Superhydrophobic Metal Research Articles

Durable Organic Coating-Free Superhydrophobic Metal Surface by Paracrystalline State Formation.

The chemical instability of traditional organically-decorated superhydrophobic metal surfaces is a significant issue, severely limiting practical applications. This is due to the susceptibility of low surface energy coatings to ion permeation, decomposition, and exfoliation, especially in harsh environments. Here, organic coating-free, durable superhydrophobic surfaces on Al alloys by developing the paracrystalline state of a bionic anthill tribe structure is successfully achieved, using femtosecond laser element-doping microstructuring followed by repetitive annealing processes. Remarkably, the inherent superhydrophobic properties of the sample are maintained for ≈2000 h in a corrosive 3.5 wt.% NaCl aqueous solution, significantly surpassing the performance of traditional organic coatings. Moreover, this inherent superhydrophobicity remains nearly unchanged, even after rigorous electrochemical reaction measurements. Additional tests involving UV irradiation (>100 h), freezing cycles (>100 cycles), and acid/alkali resistance (>65 h) further demonstrate that the environmental adaptability of the surface far exceeds that of silane-coated surfaces. Ab initio calculations reveal that the formation of the paracrystalline state reduces surface energy and enhances chemical stability, thereby extending the durability of the superhydrophobic metal. These findings offer a powerful strategy for utilizing atomic-level structural rearrangements to design inherent superhydrophobic surfaces without the need for organic coatings.

Two-dimensional superhydrophobic metal–organic monoacid framework composite meshes with exceptional chemical stability for oil/water separation

Metal-organic frameworks (MOFs) possess versatile architectures, large surface area, and customizable chemical functionalities, which provide them great opportunities in a variety of applications. However, the applications of MOFs are limited due to their weak chemical stability under humid conditions. In this research, a new class of intrinsically superhydrophobic two-dimensional (2D) Metal (zinc)-organic monoacid frameworks-oleic acid (ZOmAF-OA) was fabricated to improve the chemical stability in the aqueous environment. In the meantime, an ultra-facile seeding-free approach to fabricating ZOmAF-OA composite stainless steel (SS) mesh was reported. A thick, continuous layer of well-intergrown ZOmAF-OA nanosheets was successfully synthesized on various stainless steel meshes at ambient conditions. The ZOmAF-OA-SS composite mesh demonstrated extraordinary chemical stability even in harsh conditions. The ZOmAF-OA coatings exhibited excellent stability with their coverage and morphology remaining intact even after 30 days in concentrated NaCl solution. More importantly, the ZOmAF-OA-SS composite mesh retained its superhydrophobicity after 30 days in an acidic solution with no apparent damage to the coating. The ZOmAF-OA-SS composite mesh demonstrated excellent oil/water separation performance for a variety of oil/water mixtures with separation efficiencies up to 98.3 ± 1.4 %.

Fabrication of robust superhydrophobic surface on TC4 alloy by wire electrical discharge machining

Superhydrophobic metal surfaces have significant applications in various areas such as surface self-cleaning, resistance reduction, anti-corrosion, etc. However, inexpensive preparation methods for superhydrophobic surfaces with a good mechanical stability are still to be developed. In this study, microarray structures on TC4 alloy were readily fabricated using a wire electrical discharge machining technology. Following the treatment with a fluorinating reagent, the microarray surface exhibited excellent superhydrophobic properties, where the largest contact angle and the smallest sliding angle reached 159° and 3°, respectively. Influences of the dimensions of microarray structure on the TC4 alloy surface wettability were also investigated in this study. Experiments show that this superhydrophobic surface possesses favorable self-cleaning, good mechanical stability, and promising anti-corrosion properties. In addition, by controlling the dimensions of the microstructure a superhydrophobic surface with a gradient wettability was also fabricated, which exhibits the property of doing nondestructive transportation of liquids.

Framework reinforced orderly-woven superhydrophobic metal–carbon composites for efficient emulsion separation in harsh environments

The primary barrier to the widespread use of super-wetting materials is the surface's limited resistance to physical damage, which leads to poor mechanical qualities. In this study, framework-reinforced orderly-woven superhydrophobic metal spiral coil-carbon fibers composites (SMSC-CFsC) with a durable uniform micro-structure were prepared by nested carbon fibers into metal spiral coils cleverly and woven them into a three-dimensional porous material innovatively. The separation purity of the prepared metal–carbon composites on several commonly used industrial lubricating oil emulsions was better than 99.90 % and the flux was greater than 1000 L/m2h. More significantly, computational fluid dynamics was used to establish a simulation model for emulsion separation that revealed the real-time dynamic motion trajectory and volume changes of water droplets. Additionally, even after high-temperature, compression, wear, and corrosion experiments, it still showed dependable separation purity and stable flux. As a result, it has been demonstrated that the proposed metal–carbon composite has a long oil–water separation service life in harsh environments and has great potential for developing efficient and durable emulsion separation materials.

3D Xanthium-like of Ni-Co-Zn ternary alloys as superhydrophobic coatings toward porous Ti surface for its anti-icing performances

Super-hydrophobic surface has attracted great interests as functional coatings in spacecraft wings and wind-turbine fans. With the ever-increasing demands of durability and low cost, the scopes for industrial application of hydrophobic coatings have been restricted. Herein we proposed an innovative and simple approach for electroplating Ni0.12Co0.88-xZnx (x = 0–0.36) coatings toward porous Ti substrate. Featuring as 3D Xanthium-like spherical textures, the Ni-Co-Zn ternary alloy coatings were achieved by optimizing the Zn2+ concentration and complexing agent (Na3Cit) in bath. Results validated that its crystal size was refined into ∼300 nm, leading into pinning growth through hole-hole linked porous channel of Ti substrate to increase interfacial strength. Based on the wettability tests, it depicted the water-droplet contact angle (WCA) value of 126.3° attached with sliding angle (SA) of 17.5° for coating samples after being exposed in air for 14 days. Further studies of different ageing treatments on micro structural evolution and super-hydrophobic characteristics were well explored. Through artificial ageing at 200 °C, its attained super-hydrophobic surfaces shorted than 7 days, showing the maximal WCA value up to 153.2° and SA ≤ 7.8° for Ni0.12Co0.88-xZnx (x = 0.24) samples, which was mainly contributed to the self-assembly of multi-tentacles ZnO dendrites. Meanwhile the anti-icing behaviors were compared and featured as peach blossom at −10 °C for all the samples. The icing-delay time of water droplets on coating samples was >1425 s, which was 20 times longer than that of porous Ti substrate. Similarly, it was higher than 90 % for its self-cleaning efficiency based on salt pollutants. Besides the mechanical durability of tested samples against the abrasion-resistant tests and water impact-resistance tests were studied. Results implied that good durability was achieved for Ni-Co-Zn superhydrophobic coatings, but sanded surfaces within a serious decrease of WCA was obtained after a continuous testing for 30 min by abrasion-resistant tests because of the partial destruction of Xanthium-like spherical textures. With the respect to reconstructing of multi-tentacles ZnO dendrites onto the Ni-Co-Zn coatings in air, it was the bio-inspired strategies for self-healing super hydrophobic metal coatings used in warship surfaces, etc.

Superhydrophobic aluminum surfaces with nano-micro hierarchical composite structures: A novel and sustainable approach to corrosion protection

The unique properties of aluminum (Al) and its alloys make Al one of the most versatile, economical, and widely-used materials in various industries. However, the corrosion and leaching of Al can cause significant issues for the lifetimes of mechanical structures and machine components as well as environment and health problems. In the present study, a simple, eco-friendly, and rapid fabrication of superhydrophobic Al surfaces was introduced. The superhydrophobic Al surfaces with hierarchical composite structures combining microstructures prepared by laser texturing, the new formation of pseudo-boehmite nanostructures prepared by boiling water treatment, and low surface energy prepared by silicone oil heat treatment showed excellent corrosion resistance. The mechanism for wettability change and anti-corrosion were analyzed. The influence of laser parameters and surface modification procedures on the wettability and corrosion resistance of Al surfaces was also analyzed systematically through a series of surface characterization techniques, potentiodynamic polarization tests, and electrochemical impedance spectroscopy tests. The corrosion protection efficiency of the fabricated superhydrophobic Al surface has reached up to 99.40 % as compared with an untreated flat surface. Furthermore, the fabricated superhydrophobic surfaces show good stability even after prolonged exposure to air, fresh water, seawater, and high temperature environments. The performance of the non-wetting surfaces is demonstrated through self-cleaning, water jetting, and water droplet bouncing phenomena. This research provides a novel and sustainable approach for superhydrophobic metal surfaces and improved corrosion resistance for potential practical applications.

Biocompatible superhydrophobic surface on Zr-based bulk metallic glass: Fabrication, characterization, and biocompatibility investigations

Superhydrophobic metal materials are promising candidates for preparing the precision blood-contacting medical devices. Finding a metal material with excellent biocompatibility and superplastic forming ability to fabricate superhydrophobic surface is of great practical significance. Zr-based bulk metallic glass with high glass-forming ability was selected as the experimental sample. Micro-nano hierarchical structure was etched by electrochemical method in the ultrasonic environment, and the superhydrophobic surface with good biocompatibility was obtained after further modification. Electrochemical polarization tests show that the superhydrophobic surface can maintain long-term corrosion resistance in simulated body fluids. Blood and cell tests indicate that the superhydrophobic sample has an extremely rate of hemolysis and exhibits the ability to effectively inhibit the adhesion of platelets and smooth muscle cells. In addition, the superhydrophobic sample surface also exhibits good mechanical durability and chemical stability. This study offers a new perspective on the application of Zr-based bulk metallic glass in blood-contacting medical devices.

Determination of the resistance of water-repellent properties to ultraviolet radiation on self-hydrophobized surface textures of AISI 304 steel

In this work, the object of the study were femtosecond laser textured steel samples. Using a femtosecond laser to texture the surface both in the direct-beam mode, which provides microtextures, and in the reflection mode, which leads to the formation of LIPSS-type nanostructures on the surface. Such hybrid complexes are optimal in terms of water repellency as they embody the principle of hierarchical textures. This approach is one of the promising ways to solve the problem of scaling the process of obtaining superhydrophobic metal surfaces. The aim of the work is to establish the stability of water-repellent properties of micro- nanotextures obtained on the surface of AISI 304 steel after spontaneous hydrophobization under the action of UV radiation. The study of the obtained textured surface by scanning electron microscopy to confirm the presence of nanotexture and by energy-dispersive X-ray spectroscopy to establish the elemental composition of the obtained microtexture were made in the work. The paper shows that the water repellency of AISI 304 steel surfaces textured at micro and nano levels by femtosecond laser after long exposure to the atmosphere increases to a superhydrophobic state with the value of contact angles up to 155°. It has been shown that such surfaces are sensitive to UV radiation. Depending on the type of structure, the loss of hydrophobicity under experimental conditions occurs in 15-45 minutes of exposure, and complete hydrophilization of the surface occurs after 100 minutes of irradiation. As a result, the obtained self-hydrophobic surfaces are not suitable for operation under the influence of sunlight. However, ultraviolet radiation can be used to pre-clean such surfaces from adsorbed organic contaminants.

Superhydrophobic Mn(II)-coordinated technical cashew nut shell liquid-based bactericidal and corrosion-resistant advanced polyurethane coatings

A facile route has been reported to formulate mesoporous and covalently tethered superhydrophobic (160°) metal (Mn(II)) coordinated bio-polyurethane (PU) films/coatings. Technical cashew nut shell liquid-Formaldehyde (TCNSL-F) pre-polymer was used to prepare three different metal-coordinated polyurethane {Mn(II)TCNSL-F-PU20/25/30} films/coatings by using toluene diisocyanate (TDI) (20 %, 25 %, and 30 % w.r.t. polyol) as chain extender. Fourier transform infrared (FTIR) spectroscopy analyzes the chemical structures and changes in functional groups (-OH, >CO, -NCO), while X-ray diffraction (XRD) patterns reveal the amorphous nature of these films. The coordination with metal ions improves the chemical resistance, swelling ability (pH 4, 7.4, and 10), physicomechanical properties (scratch resistance (2.2 lb), impact resistance (150 lb/in.), bending (1/8 in.), adhesion, and gloss (98 GU) of the final coatings. Thermogravimetric analysis and its derivative (TGA and DTA) demonstrate the relatively high thermal stability (up to 200 ℃) and flame retardancy with a limited oxygen index value of 27.58. Optical microscopy, field emission scanning electron (FE-SEM), and transmission electron microscopy (TEM) images confirm the development of a well-patterned spherical nanostructure within the resin. The N2 adsorption/desorption studies reveal that Mn(II)TCNSL-F-PU25 has a Brunauer-Emmett-Teller surface area of 340.783 m2/g with a 3–3.2 nm pore diameter. Electrochemical impedance spectroscopy (EIS) demonstrates (3.5 wt% NaCl solution) a superior anticorrosion performance, protective capabilities, and compactness to a metal-coordinated substrate. The high impedance, solvent resistance, and low capacitance of coatings support the potential protective capabilities of the coating for the given immersion times. In addition, antibacterial activity ascertains the inhibition ability of the coordinated films against various bacterial strains i.e., E. coli, S. aureus, K. pneumonia, and B. subtilis. The formulated Mn(II)-coordinated PU has potential to become multi-functional surface-protective material.

Robust Superhydrophobic PDMS@SiO2@UiO66-OSiR Sponge for Efficient Water-in-Oil Emulsion Separation.

A major challenge in oil/water separation is the processing of surfactant-stabilized emulsions from the water medium. One of the feasible schemes of emulsion separation is the porous melamine sponge coupled with functional particles. Here, we proposed a novel superhydrophobic metal-organic framework (MOF)-based sponge for water-in-oil emulsion separation. The porous melamine sponge was combined with poly(dimethylsiloxane) (PDMS)-coated hydrophobic SiO2 and UiO66-OSiR particles were prepared for demulsification via the one-step dipping method for the first time. The PDMS@SiO2@UiO66-OSiR sponge revealed excellent superhydrophobicity at a water contact angle of 160.7° and superlipophilicity at an oil contact angle of 0°. Compared with the pristine melamine sponge, the size-controllable PDMS@SiO2@UiO66-OSiR sponge could separate stabilized water-in-oil emulsions with ultrahigh separation efficiency (>98.64%) and high flux (e.g., 970 L·m-2·h-1). Meanwhile, the PDMS@SiO2@UiO66-OSiR sponge exhibited superior durability and mechanical reusability. Under harsh conditions such as strong acid and alkali, organic solvent corrosion, etc., all water contact angles of the PDMS@SiO2@UiO66-OSiR sponge were over 152°. Furthermore, the stress decreased by 5% when the sponge was subjected to 10 loading/unloading compression cycles at a constant strain of 60%. These results demonstrate that the PDMS@SiO2@UiO66-OSiR sponge can efficiently separate water-in-oil emulsions through its adjustable porous structure coupled with demulsification and hydrophobic particles. This study provides a step forward in developing a feasible strategy for the MOF-based sponge for emulsion separation.

Robust, Superhydrophobic Aluminum Fins with Excellent Mechanical Durability and Self-Cleaning Ability

The self-cleaning ability of superhydrophobic metal surfaces has attracted extensive attention. The preparation of superhydrophobic material using the coating method is a common processing method. In this experiment, aluminum fins were processed by laser etching and perfluorinated two-step coating. The aluminum surface was modified using a femtosecond laser and 1H,1H,2H,2H- perfluorooctane triethoxysilane (PFOTES). A superhydrophobic aluminum surface with excellent mechanical stability and self-cleaning properties was obtained with the superhydrophobic contact angle (WCA) of 152.8° and the rolling angle (SA) of 0.6°. The results show that the superhydrophobic surface has an excellent cleaning effect compared with an ordinary surface in unit time. Then, a wear resistance test of the superhydrophobic surface was carried out by using the physical wear method. The results show that physical wear had a low influence on the hydrophobic property of the specimen surface. Finally, the Vickers hardness analysis found that the superhydrophobic surface hardness was significantly better than the ordinary surface hardness compared with the superhydrophobic surface hardness. Based on the excellent self-cleaning properties, wear resistance, and robustness of superhydrophobic materials, the laser-etched and perfluorinated superhydrophobic aluminum fins designed and manufactured in this study have broad application prospects in improving the heat transfer efficiency of finned heat exchangers.

A non-fluorinated superhydrophobic composite coating with excellent anticorrosion and wear-resistant performance.

The facile and low-cost fabrication of fluorine-free superhydrophobic metal surfaces for anticorrosion remains a challenging issue. Here, we report a superhydrophobic coating based on polyacrylate/SiO2 nanoparticles/graphene oxide sheets through a simple yet environmentally friendly method. The as-prepared composite coating sprayed on metal surfaces exhibits excellent superhydrophobic and corrosion-resistant properties. Furthermore, the coating surface possesses good anti-wear performance and remains superhydrophobic after harsh abrasion tests. Prospectively, the developed non-fluorinated superhydrophobic coating opens up opportunities for the application in industrial anticorrosion field.

Effects of hot water on the wettability of superhydrophobic metal surfaces

Super-hydrophobic surfaces were used in self-cleaning, anti-corrosion, anti-fog, drag reduction, oil–water separation, etc., but many super-hydrophobic surfaces were not resistant to hot water. Within a certain range, the change of hot water temperature had little effect on wettability, but beyond the range, the effect of water temperature on wettability was very significant. Here, the superhydrophobic metal surfaces of pure titanium, pure nickel, and 304 stainless steel with hierarchical micro-nano structures were prepared by nanosecond laser combined with heat treatment. By immersing in hot water at 25, 50, 75, and 100 °C, it was found that hot water could not significantly change the surface structure. At the same time, the content of total polar bonds on the metal surface increased, resulting in surface free energy rising. Thus, the superhydrophobicity of the surface was transformed into hydrophilicity with a water contact angle between 10 and 20°. This preparation method was non-toxic and pollution-free and was easy to repeat. The experimental results provided a reference for suppressing the change of superhydrophobic surface composition after hot water immersion.

Facile Construction and Fabrication of a Superhydrophobic and Super Oleophilic Stainless Steel Mesh for Separation of Water and Oil.

The fluoride-free fabrication of superhydrophobic materials for the separation of oil/water mixtures has received widespread attention because of frequent offshore oil exploration and chemical leakage. In recent years, oil/water separation materials, based on metal meshes, have drawn much attention, with significant advantages in terms of their high mechanical strength, easy availability, and long durability. However, it is still challenging to prepare superhydrophobic metal meshes with high-separation capacity, low costs, and high recyclability for dealing with oil–water separation. In this work, a superhydrophobic and super oleophilic stainless steel mesh (SSM) was successfully prepared by anchoring Fe2O3 nanoclusters (Fe2O3-NCs) on SSM via the in-situ flame synthesis method and followed by further modification with octadecyltrimethoxysilane (OTS). The as-prepared SSM with Fe2O3-NCs and OTS (OTS@Fe2O3-NCs@SSM) was confirmed by a field emission scanning electron microscope (FESEM), transmission electron microscope (TEM), energy dispersive spectrometer (EDS), X-ray photoelectron spectrometer (XPS), and X-ray diffractometer (XRD). The oil–water separation capacity of the sample was also measured. The results show that the interlaced and dense Fe2O3-NCs, composed of Fe2O3 nanoparticles, were uniformly coated on the surface of the SSM after the immerging-burning process. Additionally, a compact self-assembled OTS layer with low surface energy is coated on the surface of Fe2O3-NCs@SSM, leading to the formation of OTS@Fe2O3-NCs@SSM. The prepared OTS@Fe2O3-NCs@SSM shows excellent superhydrophobicity, with a water static contact angle of 151.3°. The separation efficiencies of OTS@Fe2O3-NCs@SSM for the mixtures of oil/water are all above 98.5%, except for corn oil/water (97.5%) because of its high viscosity. Moreover, the modified SSM exhibits excellent stability and recyclability. This work provides a facile approach for the preparation of superhydrophobic and super oleophilic metal meshes, which will lead to advancements in their large-scale applications on separating oil/water mixtures.

Electrochemical polishing assisted selective laser melting of biomimetic superhydrophobic metallic parts

Metallic superhydrophobic surfaces can be widely used in pipeline transportation, oil–water separation, anti-icing, biomedicine and industrial production owing to their excellent properties. The biologically non-smooth superhydrophobic structure provides a biomimetic prototype for superhydrophobic metal surface processing. However, processing micro-nano biomimetic structures on the internal surface of complex pipelines is difficult because of the limitations of traditional molding processes. Herein, a superhydrophobic butterfly wing is imitated via the selective laser melting technology to print a pit prototype on the surface during the complex parts forming, and then the bio-inspired superhydrophobic internal surface of the 316L stainless steel is successfully prepared by the processes of electrochemical polishing, chemical etching, fluorosilane modification, and low temperature drying, sequentially. The morphology, wettability, corrosion resistance, and elemental composition of the obtained surface are characterized. The results show that a uniform pit-shaped micro-nano composite structure is formed on the surface, the contact angle is up to 155°, the rolling angle is less than 10°, and the corrosion resistance is significantly improved. Finally, a complex superhydrophobic inner surface square tube with application value is successfully prepared, and its excellent superhydrophobicity and self-cleaning properties are verified. This fabrication method provides an idea for the complication of metal superhydrophobic structures, and will promote the application of additive manufacturing in the engineering field.

Effects of Hot Water on the Wettability of Superhydrophobic Metal Surfaces

Effects of Hot Water on the Wettability of Superhydrophobic Metal Surfaces

Superhydrophobic nanocontainers for passive and active corrosion protection

A superhydrophobic metal organic framework (MOF) nanocontainer strategy, other than conventional hydrophilic MOF nanocontainer process, was proposed for anticorrosion. Compared with the hydrophilic nanocontainers, the superhydrophobic MOFs have better compatibility with polyvinyl butyral (PVB) resin and provide reduced water absorption of the composite coating. In addition, the superhydrophobic property ensures slower release rate of encapsulated inhibitors from the nanocontainers. Thereby, the corrosion resistance of the PVB coating on copper substrates embedded with superhydrophobic MOF nanocontainers pre-loaded with 2-Amino-5-mercapto-1,3,4-thiadiazole (AMT) has been significantly improved. The molecular dynamics simulation was applied to understand the experimental results.

Ultralow Adhesion and Phase Change Behaviors of Sulfur Droplets on the Superhydrophobic Surface and Its Application in the Granulation Process.

Traditional sulfur granulation process is often accompanied by high dust and mechanical friction, which are dangerous and harmful to the environment. In this work, the application of the superhydrophobic surface to sulfur granulation is expected to solve the above problem. Two superhydrophobic metal sheets were prepared, and the rolling angles of the two samples are both less than 10°. The contact angles of liquid sulfur are 152.7 ± 0.5 and 151.3 ± 0.1°, respectively. The adhesion rates of both samples are less than 0.5 wt %. The solidifying process of a sulfur drop on the superhydrophobic surface was recorded and simulated, conforming that the substrate temperature has a great influence on the solidifying process. Based on the above findings, static granulation and rolling to granulation were proposed. The product obtained by the two methods has uniform particle size distribution and excellent compressive strength, showing a good industrial application prospect. This study provides a referral strategy for an economical and environmentally friendly sulfur granulation process.

Facile fabrication and repair of superhydrophobic metal surfaces via electric spark deposition with oil

Recent research has focused on the durability of superhydrophobic surfaces, and some methods have reported improvements in the resistance of surfaces to abrasion from several sandpaper treatment cycles with the goal of maintaining a contact angle (CA) > 150°. However, the surface water repellency is lost because of the numerous abrasive cycles causing significant mechanical damage. Repairing the superhydrophobicity of the material is necessary when the surface is damaged. Current repair methods have different limitations, such as special abrasion conditions or limits on the substrate size and working conditions. Here, we demonstrate that using electric spark deposition with oil can create a superhydrophobic surface in a single step. This represents a facile method that can be carried out by hand with fewer limitations on its working conditions and the substrate location and shape. The morphology and chemical composition of the coating was investigated. The addition of octadecanoic acid to the oil provided a stable CA > 150° for the coated surface. The coated surface lost superhydrophobicity after being subject to three different damaging processes, and the superhydrophobicity could be recovered after recoating.

Preparation of Superhydrophobic Metal–Organic Framework/Polymer Composites as Stable and Efficient Catalysts

Metal-organic frameworks (MOFs), as a chemical platform, combined with multifunctional polymers are of interest in catalytic applications, which can not only inherit the outstanding properties of the two components but also lead to unique synergistic effects. Nonetheless, most MOFs possess varying degrees of water instability, which limits their real application. Herein, we fabricated highly hydrophobic MOF/polymer composites via a universal post-synthetic polymerization strategy as efficient catalysts. Polyaniline (PANI) was first hybridized with MOFs by vapor deposition polymerization, and then, hydrophobic molecules were grafted to the PANI by a covalent linking process, thereby forming a superhydrophobic MOF/PANI hybrid material (MOF/PANI-shp). The resultant MOF/PANI-shp not only obtains superior moisture/water resistance without significantly disturbing the original features but also exhibits a novel catalytic selectivity in styrene oxidation because of the accessible sites and synergistic effects. Such a synthetic strategy for the MOF/polymer catalyst opens a new avenue for the design of a unique catalyst with outstanding catalytic efficiency, selectivity, and stability.