Name: Gyroid Nickel Nanostructures from Diblock Copolymer Supramolecules (Video) | JoVE Journal
Uploaded: 2014-04-28T13:00:00.000+00:00
Duration: 8 min 40 s
Description: Learn to prepare ordered nickel nanofoams with inverse gyroid morphology using diblock copolymer supramolecular templates and electroless deposition. This method enables synthesis of nanoporous metal structures for catalysis and energy applications.

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5 minutes

We acknowledge financial support by the Zernike Institute for Advanced Materials, University of Groningen.

1. Preparation and Characterization of PS-b-P4VP(PDP) Complexes with Double Gyroid Morphology
<ol>
	<li>Weigh out polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) and pentadecylphenol (PDP, Mr = 304.51 g/mol). In order to obtain the gyroid morphology, carefully select the amount of PDP should be (the weight fraction of P4VP(PDP) block (fP4VP(PDP))should be ca. 0.6 according to the phase diagram of linear AB diblock copolymers). Usually, 0.15-0.2 g of a PS-b-P4VP leads to PS-b-P4VP(PDP) films 50-100 μm thick (given that the diameter of a Petri dish used in the step 1.3 is 5-6 cm). Calculate the amount of PDP according to the following equations: 
	<img alt="Polymer composition equation, f(P4VP(PDP)) ratio, calculation of polymer mass fractions." src="/files/ftp_upload/50673/50673eq1.jpg" data-altupdatedat="1787630408000" data-alt="Equation 1"> 
	<img alt="Mathematical equation for copolymer mass; m(P4VP)=f(P4VP)×m(copolymer); polymer chemistry." src="/files/ftp_upload/50673/50673eq2.jpg" data-altupdatedat="1787630408000" data-alt="Equation 2"> 
	<img alt="Polymer composition formula: f(P4VP)=Mn(P4VP)/Mn(copolymer), ratio calculation, diagram." src="/files/ftp_upload/50673/50673eq3.jpg" data-altupdatedat="1787630408000" data-alt="Equation 3"> 
	<img alt="Polymer mass calculation equation; chemical composition; educational diagram." src="/files/ftp_upload/50673/50673eq4.jpg" data-altupdatedat="1787630408000" data-alt="Equation 4"></li>
	<li>Dissolve PS-b-P4VP and PDP in chloroform and stir it for a couple of hours at room temperature. Maintain the concentration of polymer below 2 wt% to ensure the homogeneous complex formation.</li>
	<li>Pour the solution into a glass Petri dish.</li>
	<li>Place the dish into a saturated chloroform atmosphere.</li>
	<li>After about one week, take out the Petri dish. A film of the supramolecular complex is formed.</li>
	<li>Dry the film in vacuum at 30 °C overnight.</li>
	<li>Place the film in a specially designed container, remove the air from the container and then fill it with nitrogen. Anneal the film for 4 days in the oven at 120 °C under N2 atmosphere with 1 bar overpressure.</li>
	<li>Cut the small piece of the film, embed in epoxy and cure it overnight at 40 °C.</li>
	<li>Microtome the sample to a thickness of about 80 nm using a diamond knife at room temperature. The microtomed section will float on water. Pick them up and place on Cu grids.</li>
	<li>Put the grids containing the microtomed sections into a jar with iodine. After 45 min samples are stained and ready for transmission electron microscopy.</li>
	<li>Insert the Cu grids with stained sections in the transmission electron microscope operating at an accelerating voltage of 120 kV and image the sample.</li>
	<li>Insert the piece of the film (obtained after step 1.7) into the sample holder for small angle X-ray scattering and fix it with a Kapton tape. Place the prepared sample holder into the machine for SAXS. Open the X-ray shutter and acquire the 2D scattering pattern. Integrate the obtained 2D pattern and analyze the position of the peaks in 1D pattern.</li>
</ol>
2. Generation and Characterization of the Porous Structure
<ol>
	<li>Put the piece of the film (obtained after step 1.7) in ethanol and keep it for three days.</li>
	<li>Dry the sample.</li>
	<li>Prepare the samples for 1H NMR measurements. Dissolve PDP powder, PS-b-P4VP powder, supramolecular complex PS-b-P4VP(PDP) (after step 1.7), and porous film (after step 2.2) in CDCl3. Record 1H NMR spectra at room temperature.</li>
	<li>Analyze PS-b-P4VP powder, supramolecular complex PS-b-P4VP(PDP) (after step 1.7), and porous film (after step 2.2) by differential scanning calorimetry. Use a modulated mode with a heating/cooling rate of 1 °C/min, an oscillation amplitude of 0.5 °C, and an oscillation period of 60 sec. Equilibrate the samples at -30 °C, heat to 180 °C, cool to -30 °C, and then heat again to 180 °C. Use the data from the second heating cycle for the analysis.</li>
	<li>Outgas the porous sample (after step 2.2) for 8 hr at room temperature and for 18 hr at 70 °C and perform nitrogen adsorption measurements at 77 K.</li>
	<li>Use the appropriate software (for example, WinADP) and models to analyze the obtained isotherms.</li>
	<li>Dry the porous sample (after step 2.2) at 50 °C for 8 hr and degas it at room temperature and pressure of 0.5 Pa for 2 hr.</li>
	<li>Perform mercury porosimetry.</li>
</ol>
3. Inserting Nickel in the Polymer Template
<ol>
	<li>Weigh out tin chloride (SnCl2, Mr = 189.60 g/mol) and prepare an aqueous solution (0.1 M SnCl2 / 0.1 M HCl; 1.896 g SnCl2, 0.8 ml HCl, and 100 ml H2O). Put the solution on a shaker overnight to ensure the complete dissolution of SnCl2.</li>
	<li>Weigh out palladium chloride (PdCl2, Mr = 177.33 g/mol) and prepare an aqueous solution (0.0014 M PdCl2 / 0.25 M HCl; 0.025 g PdCl2, 2 ml HCl and 100 ml H2O).</li>
	<li>Prepare part 1 of the nickel plating bath: weigh out 6.78 g nickel sulfate hexahydrate (NiSO4•6H2O, Mr = 262.85 g/mol) and 2 g sodium citrate (Na3C6H5O7, Mr = 258.06 g/mol) and dissolve them in 80 ml of water. Add 828 μl 85% lactic acid (C3H6O3, Mr = 90.08 g/mol).</li>
	<li>Prepare part 2 of the nickel plating bath: weight out 0.2 g borane dimethylamine complex ((CH3)2NHBH3, Mr = 58.92 g/mol) and dissolve it in 20 ml of water. Borane dimethylamine complex should be handled in a well-ventilated fume hood.</li>
	<li>Immerse the porous film (after step 2.2) in the aqueous solution of tin chloride (step 3.1) for 1 hr.</li>
	<li>Rinse the film thoroughly with deionized water.</li>
	<li>Immerse the film in the aqueous solution of palladium chloride (step 3.2) for 1 hr.</li>
	<li>Rinse the film thoroughly with deionized water.</li>
	<li>Mix part 1 (3.3) and part 2 (3.4) of the nickel plating bath. Adjust the pH to 7.0 using ammonium hydroxide.</li>
	<li>Immerse the film in the nickel plating bath for 1 hr.</li>
	<li>Rinse the film thoroughly with deionized water.</li>
	<li>Dry the sample.</li>
	<li>Prepare the plated sample for electron microscopy as described in steps 1.8-1.9.</li>
	<li>Image the sample as described in step 1.11.</li>
	<li>Insert Cu grids containing the sections of the plated sample in the high-resolution transmission electron microscope. Acquire high-resolution TEM micrographs. Observe the sample under the microscope and choose the area for elemental analysis by EDX (Energy Dispersive Analysis of X-Rays). Perform the EDX analysis of the chosen area and analyze the obtained pattern.</li>
</ol>
4. Exposure of the Inverse Gyroid Nickel Foam
<ol>
	<li>Put the nickel-plated film (after step 3.12) in an oven at 350 °C and keep it from 1 hr up to 4 days.</li>
	<li>Attach the sample to the sample holder using a silver paste.</li>
	<li>Insert the sample into the scanning electron microscope. Acquire several images of the sample.</li>
	<li>Insert the sample into the scanning electron microscope. Observe the sample under the microscope and choose the area for elemental analysis by EDX. Perform the EDX analysis of the chosen area and analyze the obtained pattern.</li>
</ol>

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</ol>

The authors declare no competing financial interests.

Supramolecular complexes are successfully applied as precursors for well-ordered metal nanofoams. In this method, the crucial step is to acquire the appropriate template, i.e.&#160;a template with gyroid morphology. In the phase diagram of block copolymers the gyroid region is very small and it is rather difficult to target. This means that if conventional block copolymers are used as starting materials, the quite elaborate synthesis has to be repeated until the desired composition, that gives rise to the gyroid...

There are several techniques available for the preparation of metal nanofoams: dealloying1-3, sol-gel approaches4,5, nanosmelting6,7, and combustion synthesis8. In the dealloying process, the starting material is usually a binary alloy, for example, an alloy of silver and gold. The less noble metal, silver in this case, can be removed either chemically or electrochemically resulting in a disordered porous gold foam with nanosized ligaments. In combustion synthesis, metal is mixed with an energetic precursor that releases energy during its decomposition and drives the formation of metal nanofoam8. Studies on the mechanical behavior of metal foams indicate that in disordered architectures stresses cannot be transmitted effectively from the ligament nanoscale to the overall macroscale9-11.&#160;Thus well-ordered metal nanofoams are expected to have superior mechanical properties in comparison to the disordered ones.
The idea represented here is to employ block copolymers that self-assemble into ordered nanostructures as precursors to metal nanofoams. Depending on the composition of a block copolymer, the total number of monomer units and the extent of repulsion between the chemically connected blocks, various morphologies appear such as: spherical, cylindrical, lamellar, double gyroid, hexagonally perforated lamellar, and others12-14. Furthermore, polymer blocks can be degraded selectively leading to nanoporous materials15. The most common methods include: ozonolysis16-18, UV irradiation19, reactive ion etching20-22, and dissolution23-26. The generated porous structures can be backfilled with various inorganic materials. Metal oxides (e.g.&#160;SiO2, TiO2) are usually introduced via sol-gel method into the template&#39;s channels27-29. Electrochemical and electroless plating are commonly used to deposit metal into or onto templates30-33. Finally, the remaining polymer can be removed from the polymer/inorganic nanohybrid via pyrolysis2, dissolution34,35, UV degradation28,29, etc.
In our approach, we start from a supramolecular complex of polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) diblock copolymer and amphiphilic pentadecylphenol (PDP) molecules. This complex is a result of the hydrogen bonding between PDP and pyridine rings (Figure 1a). The composition of the starting block copolymer and the amount of added PDP are chosen in such a way that the obtained system self-assembles in the bicontinuous double gyroid morphology with a PS network and a P4VP(PDP) matrix (Figure 1b). PDP molecules become selectively dissolved in ethanol and P4VP chains collapse onto the PS network (Figure 1c). Subsequently, using electroless plating method, nickel is deposited into the pores of the template (Figure 1d). After the removal of the remaining polymer via pyrolysis, a well-ordered gyroid nickel nanofoam is obtained (Figure 1e).

<table><tbody><tr><td colspan="4">&lt;strong&gt;Reagents&lt;/strong&gt;</td></tr><tr><td>PS-&lt;em&gt;b&lt;/em&gt;-P4VP, CAS: 26222-40-2</td><td>Polymer Source Inc.</td><td>P9009-S4VP&lt;br/&gt; P136-S4VP&lt;br/&gt; P5462-S4VP&lt;br/&gt; P3912-S4VP</td><td>additional information are provided in a separate table</td></tr><tr><td>PDP</td><td>Aldrich</td><td>P4402-100G-A</td><td>recrystallized twice from petroleum ether</td></tr><tr><td>SnCl&lt;sub&gt;2&lt;/sub&gt;</td><td>Acros Organics</td><td>196981000</td><td></td></tr><tr><td>PdCl&lt;sub&gt;2&lt;/sub&gt;</td><td>Aldrich</td><td>76050</td><td></td></tr><tr><td>NiSO&lt;sub&gt;4&lt;/sub&gt;&amp;bull;H&lt;sub&gt;2&lt;/sub&gt;O</td><td>Sigma-Aldrich</td><td>227676</td><td></td></tr><tr><td>Lactic acid</td><td>Aldrich</td><td>W261106</td><td></td></tr><tr><td>Citric acid trisodium salt</td><td>Sigma-Aldrich</td><td>C3674</td><td></td></tr><tr><td>Borane dimethyl amine complex</td><td>Aldrich</td><td>180238</td><td></td></tr><tr><td>&lt;strong&gt;PS-&lt;em&gt;b&lt;/em&gt;-P4VP catalogue number&lt;/strong&gt;</td><td>&lt;strong&gt;Mn (PS), g/mol&lt;/strong&gt;</td><td>&lt;strong&gt;Mn(P4VP), g/mol&lt;/strong&gt;</td><td>&lt;strong&gt;PDI&lt;/strong&gt;</td></tr><tr><td>P9009-S4VP</td><td>24000</td><td>9500</td><td>1.1</td></tr><tr><td>P136-S4VP</td><td>31900</td><td>13200</td><td>1.08</td></tr><tr><td>P5462-S4VP</td><td>37500</td><td>16000</td><td>1.3</td></tr><tr><td>P3912-S4VP</td><td>41500</td><td>17500</td><td>1.07</td></tr></tbody></table>

gyroid nickel nanostructures from diblock copolymer supramolecules

Gyroid Nickel Nanostructures from Diblock Copolymer Supramolecules

Nanoporous metal foams possess a unique combination of properties - they are catalytically active, thermally and electrically conductive, and furthermore, have high porosity, high surface-to-volume and strength-to-weight ratio. Unfortunately, common approaches for preparation of metallic nanostructures render materials with highly disordered architecture, which might have an adverse effect on their mechanical properties. Block copolymers have the ability to self-assemble into ordered nanostructures and can be applied as templates for the preparation of well-ordered metal nanofoams. Here we describe the application of a block copolymer-based supramolecular complex - polystyrene-block-poly(4-vinylpyridine)(pentadecylphenol) PS-b-P4VP(PDP) - as a precursor for well-ordered nickel nanofoam. The supramolecular complexes exhibit a phase behavior similar to conventional block copolymers and can self-assemble into the bicontinuous gyroid morphology with two PS networks placed in a P4VP(PDP) matrix. PDP can be dissolved in ethanol leading to the formation of a porous structure that can be backfilled with metal. Using electroless plating technique, nickel can be inserted into the template&#39;s channels. Finally, the remaining polymer can be removed via pyrolysis from the polymer/inorganic nanohybrid resulting in nanoporous nickel foam with inverse gyroid morphology.

The morphology of supramolecular complexes PS-b-P4VP(PDP)x is examined by TEM and SAXS. Figures 2a and 2b display typical gyroid patterns of a representative supramolecular complex: the double-wave and the wagon-wheel patterns that are known to represent projections through the (211) and the (111) plane of the gyroid unit cell, respectively. The PS block domains appear bright while the P4VP(PDP)x block domains appear dark due to iodine staining. Figure 2c repres...

This article describes the preparation of well-ordered nickel nanofoams via electroless metal deposition onto nanoporous templates obtained from self-assembled diblock copolymer based supramolecules.

Nanoporous metal foams possess a unique combination of properties - they are catalytically active, thermally and electrically conductive, and furthermore, ...

The overall goal of this procedure is to prepare ordered metal nanofoams, starting from a supramolecular complex, polystyrene block poly for vinyl purine penedes LPH phenol. This is accomplished by first selecting the appropriate system parameters that would give rise to the double gyro morphology in supramolecular complexes. The second step is to selectively remove one component of the complex, namely penad sylph phenol, which forms part of the gyro matrix.Next, the porous template is backfilled with nickel via an electros plating procedure. The final step is removal of the remaining polymer by pyrolysis at 350 degrees Celsius. Ultimately, block co-polymer template directed synthesis is used to generate well ordered nano porous metal foams with inverse gyro morphology.So the main advantage of this technique over existing methods is that we are able in a straightforward way to obtain a double GY morphology in blocker polymers. After that, once we have a double gyre morphology, we can take our sample, soak it in ethanol, and then remove Amphiphilic pandaol in a very simple way. Then when we have apor structure, we do electroless metal plating to insert metal into a complex PO pathways in a such a way, obtain metal nanofoam at the end.This method provides an intuitive way to form ordered nano porous networks from a wide variety of metals. First dissolve polystyrene block poly for vinyl purine and penedes phenol in chloroform, and stir the solution for a couple of hours at room temperature. Pour the solution into a glass petri dish, then place the dish into a saturated chloroform atmosphere.After approximately one week, remove the Petri dish from the saturated chloroform atmosphere. Dry the supramolecular complex film in a vacuum at 30 degrees Celsius overnight. After removing the film from the oven, place it in a specially designed container.Then remove the air from the container and fill it with nitrogen when finished. Ane the film for four days in the oven at 120 degrees Celsius under nitrogen atmosphere with one bar over pressure. Once the an kneeling process is complete, cut a small piece of the film and embed it in epoxy.Then cure the sample overnight at 40 degrees Celsius. Microtome the sample to a thickness of about 80 nanometers using a diamond knife at room temperature. Place the micro toed sections on copper grids.Following this transfer, the grids containing the microtome sections to a jar with iodine. After 45 minutes, remove the stained samples. In preparation for TEM, insert the copper grids with stained sections in the transmission electron microscope.Operating at an accelerating voltage of 120 kilovolts and image the sample. Then insert a piece of a kneeled film into the sample holder for sacks and fix it with cap on tape. Place the prepared sample holder into the machine.Open the x-ray shutter and acquire the 2D scattering pattern. At this point, immerse another small piece of a kneeled film in ethanol for three days. Once the porous film has been dried, immerse it in an aqueous solution of tin chloride for one hour.After removing the film from the solution, rinse it thoroughly with deionized water. Next, immerse the film in an aqueous solution of palladium chloride. After one hour, remove the film from the solution and rinse it with deionized water.To prepare the nickel plating bath, mix a nickel sulfate hexahydrate solution with a Bo dimethyl amine complex solution at a four to one ratio and adjust the pH to seven. Using ammonium hydroxide, immerse the film in the nickel plating bath for one hour. After rinsing with deionized water, dry the film in a fume hood.After prepare the plated sample for electron microscopy as previously described. Image it using the same conditions as before. Following this place the nickel plated film in an oven at 350 degrees Celsius for one hour to four days.Once the film has cooled to room temperature, attach it to the sample holder using a silver paste. Then insert the sample holder into the scanning electron microscope. Acquire SEM micrographs and perform EDX analysis.Double wave and wagon wheel. Gyro patterns represent projections through the 2 1 1 and 1 1 1 plane of the gyro unit cell respectively. Polystyrene block domains appear bright while poly.Four vinyl purine pentyl phenol block domains appear dark from iodine. Staining the double wave pattern of another sample shows a periodicity decrease sax peaks at square root of six Q star square root of eight QStar square root of 14 QStar square root of 22 QStar and square root of 50 QStar. Confirm the bi continuous IA 3D morphology after ethanol treatment.Penad sylph phenol proton NMR signals are absent. DSC data imply that the thermal behavior of the ethanol treated sample and DI block copolymer is identical. The porous gyro template has a high BET specific surface area of 104 square meters per gram and occupies almost 60 volume percent.The average pore diameter is 40 nanometers with narrow pore size distribution. The contrast in the unstained nickel plate gyro, TEM micrograph originates from metal deposited in the nano channels. The wagon wheel pattern confirms preservation of the double gyro morphology.High resolution TEM Micrographs show large interconnected nickel crystalite and EDX analysis reveals the plated sample. Chemical composition. Carbon nickel and oxygen peaks are observed, which indicates oxidation of the nickel nanofoam when stored in air.The nickel network remains intact during polymer decomposition by isothermal heating. The exposed nickel replica preserves the inverse gyro morphology as confirmed by SEM. Using the method that we've just shown, we were able to obtain and to characterize highly ordered metal nanofoams.These highly ordered metal nanofoams can potentially be used as actuators. This method opens a path for the investigation of the differences in the behavior of ordered and disordered nano porous metals. Don't forget that working with chemicals used for electrodes, metal plating can be extremely hazardous and one should always use personal protective equipment when performing this procedure.

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Learn to prepare ordered nickel nanofoams with inverse gyroid morphology using diblock copolymer supramolecular templates and electroless deposition. This method enables synthesis of nanoporous metal structures for catalysis and energy applications.

Gyroid Nickel Nanostructures from Diblock Copolymer Supramolecules

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