm from Yi Tian Metal Products Co., Ltd., Shanghai, China. The chemicals that were employed were N, N’-dimethylformamide (DMF, ≥99.9%), 2-methylimidazole (mim), ethanol, and zinc nitrate hexahydrate. (Sinopharm Chemical Reagent Co., Ltd., Shanghai, China, analytical grade).

2.2. Preparation of the ZIF-8 Film

As the substrate, 20 mm by 30 mm zinc foil was utilized. Before the synthesis began, the zinc foil was cleaned by ultrasonically degreasing it in absolute ethanol for five minutes, rinsing it with ultrapure water, and abrading it with emery papers rated 200, 400, and 800#. In order to prepare the growth solution of ZIF-8 film grown in situ, 2-methylimidazole and Zn(NO3)2 were dissolved in DMF solution and stirred magnetically for 10 min to obtain mixed solution concentrations of 0.024 mol/L mim and 0.030 mol/L Zn(NO3)2. A growth solution was made for the in-situ growth of ZIF-8 film by dissolving 0.0457 g of 2-methylimidazole and 0.1812 g of Zn(NO3)2·6H2O in 20 milliliters of DMF solution. First, clean Zn foil was positioned vertically in a stainless steel autoclave lined with Teflon, and 20 milliliters of growth fluid were added. After that, the autoclave was covered with a lid, kept at 150 °C for a predetermined amount of time, and then allowed to cool to room temperature. Then, the Zn foil was removed and dried in air. For comparison, the zinc foil was treated in a quite similar procedure, with methanol instead of DMF or without 2-methylimidazole.

2.3. Characterization

The treated Zn foil surface’s morphological structures were investigated using scanning electron microscopy (SEM, Hitachi S-4800, Tokyo, Japan). Utilizing an X-ray diffraction machine (XRD, Rigaku D/MAX-2500PC, Tokyo, Japan), the phase constitutions were examined. Using Fourier transform infrared spectroscopy (FTIR, Nicolet iN10, Waltham, MA, USA), the samples’ infrared spectra were examined. A Thermoelectron ESCALAB 250 X-ray photoelectron spectrometer (Thermo Fisher Scientific, Waltham, MA, USA) was used to analyze the samples’ surface chemical composition.

3. Results and Discussion

3.1. Synthesis and Characterization of ZIF-8 Film

Typical SEM pictures of the zinc foil following solvothermal treatment for 24 h are given in Figure 2. The SEM image (Figure 2a) at low magnification shows that zinc foil is growing a well-intergrown crystal layer. A higher magnification image of the treated Zn foil (Figure 2b) shows well-formed crystal facets that some small polyhedral crystals randomly distributed with a diameter of 1–3 μm. The cross-sectional view in Figure 2c demonstrates that the film consists of intergrown crystals. The crystals penetrate inside the substrate, making the boundary of the crystals and support very undistinguishable, but a careful inspection still illustrates that the film is of thickness of about 40–50 μm. The treated zinc foil’s typical XRD pattern is displayed in Figure 2d. In addition to the prominent zinc substrate diffraction peaks, a portion of the remaining diffraction peaks (2θ > 30°) can be satisfactorily indexed to the wurtzite hexagonal ZnO structure, indicating that the as-prepared film is primarily composed of ZnO and ZIF-8.
The XPS detection was used to look into the chemical condition and surface composition of ZIF-8 film. The O element and all ZIF-8 (C8H10N4Zn) characteristic elements, such as zinc (coordinating metal), nitrogen, and carbon (imidazole linker), are visible in the XPS survey spectrum (Figure 3a). Three components originating from adventitious carbon (284.6 eV), C-N-C (286.2 eV), and C=C (288.6 eV) could be deconvoluted from the C 1s high-resolution spectrum (Figure 3b) [39]. Two peaks can be identified in the N 1s high-resolution spectrum (Figure 3c) for ZIF-8 film: a larger peak at 399.0 eV and a smaller peak at 400.5 eV, which are attributed to the imidazole and secondary amine groups [22]. DMF breakdown and a trace amount of uncoordinated methylimidazole linkers can produce secondary amines. The autoclaves of the former emit a distinct and powerful fishy odor upon opening for each synthesis. Moreover, Zn2+ of the ZIF-8 is responsible for the Zn 2p 3/2 and Zn 2p 1/2 peaks, which are located at approximately 1021.9 and 1044.9 eV, respectively (Figure 3d) [40].
Furthermore, FTIR spectroscopy was used to investigate the ZIF-8 film’s distinctive functional groups. Zn-N stretching bands exhibit a distinctive absorption peak at 418 cm−1, as depicted in Figure 4. The mim ring’s out-of-plane and in-plane bending are attributed to the bands at 600–800 cm−1 and 900–1350 cm−1, respectively [41,42]. The imidazole’s whole ring stretching is situated between 1350 and 1500 cm−1 [41,42]. The methyl groups from the mim linker’s aliphatic C-H stretching bands may be identified as the peak at 1310 cm−1, while the N-H bending vibration of mim is linked to the peak at 1543 cm−1 [43]. The spectral area of 2900–3200 cm−1 derives from the aliphatic and aromatic C-H stretching of mim. The XRD and XPS results and this result match one another quite well. Therefore, it can be concluded that ZIF-8 completely covers the ZnO layer.

3.2. Evolution of the ZIF-8 Film Formation

A number of operations with varying synthesis times (1 h, 3 h, 6 h, and 12 h) were carried out in order to investigate the formation process of ZIF-8 film in this in-situ approach. After the reaction ran for one hour, the majority of the substrate was covered in randomly distributed tiny protrusions on the zinc foil, as shown in the low-magnification SEM image of the foil (Figure 5a). From the high-resolution SEM image (Figure 5b), the protrusions show irregular polyhedron structure. After just 3 h, some cubes with truncated edges with a diameter of 20 μm and a large number of hexagonal plate-like structures with a diameter of 3–5 μm and a thickness of 0.50–1.4 μm are observed in Figure 5c and d. As reported, the cube with truncated edges is a typical intermediate shape of ZIF-8 (Figure S1, in ESI) [44,45]. The plate-like structures are highly similar to ZnO prepared without mim (Figure 7c). Furthermore, the elemental composition of different morphology protrusions was tested by EDS, and elemental mapping of the sample confirmed that the polyhedron was ZIF-8 crystal, whereas the hexagonal plate-like structure was ZnO (Figure S2, in ESI). Furthermore, the elemental composition of different morphology protrusions was tested by EDS, and elemental mapping of the sample confirmed that the polyhedron was ZIF-8 crystal, whereas the hexagonal plate-like structure was ZnO (Figure S3, in ESI). After just 6 h, a small amount of well-defined independent rhombic dodecahedral crystal protrusions with an average size of 12–18 μm are obtained (Figure 5e), which is a stable equilibrium morphology of ZIF-8 [46,47,48,49]. For the non-protuberant section between the rhombic dodecahedral protrusions (Figure 5f), the small-sized (1–3 μm) interconnected crystals and several hexagonal plate-like structures are obtained. After just 12 h, rhombic dodecahedral crystals become larger and interdigitated with a diameter of 40–60 μm (Figure 5g), and cross-linking small crystals become denser in the non-protuberant section (Figure 5h). When the reaction time was extended to 24 h, the lamellar structure disappeared completely and the polyhedron ZIF-8 was observed (Figure 5i). In addition, small particles of polyhedral crystals have also been observed (Figure 5j). Based on the above results, we can conclude that the hexagonal plate-like ZnO layer is preferentially grown and a dense and crosslinked ZIF-8 crystal layer is obtained on the zinc substrate through nucleation, evolution, and growth processes.
Additionally, the ZIF-8 film underwent time-dependent XRD testing, the results of which are displayed in Figure 6. As seen in Figure 6 and Figure S3, weak characteristic diffraction peaks of ZnO are detected just after 1 h of treatment. Moreover, the peaks of ZnO are also observed for different synthesis times. These results indicate that zinc oxide grows preferentially and is present throughout the process. It is noted that the diffraction pattern of ZIF-8 is detected for the 6h sample, and the intensity is substantially weaker compared with that of 12 h. This is because zinc ions competitively interacted with hydroxyl groups and ligands to form ZnO and ZIF-8 in the case of an in situ process. This outcome agrees with the SEM findings (Figure 5a). Furthermore, ZIF-8’s intensity and degree of crystallinity grow steadily throughout reaction time. Thus, we can conclude that the hexagonal plate-like ZnO is formed prior to the ZIF-8 crystals, then spontaneously converts to ZIF-8, and is finally completely covered by ZIF-8 crystals.

3.3. Effect of Solvent and Reactives on ZnO Formation

To probe the formation mechanism of ZnO, some comparative experiments were carried out. When DMF is replaced by methanol alone, spherical ZnO with a diameter of 0.5–5 μm is detected (Figure 7a,b, and Figure S4a in ESI). These findings suggest that the ZnO layer’s shape and crystal growth direction are significantly influenced by the solvent. The N 1s XPS high-resolution spectrum (Figure 3c) confirms that the amine was created throughout the preparation process when these syntheses were carried out in DMF without the inclusion of a mim linker. There was also a strong, distinct, fishy smell when the autoclaves were opened. The amine may be attributed to dimethylamine decomposed by DMF at the reaction temperature [50]. Moreover, the ZnO layer is formed on a zinc substrate, which consists of a stacked hexagonal plate (Figure 7c,d, and Figure S4b in ESI). This morphology is highly similar to the sample after treatment for 3 h with ligand. These findings suggest that although the ligand aids in the growth of the ZnO layer, it is not necessary for the ZnO layer to form. Additionally, the ligand (mim) also facilitated this process, as confirmed by Carreon et al. [51] due to its weak alkaline (pKb = 7.75) [52]. According to Carreon et al. [51], the mim might function as an organic amino group catalyst that encourages ZnO production. The morphology of the synthesis gel takes on the shape of a hexagonal plate when organic amino groups are added. Zinc oxide nanoplates, for instance, have been created while hexamethylenetetramine and diethylenetriamine are present [53,54,55].

3.4. Formation Mechanisms of ZIF-8 Film

The direct manufacturing of MOF film on metal substrates at large geometrical scales has been tried in a few prior investigations. But only three methods—(i) forming metal oxide overlayer on metal substrates via an earlier oxidation step [27], (ii) adding oxidation reagents in the synthesis solution to oxidize the metal surface [56], or (iii) reducing solvents or introducing reducing gases [21]—can successfully construct ZIF-8 film. Note that no extra chemicals or preparation procedures were used in the construction of the ZIF-8 films given in this study; instead, they were created utilizing a one-step in-situ method. The solvothermal technique is environmentally friendly since it only uses organic ligands and metal substrates. The ZIF-8 film production techniques in this work differ significantly from the earlier methods. ZnO formation and ZIF-8 synthesis processes can occur on the surface of zinc substrates in an aqueous precursor solution. The feasible creation methods of the ZIF-8 film might be postulated as represented in Figure 8.
In the initial stage, the zinc substrate, amphoteric metal, was etched by amine derived from DMF decomposition to release zinc ions. A rich hydroxyl species solution environment is created when the amine is present. Therefore, it is expected that the OH- will react to create Zn(OH)2 with the Zn2+ ions from the zinc reagent and etched zinc substrate. The coordination compounds can be adsorbed on the zinc substrate surface due to electrostatic effects [57]. ZnO is then formed when these hydroxyl species are dehydrated. Additionally, the ligand (mim) also enhances the production of ZnO.
In general, the nucleation of ZIF-8 crystals is affected by deprotonation equilibrium and coordination [58]. According to Cravillon et al. [58], the ZIF-8′s deprotonation equilibrium can be controlled by a modulator. More basic modulating ligands (pKa > 10.3) can deprotonate ligands effectively, resulting in a high nucleation rate, but less basic modulating ligands (pKa < 10.3) cannot. The organic amines from decomposed DMF deprotonate the organic ligands, which act as protonation agents in the synthesis solution. In our case, deprotonation of mim is inhibited by consumed amines for ZnO. Moreover, the amine may hinder the synthesis of ZIF-8 by competing with the mim ligand to coordinate with the Zn2+ on the substrate to generate coordination compounds. Therefore, the ZnO layer’s growth supersedes the ZIF-8 film. The growth of ZnO continues until it is completely covered with ZIF-8.
During this process, nucleation of ZIF-8 may take place once the deprotonated ligand binds to Zn2+ in the solution. Then the heterogeneous nucleation and crystallization of ZIF-8 on the ZnO surface are triggered. The crystallization of ZIF-8 immediately resulted in the formation of nanocrystals on the ZnO surface due to the tendency of ZIFs to preferentially nucleate on ZnO crystals [59] and supersaturated interface near the ZnO surface. The nanocrystals acting as seed crystals are further crystallized, and then microcrystals are gradually formed on the surface of ZnO. According to the SEM and XRD results, ZIF-8 crystals grow gradually after 3 h treatment. The dense and continuous ZIF-8 layer is formed by the fusing of nanoparticles between the big particles, which seals the grain boundaries and imperfections and ensures effective ZIF-8 surface coverage. In addition, ZnO crystals may be etched by mim ligand in this process, resulting in more mobile Zn2+ for ZIF-8 crystal growth.

3.5. Adhesion Test of the ZIF-8 Film on Metal Substrate

For prospective uses, ZIF film must have strong adhesion between the film and its substrate. Therefore, the adhesion strength of ZIF-8 film to the substrate was evaluated by a sonication method [27]. Additionally, during the ultrasonic treatment, we employed an SB-5200 ultrasonic cleaner from Ningbo Xinzhi Bio-Technology Co., Ltd., Ningbo, China. The ultrasonic procedure involved placing the substrate with the film into a beaker containing ethanol and then placing the beaker in the ultrasonic cleaner for treatment. Figure 9 shows the morphology of the ZIF-8 film before and after 30 min of sonication treatment in ethanol. As compared with that of a sample without sonication treatment (Figure 9a–c), no obvious shedding and damage is observed on the ZIF-8 film surface (Figure 9d–f), indicating that the prepared ZIF-8 film remained intact and firmly attached to the zinc substrate. The strong adhesion of the ZIF-8 film to the substrate can be attributed to the extra binding strength stemming from the in-situ grown ZnO layer. The ZnO layer served as an anchoring site between the ZIF-8 film and substrate for reinforcing the film’s stability.

4. Conclusions

In summary, a strong bonding ZIF-8 film is successfully constructed on a zinc substrate by a direct in-situ solvothermal process. The strong bonding ZIF-8 film can be attributed to the spontaneous in-situ grown ZnO interlayer between the ZIF-8 and substrate. The growth process demonstrated that the ZnO interlayer is preferentially formed on the zinc substrate and subsequently covered by ZIF-8 crystals. The zinc ions and the solvent’s breakdown products combine to form the ZnO interlayer. The ZnO interlayer not only acts as an active seed for the nucleation and continuous growth of ZIF-8 film but also acts as an anchoring site between ZIF-8 film and substrate for reinforcing the film adhesion to the substrate. The zinc reagent and solvent’s breakdown products encourage the formation of the ZnO interlayer. We firmly believe that the strategy opens up a simple direct growth route for achieving a strong bonding ZIF-8 film on a metal substrate, and a basic understanding of the formation mechanisms of ZIF film is beneficial for the efficient fabrication of advanced MOF film on a metal substrate. Future research could build upon this method to prepare more efficient and strongly bonded thin films on metal substrates. Additionally, this approach can be experimentally applied to other metal substrates to further investigate the complete thin film formation mechanism. Such studies would provide a more comprehensive theoretical foundation for the preparation of thin films on metal substrates.

Supplementary Materials

The following are available online at https://www.mdpi.com/article/10.3390/met14121403/s1, Figure S1: Illustration of the crystal morphology evolution with time, Figure S2: (a) SEM images of Zn foil after 3 h and (b) elemental mapping by energy-dispersive X-ray spectroscopy (EDS), Figure S3 XRD patterns of Zn foil after 1 h, and Figure S4. (a) SEM image of zinc foil treated with the methanol-based protocol and (b) SEM image of zinc foil treated with DMF-based synthesis without mim.

Author Contributions

Conceptualization, H.W. methodology, B.L. and Y.Z. validation, P.W., Z.Z. and X.W. data curation, H.W., Y.Z. and X.W. visualization, Z.Z., X.R. and J.L.; formal analysis, H.W. resources, H.W. writing—original draft preparation, H.W.; writing—review and editing, J.L. supervision; Y.Z. funding acquisition, B.L., Y.Z., P.W. and X.R. All authors have read and agreed to the published version of the manuscript.

Funding

The authors gratefully acknowledge the Central Guiding Science and Technology Development of Local Fund (Grant No. YDZJSK20231A046), National Natural Science Foundation of China (Grant No. 52071227), Shanxi Province Patent Transformation Project (Grant Nos. 202402004, 202402019), and Fundamental Research Program of Shanxi Province (Grant Nos. 202203021222188 and 202303021211166).

Data Availability Statement

The original contributions presented in the study are included in the article/Supplementary Material, further inquiries can be directed to the corresponding authors.

Conflicts of Interest

The authors declare no conflict of interest.

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Figure 1. Schematic diagram of the in situ synthesis process of ZIF-8 film on zinc substrate. (ZIF-8: gray means C, orange means N, blue means Zn, and white means H).
Figure 1. Schematic diagram of the in situ synthesis process of ZIF-8 film on zinc substrate. (ZIF-8: gray means C, orange means N, blue means Zn, and white means H).
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Figure 2. SEM of the zinc foil after solvothermal treatment for 24 h: (a,b) Top view and (c) cross-section, (d) XRD patterns of the treated zinc foil.
Figure 2. SEM of the zinc foil after solvothermal treatment for 24 h: (a,b) Top view and (c) cross-section, (d) XRD patterns of the treated zinc foil.
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Figure 3. XPS (Al Kα) spectra of the zinc foil after solvothermal treatment for 24 h: (a) survey, (b) C 1s, (c) N 1s, and (d) Zn 2p.
Figure 3. XPS (Al Kα) spectra of the zinc foil after solvothermal treatment for 24 h: (a) survey, (b) C 1s, (c) N 1s, and (d) Zn 2p.
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Figure 4. FTIR spectra of the zinc foil after solvothermal treatment for 24 h.
Figure 4. FTIR spectra of the zinc foil after solvothermal treatment for 24 h.
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Figure 5. SEM images of zinc foil after the different treatment times: (a,b) 1 h, (c,d) 3 h, (e,f) 6 h, (g,h) 12 h, and (i,j) 24 h.
Figure 5. SEM images of zinc foil after the different treatment times: (a,b) 1 h, (c,d) 3 h, (e,f) 6 h, (g,h) 12 h, and (i,j) 24 h.
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Figure 6. XRD patterns of Zn foil after the different treatment times.
Figure 6. XRD patterns of Zn foil after the different treatment times.
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Figure 7. (a) SEM image and (b) XRD patterns of zinc foil treated with the methanol-based protocol; (c) SEM image and (d) XRD patterns of zinc foil treated with DMF-based synthesis without mim.
Figure 7. (a) SEM image and (b) XRD patterns of zinc foil treated with the methanol-based protocol; (c) SEM image and (d) XRD patterns of zinc foil treated with DMF-based synthesis without mim.
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Figure 8. Schematic diagram of the formation mechanism of ZIF-8 film.
Figure 8. Schematic diagram of the formation mechanism of ZIF-8 film.
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Figure 9. Micrographs of ZIF-8 coatings before and after ultrasonic testing: (a–c) before testing and (d–f) after testing.
Figure 9. Micrographs of ZIF-8 coatings before and after ultrasonic testing: (a–c) before testing and (d–f) after testing.
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MDPI and ACS Style

Wang, H.; Liu, J.; Liu, B.; Zhang, Z.; Ren, X.; Wang, X.; Wu, P.; Zhang, Y. Direct In Situ Fabrication of Strong Bonding ZIF-8 Film on Zinc Substrate and Its Formation Mechanism. Metals 2024, 14, 1403. https://doi.org/10.3390/met14121403

AMA Style

Wang H, Liu J, Liu B, Zhang Z, Ren X, Wang X, Wu P, Zhang Y. Direct In Situ Fabrication of Strong Bonding ZIF-8 Film on Zinc Substrate and Its Formation Mechanism. Metals. 2024; 14(12):1403. https://doi.org/10.3390/met14121403

Chicago/Turabian Style

Wang, Haidong, Jie Liu, Baosheng Liu, Zhechao Zhang, Xiaoxia Ren, Xitao Wang, Pengpeng Wu, and Yuezhong Zhang. 2024. "Direct In Situ Fabrication of Strong Bonding ZIF-8 Film on Zinc Substrate and Its Formation Mechanism" Metals 14, no. 12: 1403. https://doi.org/10.3390/met14121403

APA Style

Wang, H., Liu, J., Liu, B., Zhang, Z., Ren, X., Wang, X., Wu, P., & Zhang, Y. (2024). Direct In Situ Fabrication of Strong Bonding ZIF-8 Film on Zinc Substrate and Its Formation Mechanism. Metals, 14(12), 1403. https://doi.org/10.3390/met14121403

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