HPLC Methods For Simultaneous Determination of Ascorbic and Dehydroascorbic Acids

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Article
One-step Preparation of Highly Hydrophobic and Oleophilic
Melamine Sponges via Metal-ion Induced Wettability Transition
Yichun Ding, Wenhui Xu, Ying Yu, Haoqing Hou, and Zhengtao Zhu
ACS Appl. Mater. Interfaces, Just Accepted Manuscript • Publication Date (Web): 29 Jan 2018
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Page 1 of 25 ACS Applied Materials & Interfaces
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One-step Preparation of Highly Hydrophobic and
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Oleophilic Melamine Sponges via Metal-ion
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Induced Wettability Transition
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Yichun Ding,† Wenhui Xu,‡ Ying Yu,‡ Haoqing Hou,‡ and Zhengtao Zhu*†
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24 Biomedical Engineering Program, Department of Chemistry and Applied Biological Sciences,
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26 South Dakota School of Mines and Technology, Rapid City, SD 57701, USA
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29 ‡
Department of Chemistry and Chemical Engineering, Jiangxi Normal University, Nanchang,
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32 330022, China
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35 KEYWORDS. Melamine sponge; Hydrophobic effect; Metal complex; Oil absorbent; Surface
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37 chemistry
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43 ABSTRACT. Hydrophobic and oleophilic absorbent materials have received wide attentions in
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46 recent years for potential applications in pollutant removal from accidental spills of oil or
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48 organic chemicals. In this work, we report a Metal-Ion Induced Hydrophobic Melamine
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50 Sponge (MII-HMS) prepared by a one-step solution immersion process. The commercial
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53 melamine sponge (intrinsically superhydrophilic with a water contact angle of ~ 0°) is immersed
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55 in an aqueous solution of transition metal ions (e.g., FeCl3, Fe(NO3)3, Zn(NO3)2, Ni(NO3)2, and
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60 ACS Paragon Plus Environment
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ACS Applied Materials & Interfaces Page 2 of 25
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3 Co(NO3)2) for a short period, followed by drying. This simple process renders the transition of
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6 the superhydrophilic melamine sponge to become highly hydrophobic (a water contact angle of
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8 ~130°). Results from the X-ray photoelectron spectroscopy (XPS) and the infrared spectroscopy
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10 suggest that the unprecedented transition is likely due to the formation of metal complexes
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during immersion. The MII-HMS is also oleophilic, exhibiting excellent oil absorption
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15 capabilities, ~ 71 to 157 times of its weight for a wide range of oils and organic solvents. Our
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17 work offers a simple, scalable, and economical approach to fabricate highly-efficient absorbent
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materials for potential applications in oil spill recovery and environmental remediation.
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26 1. INTRODUCTION
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30 Accidental oil and organic solvent spillages may cause severe environmental and ecological
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32 damage.1, 2 In particular, the oil spill accidents in waters (such as the Gulf oil spill in 2010) are
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34 the worst; the spills not only contaminate water and kill a large number of aquatic organisms,3, 4
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but also have significant long-lasting effects. Cleanup of the spilled oil in water has been
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39 challenging. At present, mechanical absorption by the porous materials is considered to be the
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41 most effective and economical method.5, 6 Conventional absorbent materials such as natural
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wood sawdust, zeolite and wool fibers, and nonwoven polypropylene/polyester fabrics typically
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46 have the drawbacks of low absorption capacities, poor selectivity, and poor recyclability.6
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49 In order to separate oil from a water medium, the absorbent material should be hydrophobic
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51 (water contact angle> 90°) and oleophilic.7, 8 The wettability of a solid surface is determined by
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54 its chemical composition and the surface roughness.8 Lowering the surface energy and
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56 increasing the surface roughness are two common strategies for preparation of hydrophobic
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3 surface. For examples, a hydrophilic surface can become hydrophobic by coating with
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6 perfluorosilanes;9-11 methods such as deposition of nanoparticles, surface etching, and
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8 electrospinning can be used to increase the surface roughness to make a hydrophobic material
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10 superhydrophobic (with a water contact angle > 150°).12-16 The melamine sponge (melamine-
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formaldehyde resin sponge) is a commercially available sponge with a highly porous open-cell
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15 structure.9, 17
It is commonly used as an insulating material for pipes and ductwork, a
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17 soundproofing material, and a kitchen cleaning sponge (e.g., Mr. Clean® Magic Eraser).
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Melamine sponge is intrinsically both superhydrophilic and oleophilic. Many studies have
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22 explored strategies of surface modification and roughing to convert the melamine sponge to a
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24 hydrophobic material. Ruan et al.9 prepared a superhydrophobic melamine sponge by depositing
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26 a thin layer of polydopamine, followed by grafting with a low surface energy molecule,
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29 1H,1H,2H,2H-perfluorodecanethiol. Pham et al.18 and Chen et al.10 hydrophobilized melamine
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31 sponges using octadecyltrichlorosilane (CH3(CH2)17SiCl3) and polydimethylsiloxane (PDMS),
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33 respectively. Melamine sponge can also be carbonized to form a hydrophobic carbon sponge.17,
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35 19-21
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Despite many significant progresses in preparation of hydrophobic and oleophilic materials
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38 in recent years, application of the hydrophobic materials as oil absorbents has been limited due to
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40 complicated manufacture processes, high cost, and difficulty to scale up.
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Herein, we report a simple, economical, and scalable method for preparation of a hydrophobic
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46 sponge for oil and organic solvent removal. Metal-ion Induced Hydrophobic Melamine Sponge
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48 (MII-HMS) is prepared by immersion of a melamine sponge in a salt solution (e.g., FeCl3,
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50 Fe(NO3)3, Zn(NO3)2, Ni(NO3)2, and Co(NO3)2) for a short period of time, followed by drying.
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53 To the best of our knowledge, the ion-induced wettability reversion in melamine sponge has not
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55 been reported previously. The metal-ion induced hydrophilic to hydrophobic transition of
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3 melamine sponge is characterized by x-ray photoelectron spectroscopy (XPS) and infrared
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6 spectroscopy. The as-prepared MII-HMS sponge exhibits excellent oil absorption capabilities
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8 that is 71 to 157 times of its own weight for a wide variety of oils and organic solvents.
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10 Furthermore, the MII-HMS sponge can be used to absorb oils/organic solvents both under and on
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water surface.
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16 2. EXPERIMENTAL SECTION
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19 Preparation of hydrophobic melamine sponge: Melamine sponge (melamine-formaldehyde
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resin sponge) was purchased from SINOYQX (Sichuan, China) and used as received. Other
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24 chemicals were purchased from Sigma-Aldrich Chemical Co. (St. Louis, MO, USA). For
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26 preparation of a hydrophobic melamine sponge (i.e., MII-HMS), a melamine sponge was
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28 immersed in a salt solution. After a set period of time, the sponge was removed from the salt
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31 solution; the solution absorbed in the sponge was squeezed out and further sucked out using
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33 towel paper. Thereafter, the sponge was dried in an oven at a setting temperature.
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35 Oil/organic solvents absorption capacity measurement: A cubic MII-HMS sample with the
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size of 2.00 × 2.00× 2.00 cm3 was used for testing the absorption capacity of the sponge to
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40 various oils and organic solvents. The absorption capacity was calculated based on the following
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42 formula.
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44 −
45 .⁄ . =
46

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48 where m0 is the mass of the prepared MII-HMS sample, m1 is the mass of the MII-HMS
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50 sample fully absorbed with organic solvent/oil. For each experiment, 5 samples were measured,
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and the average value was reported.
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3 Density and porosity measurement: A cubic pristine melamine sponge or MII-HMS with the
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6 size of 2.00 × 2.00× 2.00 cm3 was used for measuring the density (ρ) and porosity (P). The
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8 density and porosity were calculated using the following formulas.
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⁄ =
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14 and
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= 1 − # × 100%
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22 where ms is the mass of the sample, Vs is the volume (i.e., 8.00 cm3) of the sample, ρ is the
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24 density of the sample, and ρbulk is the density of the bulk melamine resin (ρbulk=1.51 g/cm3). Five
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26 samples were measured, and the average value was reported. The density of the pristine
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29 melamine sponge is 9.87±0.10 mg/cm3, and the density of the MII-HMS (prepared with a 0.1 M
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31 FeCl3 solution) is 10.16±0.06 mg/cm3; the porosity of MII-HMS (prepared with a 0.1 M FeCl3
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33 solution) is 99.3%.
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Stability test: The stability of the hydrophobicity of MII-HMS was evaluated. The MII-HMS
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38 sample was treated at different conditions, including sonication in DI water, steaming in boiling
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40 water, dipping in ethanol, and dipping in acid (0.1 M HCl & 0.1 M H2SO4) and alkali solutions
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(0.1 M NaOH), and then dried in an oven at 100 °C. The water contact angles of the samples
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45 treated in these harsh conditions were measured. Since the MII-HMS samples were hydrophobic,
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47 they were immersed in the above hydrophilic solutions forcibly during the experiment.
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49 Characterization: The morphology and structure of the sponges were characterized by Field
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52 Emission Scanning Electron Microscopy (FE-SEM, Zeiss Supra 40 VP) operated at an
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54 accelerating voltage of 2 kV. The chemical mapping using energy-dispersive x-ray spectroscopy
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3 (EDS) was conducted in the same SEM microscope operated at an accelerating voltage of 8 kV.
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6 Fourier transform infrared spectrometer (FT-IR, Tensor 27, Bruker, Germany) was used to
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8 characterize the chemical structure of the pristine melamine and MII-HMS sponges. X-ray
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10 photoelectron spectroscopy (XPS, Thermo escalab 250Xi, USA) was used to analyze the surface
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elemental information. Water contact angles were measured by Contact Angle specific surface
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15 area analyzer (OCA 15EC, Dataphysics instruments GmbH, Germany) from 2 µL droplets of de-
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17 ionized (DI) water. For each sample, the average value of the 5 to 8 measured water contact
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angles at different locations of the sample was reported; one standard deviation was reported as
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22 the error bar. Note that the water droplets for the contact angle measurement were not dyed; in
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24 the case that the water or oil droplets were on the surface of the sponges for photo and video
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26 taking, oil or water was colored by common food dyes for better visual observation, and was
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29 referred as dyed oil or water.
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33 3. RESULTS AND DISCUSSION
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Figure 1a and Movie S1 (Supporting Information) demonstrate the simplicity of the metal-ion
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38 induced wettability transition in melamine sponge. The pristine melamine sponge with a water
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40 contact angle ≈ 0° is intrinsically superhydrophilic and oleophilic (Figure 1b). A piece of
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melamine sponge is immersed in a FeCl3 solution (0.1 M) for less than 10 minutes followed by
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45 drying; this simple treatment results in a hydrophobic melamine sponge (denoted as MII-HMS).
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47 As shown in Figure 1c and Movie S2, the water droplets (dyed red) bead up on the surface of the
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49 MII-HMS, indicating that the melamine sponge becomes hydrophobic. Interestingly, MII-HMS
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52 remains oleophilic; the vegetable oil droplets are immediately absorbed into the sponge (as
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54 shown in Figure 1c and Movie S2). The hydrophobic behavior of MII-HMS is further
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3 demonstrated by photos in Figure 1d-f. A piece of MII-HMS floats on the water surface (Figure
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6 1d), and can be used to seal water in an Erlenmeyer flask (Figure 1e); the water droplet on the
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8 surface of the MII-HMS sample is readily removed by a piece of tissue paper (Figure 1f &
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10 Movie S3). When a monolith of MII-HMS is cut into several small pieces, these pieces remain
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hydrophobic (Movie S4); therefore, hydrophobilization occurs not only on the surface but also
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34 Figure 1. a) Preparation of the Metal-ion Induced Hydrophobic Melamine Sponge (MII-HMS)
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36 by immersion of the melamine sponge in a salt solution (e.g., FeCl3) followed by drying. b)
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39 Photograph of the water (dyed red with red ink) and vegetable oil droplets on the pristine
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41 melamine sponge. (c) Photograph of the water (dyed red with red ink) and vegetable oil droplets
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43 on a MII-HMS sample. d) A floating MII-HMS sample, and a sunk pristine melamine sponge
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sample in water (dyed red). e) A MII-HMS sample used as a cap sealing water in an Erlenmeyer
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48 flask. f) A droplet of dyed water on the MII-HMS sample removed by a piece of tissue paper.
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3 Figure 2a shows the water contact angle of MII-HMS prepared by immersion in a FeCl3 solution
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6 (0.1 M) for different periods followed by drying at 100 °C. After immersed in the salt solution
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8 for just a few seconds and then dried, the obtained MII-HMS sample becomes hydrophobic with
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10 a water contact angle of 122.5±2.6°; the contact angle raises to 127.4±4.4° after 2 minutes and
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remains at ~130° afterwards. The effect of the drying temperature on the water contact angle of
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15 MII-HMS is shown in Figure 2b; when dried at above 40 °C, MII-HMS has a water contact
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17 angle higher than 130°; even when dried at ambient temperature (~20 °C) after immersed in a
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FeCl3 solution, MII-HMS becomes hydrophobic with a water contact angle of 115.3±3.0°.
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Figure 2. a) Water contact angle of MII-HMS prepared by immersion in a FeCl3 solution (0.1
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50 M) for different duration, followed by drying at 100 °C. b) Water contact angle of MII-HMS
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52 prepared by immersion in a FeCl3 solution (0.1 M) for 10 minutes, followed by drying at
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different temperatures. c) Water contact angle of MII-HMS prepared by immersion in the FeCl3
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3 solutions of different concentrations. d) Water contact angle of the melamine sponge treated by
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6 immersion in DI water (blank experiment) and different salt solutions (0.1 M).
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12 The effect of the FeCl3 concentration is subsequently investigated. As shown in Figure 2c and
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14 Figure S1a (Supporting Information), after treated by the FeCl3 solutions with concentrations of
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17 0.0005, 0.001, 0.002, 0.005, 0.01, 0.02, 0.05, and 0.1 M, the resultant MII-HMS sponges have
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19 uniform and stable hydrophobic surface with the water contact angles of 130.1±5.1°, 125±6.4°,
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21 123.2±7.9°, 121.3±8.1°, 126.9±9.6°, 127.3±8.6°, 129±2.2°, and 130.7±0.9°, respectively. The
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results indicate that the water contact angle of MII-HMS does not depend on the concentration of
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26 the FeCl3 solution in the range of 0.0005 to 0.1 M. It is quite remarkable that the melamine
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28 sponge becomes hydrophobic (water contact angle of 130.1±5.1°) even when treated by a FeCl3
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solution with concentration as low as 0.0005 M (i.e. 0.5 mM). When the melamine sponges are
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33 treated with the FeCl3 solutions with concentrations of 0.00005 M and 0.0001 M (i.e., 0.05 mM
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35 and 0.1mM), the resultant sponges show unstable/nonuniform hydrophobic behavior; some areas
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37 of the sponge surface are hydrophobic with the contact angles higher than 120° and the water
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40 droplets beading up, whereas some areas are hydrophilic with the contact angles of 0~20° and
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42 the water droplets sinking in the sponge (as shown in Figure 2c and Figure S1a). When the
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44 FeCl3 solution of 0.00001 M (i.e., 0.01 mM) is used, the treated melamine sponge remains
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completely hydrophilic and no change of wettability is observed. As we will discuss later, the
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49 hydrophilic to hydrophobic transition is attributed to the metal complex formation between Fe3+
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51 and N of the melamine sponge. Since the melamine sponge is highly porous with a porosity of
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99.3%, the weak FeCl3 concentration dependence during preparation of MII-HMS suggests that
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56 the Fe3+ and N complexes are formed uniformly through the sponge when the concentration of a
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3 FeCl3 solution is higher than 0.0005 M (i.e. 0.5 mM); when the Fe3+ concentration is too low
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6 (e.g. 0.1 mM) to form complexes uniformly in the sponge, the treated sponge shows nonuniform
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8 surface properties with patches of hydrophobic and hydrophilic areas. Such nonuniform surface
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10 behavior suggests that there are not enough Fe3+ ions to interact with the melamine sponge
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uniformly at very low concentrations; some areas with sufficient complexes formation would
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15 render the hydrophilic to hydrophilic transition, whereas some patches could not form sufficient
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17 complexes to induce the wettability transition. On the other hand, when the concentration of
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FeCl3 for preparation of MII-HMS is too high, the water contact angle of MII-HMS decreases, as
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22 shown for the samples treated by 0.2 and 0.5 M FeCl3 solutions in Figure 2c. One possible
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24 explanation of the result is that the excessive FeCl3 salt at high concentration may deposit on the
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26 surface of the melamine sponge, which weakens the hydrophobicity of MII-HMS.
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30 Interestingly, the metal-ion induced hydrophilic to hydrophobic transition of the melamine
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32 sponge is not limited to the FeCl3 solution. As shown in Figure 2d and Figure S1b, similar
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34 hydrophilic to hydrophobic transition of the melamine sponge is observed when it is treated in
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the Fe(NO3)3, Zn(NO3)2, Ni(NO3)2, and Co(NO3)2 solutions. As a control experiment, the
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39 melamine sponge immersed in the DI water and then dried at 100 °C remains hydrophilic. When
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41 the melamine sponge is treated by the NaCl and CaCl2 solutions, no hydrophilic to hydrophobic
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transition is observed. Figure S1c shows that all melamine sponges treated by the NaCl solutions
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46 with different concentrations are hydrophilic. Furthermore, when the melamine sponge is treated
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48 in a NaCl solution with a trace amount of FeCl3, the sponge becomes hydrophobic. As shown in
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50 Figure S1d, when the melamine sponge is treated by as dilute as 0.0001 M FeCl3 in the 0.1 M
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53 NaCl solution (i.e., by adding 1.6 mg FeCl3 salt in 100 mL 0.1 M NaCl solution), the hydrophilic
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55 to hydrophobic transition is observed in the melamine sponge. These results suggest that the
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3 transition metal ions are required for preparation of MII-HMS and the main group metal ions do
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6 not induce the wettability change in the melamine sponge.
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9 It is worth noting that the metal-ion induced hydrophilic to hydrophobic transition is unique to
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11 the melamine sponge. A control experiment shows that no hydrophilic to hydrophobic transition
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is observed in a cellulose sponge when it is treated with the salt solutions (Figure S2). In
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16 addition, the hydrophobic melamine sponge (i.e, MII-HMS) prepared by the metal-ion induced
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18 wettability transition is very robust. As shown in Figure S3; the MII-HMS sponge remains
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highly hydrophobic after it is sonicated in DI water or dipped in boiling water, ethanol, and
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23 acid/base solutions and then dried at 100 °C.
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26 Scanning electron microscopy (SEM) images in Figure 3a-a’ and 3b-b’ show the morphology of
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28 the pristine melamine sponge and MII-HMS. The melamine sponge has a typical open cell
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31 spongy structure; and the MII-HMS prepared with a FeCl3 solution (0.1 M) shows no structural
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33 and morphological changes. Additionally, the surface of the melamine sponge prepared with
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35 different FeCl3 concentration remains smooth (Figure S4), except some degrees of roughening at
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the sporadic locations for the samples prepared with high FeCl3 concentrations (0.2 and 0.5 M),
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40 which may support our explanation that the deposition of excessive FeCl3 salt on the sponge
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42 surface results in the decreased contact angles in these samples (Figure 2c). Therefore, the SEM
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results indicate that the hydrophilic to hydrophobic transition in melamine sponge is not caused
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47 by change of the surface roughness. The composition of the MII-HMS sample prepared with the
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49 FeCl3 solution (0.1 M) is mapped by SEM Energy Dispersive Spectroscopy (EDS) analysis
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51 (Figure 3c-h); C, N, O, Fe, and Cl elements are identified on the surface, confirming that the
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54 metal ions are incorporated into the MII-HMS.
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27 Figure 3. a-a’) SEM images of the pristine melamine sponge. b-b’) SEM images of the MII-
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HMS prepared with a FeCl3 solution (0.1 M). c-h) SEM-EDS elemental mapping images
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32 acquired from a representative MII-HMS prepared with a FeCl3 solution (0.1 M).
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38 To better understand the mechanism of the hydrophilic to hydrophobic transition in MII-HMS,
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Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) are
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43 used to analyze the chemical constituents and the chemical bonds in the melamine and MII-HMS
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45 sponges. Figure 4 shows the FTIR spectra of the pristine melamine sponge and MII-HMS
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prepared with the FeCl3 solutions of different concentrations. The IR spectrum of the pristine
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50 melamine sponge shows the characteristic stretching vibration modes of C=N and C-N on
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52 triazine ring at 1542 cm-1 (C=N),13 and 1329 cm-1 (C-N),22, 23 respectively. For the spectrum of
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54 MII-HMS, the vibration modes at 1542 and 1329 cm-1 shift to the lower wavenumbers of
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3 1539~1541 cm-1 and 1321~1327 cm-1, respectively, suggesting that the triazine N atom forms the
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6 coordination bonds,24, 25 presumably with the metal ion Fe3+ . The vibration mode of the amino
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8 C-NH shifts from 1468 cm-1 in the pristine melamine sponge to the higher wavenumbers of
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10 1471~1478 cm-1 in MII-HMS, supporting the formation of the coordination bonds between the
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amino N atom and the metal ion.26
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32 Figure 4. FTIR spectra of the melamine sponge and the MII-HMS samples prepared with the
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34 FeCl3 solutions of different concentrations.
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37 XPS analysis further confirms the interaction between the metal ion and the melamine sponge.
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The XPS spectrum of the pristine melamine sponge shows the peaks of C, N and O, whereas the
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42 peaks of Fe and Cl are observed in the spectrum of MII-HMS (Figure 5a, 5b, and Figure S5).
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44 Compared to the XPS spectrum of the pristine melamine sponge, the C 1s and O 1s peaks in the
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46 spectra of the MII-HMS samples do not change significantly (Figure S6), whereas the N 1s peak
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49 shifts significantly to the higher binding energy (Figure 5c). In the melamine sponge, there are
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51 two types of the N atoms: N of the triazine ring (=N-) and N of the amino group (–NH-). As
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53 shown in Figure 5d, the N 1s peak of the pristine melamine sponge is de-convoluted to two peaks
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at 397.98 eV and 399.06 eV, which are assigned to the =N- and –NH- groups, respectively.27, 28
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3 The N 1s peak of MII-HMS prepared with the FeCl3 solution (0.1 M) is de-convoluted to three
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6 peaks at 397.98 eV, 399.06 eV and 399.53 eV, among which the new peak at 399.53 eV would
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8 be attributed to the formation of the coordination bonds between the N atoms and the metal
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10 ions.28 The peaks of the corresponding metal elements are also observed from the XPS spectra
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of the MII-HMS samples prepared with other salt solutions (as shown in Figure 5e); the N 1s
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15 peak shows a significant shift to a higher binding energy (Figure 5f), whereas the C 1s and O 1s
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17 peaks show no changes (Figure S7). These results clearly indicate the formation of the
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coordination interactions between the metal ions and the N atoms during preparation of MII-
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22 HMS, resulting in the hydrophilic to hydrophobic transition.
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52 Figure 5. a) XPS spectra of the pristine melamine sponge and the MII-HMS sample prepared
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55 with a FeCl3 solution (0.1 M). b) XPS spectra of the pristine melamine sponge and the MII-
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1
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3 HMS sample prepared with a FeCl3 solution (0.1 M) in the energy region of Fe 2p. c) N 1s peak
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6 of the pristine melamine sponge and the MII-HMS sample prepared with the FeCl3 solutions of
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8 different concentrations. d) Fitting of the N 1s peak of the pristine melamine sponge and the
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10 MII-HMS sample prepared with the FeCl3 solution (0.1 M). e) XPS spectra of the pristine
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melamine sponge and the MII-HMS sample prepared with different salt solutions (0.1 M). f) N
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15 1s peak of the pristine melamine sponge and the MII-HMS sample prepared with different salt
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17 solutions (0.1 M).
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Based on the results of the FTIR and XPS analysis, a mechanism of the metal-ion induced
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26 hydrophilic to hydrophobic transition is proposed. Figure 6a shows a representative metal ion-N
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28 coordination structure, in which the Fe3+ ion forms a six-coordinated complex. It is known that
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the surface energy is proportional to the polarity of the chemical bonds on the surface.12 The
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33 repeating unit of the melamine sponge is a nitrogen-containing benzoheterocyclic skeleton of
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35 2,4,6-triamino-s-triazine, in which the N atoms of the triazine are sp2 hybridized and the N atoms
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37 of the amino groups are sp3 hybridized;29 both types of the N atoms have the lone-pair electrons.
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40 The abundance of the lone-pair electrons results in a high polar surface and accordingly makes
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42 the melamine sponge intrinsically hydrophilic. The d-block transition metal ions can coordinate
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44 with the lone-pair electrons of N in the melamine sponge to form the metal complexes through
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the coordinate covalent bonds.24, 25, 28, 30-35 The nitrogen-metal ion complexes, together with the
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49 counter ions, may re-organize the chemical structure on the surface of the melamine sponge,
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51 which results in the reduced surface polarity of the melamine sponge and makes it hydrophobic.
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Similar hydrophilic to hydrophobic transition was also observed in a mesh coated with the
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15
1
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3 hydrophilic poly(acrylic acid) after the poly(acrylic acid) chelated with the metal ions (e.g., Hg2+)
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6 in solution.36
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24 Figure 6. Schematic illustrations of (a) the coordination interactions between the metal ions and
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the N atoms in MII-HMS and (b) the corresponding hydrophilic to hydrophobic transition of the
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29 melamine sponge.
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32 It is worth noting that the spongy morphology may play an important role in amplification of
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34 the hydrophilic to hydrophobic transition (Figure 6b). After the formation of complexes, which
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reduces the surface polarity of the melamine sponge and makes it hydrophobic, the highly
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39 porous/rough surface might substantially improve the hydrophobicity because of the trapped air
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41 cushion underneath the water droplet, as suggested by the Cassie model.37 This also explains
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43 that the types of salts have no significant effects on wettability transition; as long as the ions
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46 could form complexes with the melamine sponge to initiate the wettability transition, the contact
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48 angles of the hydrophobic sponge would be amplified by the porous structure.
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51 To investigate the effects of the morphology on the metal-ion induced wettability change in
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melamine polymer, the melamine resin films are prepared by cross-linking melamine with
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56 formaldehyde in a basic aqueous solution.38 The preliminary results of the wettability of the
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16
1
2
3 melamine resin films treated by salt solutions (0.1 M FeCl3, Fe(NO3)3, Zn(NO3)2, Ni(NO3)2,
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6 Co(NO3)2) are presented and discussed in the Supporting Information. Based on these
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8 preliminary results, the metal ions’ influence on the wettability of flat melamine film is not
9
10 conclusive. To further understand the metal-ion induced wettability reversion in the melamine
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materials, the melamine materials with different composition (e.g., composites of melamine and
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15 other polymers cross-linked by formaldehyde) or morphology (e.g., flat melamine film,
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17 melamine sponge with different porosity/roughness, or melamine nanofibers), the strength of the
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metal-nitrogen complex, and different ionic surfactants besides the simple transition metal ions
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22 may be interesting. Research along these directions is currently under way.
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25 MII-HMS is evaluated as an absorbent for removal of the various oils and organic solvents from
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27 a water medium, given its hydrophobic and oleophilic characteristics and other highly attractive
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30 physical properties, including high porosity (>99%), light weight (ρ=10.16±0.06 mg/cm3), open-
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32 cell structure, and good elasticity. Figure 7a and Movie S5 shows that a piece of MII-HMS can
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34 extract a puddle of heavy oil/solvent such as chloroform (dyed red) underwater quickly without
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uptake of water. In Figure 7b, a cube of MII-HMS is used to absorb the vegetable oil which
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39 floats on the water surface; the absorbed oil can be readily squeezed out from the cube. The
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41 absorption capacities of MII-HMS for the various oils and organic solvents are evaluated. As
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shown in Figure 7c, MII-HMS exhibits the excellent absorption capabilities of 71 times (for
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46 hexane) to 157 times (for chloroform) its own weight, where the absorption capability is
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48 correlated with the density of the solvents/oils. The absorption capabilities of MII-HMS are
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50 comparable or exceed those of the sponge materials prepared by more complicated methods, as
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53 shown in Table S1. Furthermore, the melamine sponge is flame retardant due to the high
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55 nitrogen content,9 and MII-HMS maintains this property. As shown in Figure 7d, MII-HMS
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1
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3 withstands the combustion of the absorbed ethanol, and no heavy smoke is released during the
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6 fire (Movie S6). Besides the excellent oil absorption capability, the total material cost of
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8 preparation of MII-HMS is estimated to be only ~ ¢0.53 per 1 inch3 (Table S2). Therefore, the
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10 method for preparation of the hydrophobic melamine sponge reported here is simple, facile, and
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economical.
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31 Figure 7. a-b) Photographs showing the absorption of (a) chloroform (dyed red) under water and
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33 (b) vegetable oil on the water surface using the MII-HMS sample; c) Absorption capacity of the
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35 MII-HMS prepared with the FeCl3 solution (0.1 M) for various organic solvents and oils; d)
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38 Photographs showing the absorption and burning of ethanol using MII-HMS.
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43 4. CONCLUSION
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45 In summary, a highly hydrophobic and oleophilic melamine sponge (MII-HMS) is prepared by
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47 one-step immersion of an intrinsically hydrophilic melamine sponge in a salt solution (e.g., FeCl3,
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50 Fe(NO3)3, Ni(NO3)2, Zn(NO3)2, and Co(NO3)2) for a short period (as short as a few seconds).
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52 FTIR and XPS results suggest that the nitrogen atoms of melamine may coordinate with the
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54 transition metal ions, leading to the wettability change from superhydrophilicity to high
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18
1
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3 hydrophobicity in the melamine sponge. The obtained hydrophobic MII-HMS exhibits excellent
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6 oil absorption capacity (up to 157 times of its own weight), and can remove both light and heavy
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8 oils on the water surface or under water, respectively. The preparation process of MII-HMS is
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10 simple, fast, economic, environmentally friendly, and readily scalable. We envision that MII-
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HMS may have great potentials for oil spill recovery and environmental remediation.
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16 ASSOCIATED CONTENT
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19 Supporting Information. Photos of the water droplets on the melamine sponge prepared with
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various salt solutions and concentrations; Cellulose sponge treated with different salt solutions
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24 (control experiment); Stability of hydrophobicity of MII-HMS; XPS spectra of MII-HMS
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26 prepared with different salt solutions; Wettability of the melamine resin films treated by salt
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28 solutions (0.1 M FeCl3, Fe(NO3)3, Zn(NO3)2, Ni(NO3)2, Co(NO3)2); Comparison of MII-HMS
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31 and other hydrophobic spongy materials for oil/organic solvent absorption; Cost estimation of
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33 the materials for preparation of MII-HMS. (PDF)
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36 Supporting videos showing various properties of MII-HMS. (AVI)
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40
AUTHOR INFORMATION
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42 Corresponding Author
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45 * Zhengtao.Zhu@sdsmt.edu
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48 Author Contributions
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51 The manuscript was written through contributions of all authors. All authors have given
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53 approval to the final version of the manuscript.
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19
1
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3 Notes
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6 The authors declare no competing financial interest.
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8
9 ACKNOWLEDGMENT
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We acknowledge financial support from the Biomedical Engineering Program of South Dakota
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14 School of Mines and Technology.
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17
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25

HPLC Methods For Simultaneous Determination of Ascorbic and Dehydroascorbic Acids

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HPLC Methods For Simultaneous Determination of Ascorbic and Dehydroascorbic Acids

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