Name: reductive electropolymerization of a vinyl-containing poly-pyridyl complex on glassy carbon and fluorine-doped tin oxide electrodes
Uploaded: 2015-01-30T15:00:00
Description: Watch this Scientific Journal Video about Reductive Electropolymerization of a Vinyl-containing Poly-pyridyl Complex on Glassy Carbon and Fluorine-doped Tin Oxide Electrodes at JoVE.com

We acknowledge the Virginia Military Institute (VMI) Department of Chemistry for support of electrochemical experiments and instrumentation (L.S.C. and J.T.H.). The VMI Office of the Dean of Faculty supported production fees associated with JoVE publications. We acknowledge the UNC EFRC: Center for Solar Fuels, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DE-SC0001011, for support of compound synthesis and materials characterization (D.P.H).

1. Synthesize 1
Synthesize&#160;1 (PhTpy is 4&#39;-phenyl-2,2&#39;:6&#39;,2&#39;&#39;-terpyridine; 5,5&#8217;-dvbpy is 5,5&#39;-divinyl-2,2&#39;-bipyridine; Figure 4) according to the procedure outlined previously.18
2. Prepare 1.3 mM Monomer Solution of 1 in an Electrolyte Solution
<ol>
	<li>Prepare a 0.1 M stock electrolyte solution of tetra-n-butylammonium hexafluorophosphate,...

<ol>
	<li>Abru&#241;a, H. D. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Coordination+chemistry+in+two+dimensions:+chemically+modified+electrodes.">Coordination chemistry in two dimensions: chemically modified electrodes.</a> Coordination Chemistry Reviews. 86, 135-189 (1988).</li><li>Waltman, R. J., Bargon, J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Electrically+conducting+polymers:+a+review+of+the+electropolymerization+reaction,+of+the+effects+of+chemical+structure+on+polymer+film+properties,+and+of+applications+towards+technology.">Electrically conducting polymers: a review of the electropolymerization reaction, of the effects of chemical structure on polymer film properties, and of applications towards technology.</a> Canadian Journal of Chemistry. 64, 76-95 (1986).</li><li>Zhong, Y. -. 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Photochemically produced molecular voids.</a> Inorganic Chemistry. 31, 5521-5525 (1992).</li><li>Devenney, 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=Excited+State+Interactions+in+Electropolymerized+Thin+Films+of+Ru(II).">Excited State Interactions in Electropolymerized Thin Films of Ru(II).</a> Os(II), and Zn(II) Polypyridyl Complexes. The Journal of Physical Chemistry A. 101, 4535-4540 (1997).</li><li>Moss, J. A., 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=Sensitization+and+Stabilization+of+TiO2+Photoanodes+with+Electropolymerized+Overlayer+Films+of+Ruthenium+and+Zinc+Polypyridyl+Complexes:+A+Stable+Aqueous+Photoelectrochemical+Cell.">Sensitization and Stabilization of TiO2 Photoanodes with Electropolymerized Overlayer Films of Ruthenium and Zinc Polypyridyl Complexes: A Stable Aqueous Photoelectrochemical Cell.</a> Inorganic Chemistry. 43, 1784-1792 (2004).</li><li>Yang, J., Sykora, M., Meyer, T. J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Electropolymerization of Vinylbipyridine Complexes of Ruthenium(II) and Osmium(II) in SiO2 Sol&#8722;Gel Films. Inorganic Chemistry. 44, 3396-3404 (2005).</li><li>Nie, H. -. J., Shao, J. -. Y., Wu, J., Yao, J., Zhong, Y. -. W. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Synthesis+and+Reductive+Electropolymerization+of+Metal+Complexes+with+5,5&#8242;-Divinyl-2,2&#8242;-Bipyridine.">Synthesis and Reductive Electropolymerization of Metal Complexes with 5,5&#8242;-Divinyl-2,2&#8242;-Bipyridine.</a> Organometallics. 31, 6952-6959 (2012).</li><li>Yao, C. -. J., Zhong, Y. -. W., Nie, H. -. J., Abru&#241;a, H. D., Yao, J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Near-IR+Electrochromism+in+Electropolymerized+Films+of+a+Biscyclometalated+Ruthenium+Complex+Bridged+by+1,2,4,5-Tetra(2-pyridyl)benzene.">Near-IR Electrochromism in Electropolymerized Films of a Biscyclometalated Ruthenium Complex Bridged by 1,2,4,5-Tetra(2-pyridyl)benzene.</a> Journal of the American Chemical Society. 133, 20720-20723 (2011).</li><li>Harrison, D. P., 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=Coordination+Chemistry+of+Single-Site+Catalyst+Precursors+in+Reductively+Electropolymerized+Vinylbipyridine+Films.">Coordination Chemistry of Single-Site Catalyst Precursors in Reductively Electropolymerized Vinylbipyridine Films.</a> Inorganic Chemistry. 52, 4747-4749 (2013).</li><li>Calvert, J. 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=Synthetic+and+mechanistic+investigations+of+the+reductive+electrochemical+polymerization+of+vinyl-containing+complexes+of+iron(II),+ruthenium(II),+and+osmium(II).">Synthetic and mechanistic investigations of the reductive electrochemical polymerization of vinyl-containing complexes of iron(II), ruthenium(II), and osmium(II).</a> Inorganic Chemistry. 22, 2151-2162 (1983).</li><li>Moss, J. A., Argazzi, R., Bignozzi, C. A., Meyer, T. J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Electropolymerization+of+Molecular+Assemblies.">Electropolymerization of Molecular Assemblies.</a> Inorganic Chemistry. 36, 762-763 (1997).</li><li>Deronzier, A., Eloy, D., Jardon, P., Martre, A., Moutet, J. -. 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W. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Electropolymerization+of+vinylpyridine+and+vinylbipyridine+complexes+of+iron+and+ruthenium:+homopolymers,+copolymers,+reactive+polymers.">Electropolymerization of vinylpyridine and vinylbipyridine complexes of iron and ruthenium: homopolymers, copolymers, reactive polymers.</a> Inorganic Chemistry. 21, 2153-2161 (1982).</li><li>Younathan, J. N., Wood, K. S., Meyer, T. J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Electrocatalytic+reduction+of+nitrite+and+nitrosyl+by+iron(III)+protoporphyrin+IX+dimethyl+ester+immobilized+in+an+electropolymerized+film.">Electrocatalytic reduction of nitrite and nitrosyl by iron(III) protoporphyrin IX dimethyl ester immobilized in an electropolymerized film.</a> Inorganic Chemistry. 31, 3280-3285 (1992).</li><li>Ikeda, T., Schmehl, R., Denisevich, P., Willman, K., Murray, R. W. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Permeation+of+electroactive+solutes+through+ultrathin+polymeric+films+on+electrode+surfaces.">Permeation of electroactive solutes through ultrathin polymeric films on electrode surfaces.</a> Journal of the American Chemical Society. 104, 2683-2691 (1982).</li><li>Concepcion, J. 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Electropolymerization offers a large range of controllable variables that are not common to other techniques. In addition to standard reaction variables like reagent (monomer) concentration, temperature, solvent, etc., electropolymerization can be additionally controlled by electrochemical experiment parameters common to electrochemical methods. CV scan rates, switching potentials, and number of cycles affect the deposition of electropolymers. For example, as the number of cycles through the ligand reduction wav...

Electropolymerization is a polymerization technique that utilizes an applied potential to initiate the polymerization of monomeric precursors directly at the surface of an electrode and has been exploited to produce thin electroactive and/or photochemically active polypyridyl films on electrode and semiconductor surfaces.1-4 Electrocatalysis,5-10 electron transfer,11,12 photochemistry,13-16 electrochromism,17 and coordination chemistry18 have been investigated in electropolymerized films. This technique was first developed at the University of North Carolina in a Meyer-Murray collaboration for the electropolymerization of vinyl3,5,7,8,11-15,19,20 and pyrrole6,9,21-24 derivatized metal complexes on a variety of conducting substrates. Figure 1 presents a number of common pyridyl based ligands that, when coordinated to metal complexes, have produced electropolymers. In reductive electropolymerization, electropolymerization of vinyl containing compounds occurs upon the reduction of pyridyl ligands conjugated to vinyl groups, while with pyrrole-functionalized ligands, electropolymerization is initiated by oxidation of the pyrrole moieties, resulting in oxidative electropolymerization (Figure 2). Electropolymerization technology was developed with the goal of providing a generalized methodology for directly attaching virtually any transition metal complex to any electrode. The versatility of the method opens the door to numerous investigations of electropolymer modified electrodes.
In contrast to other attachment strategies, which involve direct bonding to the electrode, electropolymerization offers the advantage of not requiring electrode surface pre-modification. Therefore it can be applied to any number of conducting substrates, regardless of surface composition or morphology.4,10,25,26 This versatility is a result of changing physical properties as the polymer length grows; the monomers are soluble in the electrolytic solution but as polymerization occurs and cross-linking rigidifies the film, precipitation and physical adsorption the electrode surface occurs (Figure 3).27
Compared to oxide surface-bound carboxylate, which are unstable on oxide surfaces in water, or phosphonate-derivatized complexes, which are unstable at elevated pH&#39;s, commonly used in solar fuels research, these interfacial electrode-polymer film structures offer the added benefit of stability in a variety of media including organic solvents and water over a large pH range (0-14).28-30 Electropolymerization can also deposit films with large ranges of apparent surface coverages, from sub-monolayer to dozens or hundreds of equivalents monolayer, whereas carboxylate or phosphonate-derivatized complexes-interface structures are limited to monolayer surface coverages.
Although any number of vinyl or pyrrole containing pyridyl and polypyridyl compounds are capable of polymerization, [RuII(PhTpy)(5,5&#8217;-dvbpy)(MeCN)](PF6)2, (1; PhTpy is 4&#39;-phenyl-2,2&#39;:6&#39;,2&#39;&#39;-terpyridine; 5,5&#8217;-dvbpy is 5,5&#39;-divinyl-2,2&#39;-bipyridine; Figure 4) will be utilized as a model complex to demonstrate reductive electropolymerization on glassy carbon and fluorine-doped tin oxide, FTO, electrodes in this report. 1 is an example of a modern electropolymer precursor that has potential electrocatalytic applications and, due to its metal-to-ligand charge transfer, MLCT, absorption spectrum lying in the visible region of the light spectrum, can be investigated with UV-Vis spectroscopy.18,30 Please note that some results presented here for 1 have already been published in a slightly modified form.18

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			<td height="21" style="height:21px;width:384px;">Name of Reagent/ Equipment</td>
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			<td height="20" style="height:20px;">Tetrabutylammonium hexafluorophosphate for electrochemical analysis, &#8805;99.0%,&#160;</td>
			<td>Sigma-Aldrich</td>
			<td>86879-25G</td>
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			<td height="20" style="height:20px;width:384px;">Acetonitrile&#160;(Optima LC/MS), Fisher Chemical</td>
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			<td height="20" style="height:20px;">3 mm dia. Glassy Carbon Working Electrode</td>
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			<td height="20" style="height:20px;">Non-Aqueous Ag/Ag+ Reference Electrode w/ porous Teflon Tip</td>
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reductive electropolymerization of a vinyl-containing poly-pyridyl complex on glassy carbon and fluorine-doped tin oxide electrodes

Controllable electrode surface modification is important in a number of fields, especially those with solar fuels applications. Electropolymerization is one surface modification technique that electrodeposits a polymeric film at the surface of an electrode by utilizing an applied potential to initiate the polymerization of substrates in the Helmholtz layer. This useful technique was first established by a Murray-Meyer collaboration at the University of North Carolina at Chapel Hill in the early 1980s and utilized to study numerous physical phenomena of films containing inorganic complexes as the monomeric substrate. Here, we highlight a procedure for coating electrodes with an inorganic complex by performing reductive electropolymerization of the vinyl-containing poly-pyridyl complex onto glassy carbon and fluorine doped tin oxide coated electrodes. Recommendations on electrochemical cell configurations and troubleshooting procedures are included. Although not explicitly described here, oxidative electropolymerization of pyrrole-containing compounds follows similar procedures to vinyl-based reductive electropolymerization but are far less sensitive to oxygen and water.

Electropolymer growth is most easily recognized when observing the progress of the prescribed CV experiment (Protocol Text STEP 3.3.2). Figure 5 exemplifies electropolymer growth on a 0.071 cm2 (3 mm diameter) glassy carbon electrode with 1. The first cycle of the experiment produces a voltammogram roughly resembling that which is expected for a ruthenium solution of similar concentration (Figure 5, black trace) but upon successive cycles, through the 1st...

Watch this Scientific Journal Video about Reductive Electropolymerization of a Vinyl-containing Poly-pyridyl Complex on Glassy Carbon and Fluorine-doped Tin Oxide Electrodes at JoVE.com

Reductive Electropolymerization of a Vinyl-containing Poly-pyridyl Complex on Glassy Carbon and Fluorine-doped Tin Oxide Electrodes

A procedure for performing reductive electropolymerization of vinyl-containing compounds onto glassy carbon and fluorine doped tin-oxide coated electrodes is presented. Recommendations on electrochemical cell configurations and troubleshooting procedures are included. Although not explicitly described here, oxidative electropolymerization of pyrrole-containing compounds follows similar procedures to vinyl-based reductive electropolymerization.

Controllable electrode surface modification is important in a number of fields, especially those with solar fuels applications. Electropolymerization is ...

Research

JoVE Journal

Chemistry

Improved In-gel Reductive &#946;-Elimination for Comprehensive O-linked and Sulfo-glycomics by Mass Spectrometry

Separation of proteins by SDS-PAGE followed by in-gel proteolytic digestion of resolved protein bands has produced high-resolution proteomic analysis of ...

Atomically Defined Templates for Epitaxial Growth of Complex Oxide Thin Films

Atomically defined substrate surfaces are prerequisite for the epitaxial growth of complex oxide thin films. In this protocol, two approaches to obtain ...

Transport of Surface-modified Carbon Nanotubes through a Soil Column

Carbon nanotubes (CNTs) are widely manufactured nanoparticles, which are being utilized in a number of consumer products, such as sporting goods, ...

Photochemical Oxidative Growth of Iridium Oxide Nanoparticles on CdSe@CdS Nanorods

We demonstrate a procedure for the photochemical oxidative growth of iridium oxide catalysts on the surface of seeded cadmium selenide-cadmium sulfide ...

On-line Analysis of Nitrogen Containing Compounds in Complex Hydrocarbon Matrixes

The shift to heavy crude oils and the use of alternative fossil resources such as shale oil are a challenge for the petrochemical industry. The ...

Investigations on the Ga(III) Complex of EOB-DTPA and Its 68Ga Radiolabeled Analogue

Investigations on the GaIII Complex of EOB-DTPA and Its 68Ga Radiolabeled Analogue

We demonstrate a method for the isolation of EOB-DTPA (3,6,9-triaza-3,6,9-tris(carboxymethyl)-4-(ethoxybenzyl)-undecanedioic acid) from its Gd(III) ...

Grafting Multiwalled Carbon Nanotubes with Polystyrene to Enable Self-Assembly and Anisotropic Patchiness

We demonstrate a straightforward protocol to graft pristine multiwalled carbon nanotubes (MWCNTs) with polystyrene (PS) chains at the sidewalls through a ...

Electrochemical Impedance Spectroscopy as a Tool for Electrochemical Rate Constant Estimation

Electrochemical impedance spectroscopy (EIS) was used for advanced characterization of organic electroactive compounds along with cyclic voltammetry (CV). ...

Solvothermal Synthesis of MIL-96 and UiO-66-NH2 on Atomic Layer Deposited Metal Oxide Coatings on Fiber Mats

Solvothermal Synthesis of MIL-96 and UiO-66-NH2 on Atomic Layer Deposited Metal Oxide Coatings on Fiber Mats

Metal-organic frameworks (MOFs), which contain reactive metal clusters and organic ligands allowing for large porosities and surface areas, have proven ...

Negative Additive Manufacturing of Complex Shaped Boron Carbides

Boron carbide (B4C) is one of the hardest materials in existence. However, this attractive property also limits its machineability into complex shapes for ...