Name: synthesis of platinum-nickel nanowires and optimization for oxygen reduction performance
Uploaded: 2018-04-27T12:30:00
Description: Watch this Scientific Journal Video about Synthesis of Platinum-nickel Nanowires and Optimization for Oxygen Reduction Performance at JoVE.com

Financial support was provided by the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy under contract number DE-AC36-08GO28308 to NREL.

1. Synthesis of Pt-Ni Nanowires
<ol>
	<li>To begin the displacement process, suspend the nickel nanowire template in water and heat it to 90 &#176;C.
	<ol>
		<li>Add 40 mg of commercially available, nickel nanowires to 20 mL of deionized water in a 50 mL centrifuge tube. Sonicate it for 5 min. 
		&#8203;NOTE: The nanowires are approximately 150-250 nm in diameter and 100-200 &#181;m in length.</li>
		<li>Transfer the suspended nanowires to a 250 mL glass round bottom flask and add 60 mL of deionized water. Heat th...

<ol>
	<li>Bregoli, L. J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Influence+of+Platinum+Crystallite+Size+on+Electrochemical+Reduction+of+Oxygen+in+Phosphoric-Acid.">Influence of Platinum Crystallite Size on Electrochemical Reduction of Oxygen in Phosphoric-Acid.</a> Electrochim. Acta. 23 (6), 489-492 (1978).</li><li>Debe, M. K., Parsonage, E. E. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Nanostructured+electrode+membranes.">Nanostructured electrode membranes.</a> US patent. , (1994).</li><li>Papandrew, A. 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M., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Platinum-Coated+Nickel+Nanowires+as+Oxygen-Reducing+Electrocatalysts.">Platinum-Coated Nickel Nanowires as Oxygen-Reducing Electrocatalysts.</a> ACS Cat. 4 (4), 1114-1119 (2014).</li><li>Alia, S. M., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Exceptional+Oxygen+Reduction+Reaction+Activity+and+Durability+of+Platinum-Nickel+Nanowires+through+Synthesis+and+Post-Treatment+Optimization.">Exceptional Oxygen Reduction Reaction Activity and Durability of Platinum-Nickel Nanowires through Synthesis and Post-Treatment Optimization.</a> ACS Omega. 2 (4), 1408-1418 (2017).</li><li>Norskov, J., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Origin+of+the+Overpotential+for+Oxygen+Reduction+at+a+Fuel-Cell+Cathode.">Origin of the Overpotential for Oxygen Reduction at a Fuel-Cell Cathode.</a> J. Phys. Chem. B. 108 (46), 17886-17892 (2004).</li><li>Sha, Y., Yu, T. H., Merinov, B. V., Shirvanian, P., Goddard, W. 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Funct. Mater. 20 (21), 3742-3746 (2010).</li><li>Alia, S. M., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Platinum+Coated+Copper+Nanowires+and+Platinum+Nanotubes+as+Oxygen+Reduction+Electrocatalysts.">Platinum Coated Copper Nanowires and Platinum Nanotubes as Oxygen Reduction Electrocatalysts.</a> ACS Cat. 3 (3), 358-362 (2013).</li><li>Alia, S. M., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Platinum-Coated+Cobalt+Nanowires+as+Oxygen+Reduction+Reaction+Electrocatalysts.">Platinum-Coated Cobalt Nanowires as Oxygen Reduction Reaction Electrocatalysts.</a> ACS Cat. 4 (8), 2680-2686 (2014).</li><li>Alia, S. 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These protocols have been used to produce extended surface electrocatalysts with both high surface areas and specific activities in the oxygen reduction reaction8. By depositing Pt onto nanostructured templates, the nanowires avoided low coordinated sites and minimize particle size effects, producing specific activities more than 12 times greater than carbon-supported Pt nanoparticles. Using galvanic displacement as the synthesis approach also produced an approximate coating on the Ni template<sup...

Proton exchange membrane fuel cells are partially limited by the amount and cost of platinum required in the catalyst layer, which can account for half of fuel cell costs1. In fuel cells, nanomaterials are typically developed as oxygen reduction catalysts, since the reaction is kinetically slower than hydrogen oxidation. Carbon-supported Pt nanoparticles are often used as oxygen reduction electrocatalysts due to their high surface area; however, they have specific selective activity and are prone to durability losses.
Extended thin films offer potential benefits to nanoparticles by addressing these limitations. Extended Pt surfaces typically produce specific activities an order of magnitude greater than nanoparticles, by limiting less active facets and particle size effects, and have been shown to be durable under potential cycling2,3,4. While high mass activities have been achieved in extended surface electrocatalysts, improvements have been made primarily through increases in specific activity, and the catalyst type has been limited to Pt with a low surface area (10 m2 gPt-1)3,4,5.
Spontaneous galvanic displacement combines the aspects of corrosion and electrodeposition6. The process is generally governed by the standard redox potentials of the two metals, and the deposition typically occurs when the metal cation is more reactive than the template. The displacement tends to produce nanostructures that match the template morphology. By applying this technique to extended nanostructures, Pt-based catalysts can be formed that take advantage of the high specific oxygen reduction activity of extended thin films. Through partial displacement, small amounts of Pt have been deposited, and have produced materials with high surface areas (&#62; 90 m2 gPt-1)7,8.
These protocols involve hydrogen annealing to mix Pt and Ni zones and improve oxygen reduction activity. A number of studies have theoretically established the mechanism and experimentally confirmed an alloying effect in Pt oxygen reduction. Modeling and correlating Pt-OH and Pt-O binding to oxygen reduction activity suggest that Pt improvements can be made through lattice compression9,10. Alloying Pt with smaller transition metals has confirmed this benefit, and Pt-Ni has been investigated in a number of forms, including polycrystalline, faceted electrodes, nanoparticles, and nanostructures11,12,13,14.
Galvanic displacement has been used in Pt-oxygen reduction catalyst development with a variety of other templates, including silver, copper, and cobalt nanostructures15,16,17. The synthesis technique has also been used in the deposition of other metals and has produced electrocatalysts for fuel cells, electrolyzers, and the electrochemical oxidation of alcohols18,19,20,21. Similar protocols can also be adapted for the synthesis of nanomaterials with a wider range of electrochemical applications.

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		<tr height="40">
			<td height="40" style="height:40px;width:215px;">Nickel nanowires</td>
			<td style="width:300px;">Plasmachem GmbH</td>
			<td style="width:167px;"></td>
			<td style="width:167px;"></td>
		</tr>
		<tr height="40">
			<td height="40" style="height:40px;">250 mL round bottom flask</td>
			<td>Ace Glass</td>
			<td></td>
			<td></td>
		</tr>
		<tr height="40">
			<td height="40" style="height:40px;">Hot plate</td>
			<td>VWR International</td>
			<td></td>
			<td></td>
		</tr>
		<tr height="40">
			<td height="40" style="height:40px;">Mineral oil</td>
			<td>VWR International</td>
			<td></td>
			<td></td>
		</tr>
		<tr height="40">
			<td height="40" style="height:40px;">Potassium tetrachloroplatinate</td>
			<td>Sigma Aldrich</td>
			<td></td>
			<td></td>
		</tr>
		<tr height="40">
			<td height="40" style="height:40px;">Syringe pump</td>
			<td>New Era Pump Systems</td>
			<td></td>
			<td></td>
		</tr>
		<tr height="40">
			<td height="40" style="height:40px;">Rotator</td>
			<td>Arrow Engineering</td>
			<td></td>
			<td></td>
		</tr>
		<tr height="40">
			<td height="40" style="height:40px;">Teflon paddle</td>
			<td>Ace Glass</td>
			<td></td>
			<td></td>
		</tr>
		<tr height="40">
			<td height="40" style="height:40px;">Glass shaft</td>
			<td>Ace Glass</td>
			<td></td>
			<td></td>
		</tr>
		<tr height="40">
			<td height="40" style="height:40px;">Split hinge tubular furnace</td>
			<td>Lindberg</td>
			<td></td>
			<td>Customized in-house</td>
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			<td height="40" style="height:40px;">Schlenk line</td>
			<td>Ace Glass</td>
			<td></td>
			<td></td>
		</tr>
		<tr height="40">
			<td height="40" style="height:40px;">Condensers</td>
			<td>VWR International</td>
			<td></td>
			<td></td>
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			<td height="40" style="height:40px;">Nitric acid</td>
			<td>Fisher Scientific</td>
			<td></td>
			<td></td>
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			<td height="40" style="height:40px;">2-propanol</td>
			<td>Fisher Scientific</td>
			<td></td>
			<td></td>
		</tr>
		<tr height="40">
			<td height="40" style="height:40px;">Nafion ionomer (5 wt. %)</td>
			<td>Sigma Aldrich</td>
			<td></td>
			<td></td>
		</tr>
		<tr height="40">
			<td height="40" style="height:40px;">Glassy carbon working electrode</td>
			<td>Pine Instrument Company</td>
			<td></td>
			<td></td>
		</tr>
		<tr height="40">
			<td height="40" style="height:40px;">RDE glassware</td>
			<td>Precision Glassblowing</td>
			<td></td>
			<td>Customized in-house</td>
		</tr>
		<tr height="40">
			<td height="40" style="height:40px;">Platinum wire</td>
			<td>Alfa Aesar</td>
			<td></td>
			<td>Customized in-house</td>
		</tr>
		<tr height="40">
			<td height="40" style="height:40px;">Platinum mesh</td>
			<td>Alfa Aesar</td>
			<td></td>
			<td>Customized in-house</td>
		</tr>
		<tr height="40">
			<td height="40" style="height:40px;">MSR Rotator</td>
			<td>Pine Instrument Company</td>
			<td></td>
			<td></td>
		</tr>
		<tr height="40">
			<td height="40" style="height:40px;">Potentiostat</td>
			<td>Metrohm Autolab</td>
			<td></td>
			<td></td>
		</tr>
	</tbody>
</table>

synthesis of platinum-nickel nanowires and optimization for oxygen reduction performance

Platinum-nickel (Pt-Ni) nanowires were developed as fuel cell electrocatalysts, and were optimized for the performance and durability in the oxygen reduction reaction. Spontaneous galvanic displacement was used to deposit Pt layers onto Ni nanowire substrates. The synthesis approach produced catalysts with high specific activities and high Pt surface areas. Hydrogen annealing improved Pt and Ni mixing and specific activity. Acid leaching was used to preferentially remove Ni near the nanowire surface, and oxygen annealing was used to stabilize near-surface Ni, improving durability and minimizing Ni dissolution. These protocols detail the optimization of each post-synthesis processing step, including hydrogen annealing to 250 &#176;C, exposure to 0.1 M nitric acid, and oxygen annealing to 175 &#176;C. Through these steps, Pt-Ni nanowires produced increased activities more than an order of magnitude than Pt nanoparticles, while offering significant durability improvements. The presented protocols are based on Pt-Ni systems in the development of fuel cell catalysts. These techniques have also been used for a variety of metal combinations, and can be applied to develop catalysts for a number of electrochemical processes.

Spontaneous galvanic displacement of Ni nanowires with Pt, using the specified amount, produced Pt-Ni nanowires that were 7.3 wt. % Pt (Figure 1 and Figure 2A). Some modification to the amount of Pt precursor may be required to reach the optimum Pt loading. Pt displacement is sensitive to the thickness of the surface Ni oxide layer, which can vary based on template age (air exposure) and upstream variability<sup ...

Watch this Scientific Journal Video about Synthesis of Platinum-nickel Nanowires and Optimization for Oxygen Reduction Performance at JoVE.com

Synthesis of Platinum-nickel Nanowires and Optimization for Oxygen Reduction Performance

&#160; The protocol describes the synthesis and electrochemical testing of platinum-nickel nanowires. Nanowires were synthesized by the galvanic displacement of a nickel nanowire template. Post-synthesis processing, including hydrogen annealing, acid leaching, and oxygen annealing were used to optimize nanowire performance and durability in the oxygen reduction reaction.

Platinum-nickel (Pt-Ni) nanowires were developed as fuel cell electrocatalysts, and were optimized for the performance and durability in the oxygen ...

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