Superhydrophobic Particles Derived from Nature-Inspired Polyphenol

College of Chemistry, Nankai University, Tianjin 300071, China. ‡ School of Environmental Science and Engineering, Tianjin University, Tianjin 30007...
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Letter pubs.acs.org/journal/ascecg

Superhydrophobic Particles Derived from Nature-Inspired Polyphenol Chemistry for Liquid Marble Formation and Oil Spills Treatment Shouying Huang,† Yan Zhang,† Jiafu Shi,*,‡ and Weiping Huang*,† †

College of Chemistry, Nankai University, Tianjin 300071, China School of Environmental Science and Engineering, Tianjin University, Tianjin 300072, China

‡

S Supporting Information *

ABSTRACT: Nature has given us great inspirations to fabricate high-performance materials with extremely exquisite structures. Presently, particles with a superhydrophobic surface are prepared through nature-inspired polyphenol chemistry. Briefly, adhering of a typical polyphenol (tannic acid, widely existed in tea, red wine, chocolate, etc.) is first conducted on titania particles to form a multifunctional coating, which is further in charge of reducing Ag+ into Ag nanoparticles/ nanoclusters (NPs/NCs) and responsible for grafting 1H,1H,2H,2H-perfluorodecanethiol, thus forming a lotusleaf-mimic surface structure. The chemical/topological structure and superhydrophobic property of the as-engineered surface are characterized by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), energy dispersive spectroscopy (EDS), water contact angle measurements, and so on. On the basis of the hierarchical, superhydrophobic surface, the particles exhibit a fascinating capability to form liquid marble and show some possibility in the application of oil removal from water. After particles are in situ adhered onto melamine sponges, the acquired particle-functionalized sponge exhibits an absorption capacity of 73−175 times of its own weight for a series of oils/organic solvents and shows superior ease of recyclability, suggesting an impressive capability for treating oil spills. KEYWORDS: Nature-inspired polyphenol chemistry, Particles, Superhydrophobic surface, Lotus-leaf-mimic surface structure, Sponges, Liquid marble formation, Oil spills treatment

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INTRODUCTION Particles with special surface wettability, such as superhydrophobicity, promises numerous valuable usages in practical applications, including oil/water separation,1−3 drag reduction,4 self-cleaning,5 and antifouling.6 Engineering a particle surface with superhydrophobicity is therefore highly required and has gained extensive interests. As one of the most representative instances, the lotus leaf that possesses a botanical wax with low surface energy and unique micro/nanohierarchical structure is considered as an ideal prototype of superhydrophobic surfaces. To our knowledge, tremendous efforts have been devoted to mimic the structure of lotus leaf for engineering superhydrophobic surfaces.7−10 Among the existing toolbox, nature-inspired methods have received high remarks and showed impressive potentials in practical applications, mainly as a result of its greenness, mildness, high efficiency, and sustainability. Exemplarily, mussel-inspired catecholamine chemistry has been successfully explored for engineering superhydrophobic surfaces. The general procedure can be categorized into three steps, including the generation of poly(catecholamine) coating on the substrate through oxidative self-polymerization of catecholamine, the creation of micro/ © XXXX American Chemical Society

nanohierarchical structure on the poly(catecholamine) coating, and the grafting of H2N-/HS-terminated hydrophobic molecules through Michael-addition (Schiff-base reaction) or catechol-thiol reaction.2,3,11 It was well recognized that all the three steps were dominated by the multifunctionality of catecholamine. Unfortunately, only a few kinds of catecholamine (dopamine,12 norepinephrine,13 and dopa14,15) were available to realize the engineering of superhydrophobic surfaces, among which dopamine seemed to be the most frequently used. Recently, an alternative to dopamine, called plant polyphenol that was widely existed in tea, red wine, chocolate, etc., was discovered by Messersmith and co-workers.16,17 The polyphenol with a high content of catechol/pyrogallol groups, showed high similarities in structure and property to catecholamine, and therefore, possessed the capability of adhering to a variety of substrates, catalytically reducing noble metal ions into nanoparticles, and reacting with H2N-/HS-terminated moleReceived: January 22, 2016 Revised: February 19, 2016

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DOI: 10.1021/acssuschemeng.6b00149 ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX

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Figure 1. (a) Schematic illustration for engineering the superhydrophobic surface on particles through nature-inspired polyphenol chemistry; SEM images of the (b) titania particles, (c) titania/polyphenol particles, (d) titania/polyphenol/Ag particles, and (e) superhydrophobic titania/ polyphenol/Ag particles (modified with 1H,1H,2H,2H-perfluorodecanethiol); (f) water contact angle of the superhydrophobic titania/polyphenol/ Ag particles.

Figure 2. (a) XPS spectrum (right: atom content of each element) of the superhydrophobic titania/polyphenol/Ag particles; high-resolution XPS (b) Ag 3d and (c) S 2p spectra of the superhydrophobic titania/polyphenol/Ag particles.

cules.17−22 By contrast with poly(catecholamine), polyphenols usually presented several other merits, including more rapid adhesion rate, lower cost, easier availability, more structural diversity (more than eight kinds), and so on.17 Therefore, the method based on nature-inspired polyphenol chemistry may offer a general and inexpensive platform for engineering a superhydrophobic surface on particles, which, to the best of our knowledge, has not yet been reported so far. The concept of utilizing nature-inspired methods to synthesize multifunctional materials for diverse applications well fits the principles of green chemistry that is the major part of sustainable chemistry and engineering.

dure was facile and conducted under a mild environment (nearly neutral pH, room temperature, aqueous/ethanolic solution). The potential applications of such superhydrophobic particles in liquid marble formation and oil spills treatment were demonstrated. The preparation procedure was shown in Figure 1a. Briefly, in a weakly alkaline environment, tannic acid, a typical polyphenol, could rapidly adhere onto the titania particles through metal−organic coordination.23 The acquired titania/polyphenol particles showed a slightly rough surface, indicating the successful adhering of polyphenol (Figure 1b,c). Then, the titania/polyphenol particles were immersed into AgNO3 aqueous solution to reduce Ag+ to Ag nanoparticles (NPs). Thanks to the reducing capability of polyphenol, no additional reducing agent was required for the generation of Ag NPs. As indicated in Figure 1d, Ag NPs were formed and distributed on the polyphenol coating with an average size of ∼20 nm. As was known, polyphenol and Ag NPs could react

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RESULTS AND DISCUSSION In this study, we presented an example of using titania particles as the substrate for engineering the lotus-leaf-mimic surface structure with superhydrophobic property. The entire proceB

DOI: 10.1021/acssuschemeng.6b00149 ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX

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Figure 3. EDS mapping of the superhydrophobic titania/polyphenol/Ag particles: (a) the (1) detected and (2) reference regions, (b) O, (c) F, (d) Ti, (e) Ag, and (f) S elements.

nethiol in the polyphenol/Ag layer should be 9.30%, suggesting the residual 45.81% of C element being totally from tannic acid. Also, the O element observed from the XPS spectrum only came from tannic acid. The experimental atom ratio of C to O (ARC/O, from tannic acid) was 1.66, which also closely matched the theoretical 1.65. Such accurate matching of experimental atom ratio (ARF/S and ARC/O) with the theoretical atom ratio provided strong evidence to support our hypothesis of the proposed formation process of the superhydrophobic surface. Furthermore, the element distribution on the near-surface region was examined by EDS mapping (Figure 3). As indicated, the elements, including O, F, Ti, Ag, and S elements were distributed uniformly on the near-surface region of the particles, further confirming the formation of the polyphenol/Ag coating and the grafting of 1H,1H,2H,2H-perfluorodecanethiol. Interestingly, the content and distribution of Ag element on the near-surface region of the particles (Figures 3e and S1) seemed not to be in accordance with that of Ag NPs on the particle surface as observed in the SEM image (Figure 1e). The increased content and more uniform distribution of Ag element might be originated from two parts: (1) Ag NPs on the particle surface that observed in SEM image (Figure 2e), and (2) Ag nanoclusters (NCs) within the near-surface region evidenced by the EDS mapping (Figure 3e). The water repellent property of the superhydrophobic titania/polyphenol/Ag particles was examined in the subsequent experiment. Specifically, an ethanolic solution dispersed with the superhydrophobic particles was dropped on a glass slice to form a particulate coating. When dropped through micro pipette tip onto this particulate coating, the water droplet was rapidly rebounded back to the tip within 500 ms (Figure 4a and Video S1). This interesting phenomenon strongly evidenced the superhydrophobicity of the as-synthesized particles. The superhydrophobic particles also showed great potentials in various applications. For instance, controllable transport and manipulation of small volumes of liquids have attracted increasing interest due to the ongoing needs for miniaturized systems in many biological applications.28,29 In our work, a water droplet on the particulate powder rapidly absorbed by the powder. Rolling of the water droplet on the particle bed facilitated the encapsulation of the droplet by the superhydrophobic particles, known as “liquid marble”.30 It was

with HS-terminated molecules through catechol(pyrogallol)thiol reaction and metal−thiol coordination, respectively.24−27 The molecule of 1H,1H,2H,2H-perfluorodecanethiol could be then easily grafted on the surface of titania/polyphenol/Ag particles, thus acquiring superhydrophobic titania/polyphenol/ Ag particles (Figure 1e). The diameter of the obtained particles primarily located at ∼400 nm, which was in accordance with the SEM image (Figure S2). These particles were then compressed into a plate to measure the hydrophobicity. As exhibited in Figure 1f, the compressed plate showed a water contact angle of 163.9°, indicating a satisfied superhydrophobic property. The desirable superhydrophobicity should be ascribed to the following aspects: (1) the titania/polyphenol particles and Ag NPs served as the first and secondary structure to build a two-tier roughness mimicking the hierarchal structure of lotus leaf; (2) the grafted 1H,1H,2H,2H-perfluorodecanethiol served as the chemical structure to mimic botanical wax of lotus leaf to gain low surface free energy. To understand deeply the surface chemical/elemental composition of the superhydrophobic titania/polyphenol/Ag particles, X-ray photoelectron spectroscopy (XPS) and energy dispersive spectroscopy (EDS) analysis were conducted. In Figure 2a, no Ti element could be observed in the full-scale XPS spectrum, indicating the complete capping of a superhydrophobic polyphenol/Ag layer on the particle surface. The C element that occupied most of the surface should be originated from the polyphenol coating and 1H,1H,2H,2Hperfluorodecanethiol. The appearance of signal peaks at ∼600 and ∼370 eV suggested the successful fixation of Ag on the particle surface. After the signal peak located at ∼370 eV was amplified, two peaks at 376.4 and 370.5 eV could be found, which typically suggested the existence of Ag NPs (Figure 2b). The F and S elements were also observed in full-scale and highresolution XPS spectra, presenting the successful grafting of 1H,1H,2H,2H-perfluorodecanethiol on the polyphenol/Ag layer (Figure 2a,c). Because F and S elements were only originated from the molecule of 1H,1H,2H,2H-perfluorodecanethiol, the theoretical atom ratio of F to S (ARF/S) should be 17.0. Results from XPS analysis indicated that experimental ARF/S was 16.2, which well matched the theoretical ARF/S. On the basis of the theoretical atom ratio of C to S (ARC/S = 10) in this molecule, the C content of 1H,1H,2H,2H-perfluorodecaC

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in charge of grafting 1H,1H,2H,2H-perfluorodecanethiol, finally acquiring the particle-functionalized sponges. As shown in Figure 5a, the pristine melamine sponge with high hydrophilicity rapidly sank to the bottom of the water, while the particle-functionalized sponges could float on the water surface, indicating their superhydrophobicity and low density. The superhydrophobicity of the particle-functionalized sponges could also be evidenced by the fact that a spherical water droplet could stand on their surface (Figure S4, the advancing and receding contact angles were, respectively, 162.1° and 147.0°). Such superhydrophobicity should be ascribed to the hierarchically structured surface, where numerous superhydrophobic particles were located (Figure 5b,c). The particle-functionalized sponge was then utilized to absorb a series of oils/organic solvents, including petroleum products (e.g., crude oil, pump oil, used pump oil), alcohols (e.g., methanol, ethanol, isopropyl alcohol), fats (e.g., soybean oil), hydrocarbons (e.g., hexane, heptane, n-hexadecane), aromatic compounds (e.g., toluene), ketones (e.g., acetone), and other organic solvents (e.g., dichloromethane, chloroform, dimethylformamide (DMF), dimethyl sulfoxide (DMSO)). The absorption process and capacities of oils/organic solvents by using of the particle-functionalized sponge are illustrated in Figure 6a,b. Heptane (ρheptane/ρwater = 0.68) and chloroform (ρchloroform/ρwater = 1.50) were selected as examples to demonstrate the absorption process. Specifically, once contacted with a heptane layer on the water surface, the particlefunctionalized sponge could fully absorb the heptane within 2 s (Figure 6a). After the absorption of heptane, the particlefunctionalized sponge could float on the water surface, which was mainly owing to the much lower density of heptane (ρheptane/ρwater = 0.68) and the superhydrophobicity of the sponge, suggesting an ease of recycling for the absorbents. Alternatively, once the particle-functionalized sponge was adopted to absorb chloroform at the bottom of the water (Figrue 6b), a spherical droplet of chloroform with a much higher density to water could be quickly absorbed by the particle-functionalized sponge, where a bubble was simultaneously generated. As a result of the difference in the density of the absorbed liquids, the particle-functionalized sponge showed absorption capacities ranging from 73 to 175 times of its own weight (Figure 6c). The absorption capacities were much higher than that of organosilicon-based nanowire membranes (4−20 times),31 marshmallow-like organosilicon-based gel (6− 15 times),32 and even comparable to that of another type of melamine sponge-based absorbents (98−217 times)33 and some typical carbon-based absorbents, such as graphene/

Figure 4. (a) Water droplet bounced on a glass slice coated with a layer of superhydrophobic titania/polyphenol/Ag particles; (b) water droplet rolling in the internal surface of the polypropylene tube; and (c) optical images of the oil/water separation process and the recollection of the particles.

reported that a liquid marble could act as liquid microcarriers and move arbitrarily without any leakage. The liquid marble was then transferred into a polypropylene tube, which could stand erectly and roll readily (Figure 4b and Video S2). However, in the absence of the superhydrophobic particles, the water droplet spread on the internal tube surface (Figure S3). To find out how strongly the polyphenol/Ag coating was adhered to the titania particles, the superhydrophobic particles were treated in an ultrasonic ethanolic solution for 0.5 h. The dried particles after ultrasonic treatment still showed superhydrophobic property and reserved the capability to form liquid marbles, indicating the good wetting stability. As another example, the superhydrophobic particles were utilized for absorbing oil from water. As shown in Figure 4c, the assynthesized superhydrophobic particles showed some possibility in absorbing oil. After absorption, the particles with oils trapped inside could be collected by a lab spoon. The collected particles could be then facilely recycled by dispersing in an ethanolic solution and reused for the next cycled oil/water separation. To further examine our surface-engineering method, sponges with superhydrophobic particles on the surface were in situ prepared. In brief, 50 mg of titania particles with two pieces of melamine sponges were dispersed in an aqueous solution of tannic acid. The acquired sponges were immersed into AgNO3 aqueous solution to reduce Ag+ ions into Ag NPs, which were

Figure 5. (a) Photograph of the pristine melamine sponge and the particle-functionalized sponge after contacting with the water surface (inset: a water droplet on the surface of particle-functionalized sponge); (b, c) SEM images of the particle-functionalized sponge. D

DOI: 10.1021/acssuschemeng.6b00149 ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX

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Figure 6. Snapshots of the removal process of (a) heptane (stained with oil red O) from the water surface and (b) snapshots of the removal process of chloroform (stained with oil red O) from the bottom of the water using the particle-functionalized sponge; (c) summary of the absorption capacities of the oils/organic solvents for the particle-functionalized sponge; and (d) recyclability of the particle-functionalized sponge, recycling the particle-functionalized sponge absorbed with soybean oil through the squeezing method.

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carbon nanotube foams (80−140 times)34 and twisted carbon fibers (TCF) aerogels (50−192 times). 35 Besides the absorption capacity, the reusability of the absorbent and the recyclability of the absorbed liquid were also important criteria for the cleanup of oil spills/organic pollutants in practical applications. Squeezing was a facile and effective method for the resuing and recycling purpose, which has been extensively applied. Presently, soybean oil was recovered through the squeezing method (Figure 6d). After 50 absorption/squeezing cycles, the net absorption capacity of the superhydrophobic sponge was only lowered to 82.0% of its initial absorption capacity (about 98.3 of the net absorption capacity), showing a great potential application of the particle-functionalized sponges in oil spills treatment.

ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acssuschemeng.6b00149. Experimental section; TEM image and EDS curve of the superhydrophobic particles; size distribution of the superhydrophobic particles; optical image of liquid marble and water in the internal surface of polypropylene tube; advancing and receding water contact angles of the particle-functionalized sponge (PDF) Video showing rapid rebound of water droplet (MP4) Video showing liquid marble transferred into a polypropylene tube (MP4)

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CONCLUSIONS In conclusion, a superhydrophobic surface was engineered on titania particles through nature-inspired polyphenol chemistry. In detail, metal−organic coordination between catechol/ pyrogallol groups in polyphenol and Ti atoms in titania particles was in charge of generating polyphenol coating; while high reducing potential of free catechol/pyrogallol groups was responsible for the formation of Ag NPs/NCs. Both the polyphenol coating and Ag NPs/NCs contributed to the grafting of 1H,1H,2H,2H-perfluorodecanethiol. The obtained particles exhibited high hydrophobic property with water contact angle of >160°. Liquid marbles could be obtained and capable of standing and rolling in a polypropylene tube, which showed some potential as miniature reactors. The resultant superhydrophobic titania/polyphenol/Ag particles also exhibited some possibility for oil removal from water. Besides, these superhydrophobic particles could be in situ adhered to melamine sponges, which resulted in the particlefunctionalized sponge with absorption capacity of 73−175 times for a series of oils/organic solvents, thus showing a great promise in environment protection. This concept of introducing nature-inspired methods to engineer superhydrophobic surfaces for the applications of liquid marble formation and oil spill treatment well fits the principle of green chemistry and will contribute to the sustainable chemistry and engineering.

AUTHOR INFORMATION

Corresponding Authors

*Jiafu Shi. E-mail: [email protected]. *Weiping Huang. E-mail: [email protected]. Author Contributions

All authors have given approval to the final version of the paper. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS The authors thank the financial support from the National Natural Science Funds of China (21406163, 21373120), Tianjin Research Program of Application Foundation and Advanced Technology (15JCQNJC10000).

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DOI: 10.1021/acssuschemeng.6b00149 ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX