Electrodeposition of Pt Nanoparticle Catalysts from H2Pt(OH)6 and

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Electrodeposition of Pt Nanoparticle Catalysts from HPt(OH) and Their Application in PEM Fuel Cells 2

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Jonathan James Burk, and Steven K. Buratto J. Phys. Chem. C, Just Accepted Manuscript • DOI: 10.1021/jp405302x • Publication Date (Web): 16 Aug 2013 Downloaded from http://pubs.acs.org on August 17, 2013

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The Journal of Physical Chemistry

Electrodeposition of Pt Nanoparticle Catalysts from H2Pt(OH)6 and Their Application in PEM Fuel Cells Jonathan J. Burk and Steven K. Buratto* Department of Chemistry and Biochemistry, University of California, Santa Barbara, CA 931069510 *Corresponding author. Tel: 1-805-893-3393. E-mail: [email protected].

ACS Paragon Plus Environment

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Abstract We report the electrochemical deposition of Pt nanoparticles from platinic acid H2[Pt(OH)6] using pulse potential deposition (PPD). We are able to control the size, morphology and loading of platinum nanoparticles from H2[Pt(OH)6] by controlling the deposition parameters such as the pH of the plating solution, the pulse potential, the pulse width and the duty cycle of the pulse sequence. We show that a high density of Pt nanoparticles electrodeposited can be produced on both planar and non-planar electrode supports with high surface area and high catalytic activity. Finally, we show that fuel cell electrodes can be produced using H2[Pt(OH)6] as the source of Pt via our optimized PPD technique. The fuel cells produced from these electrodes are highly efficient with less than half the Pt content of commercially available fuel cells, which results in a gravimetric power more than twice that of fuel cells produced using commercially-available electrodes.

KEYWORDS. nucleation, growth, electrocatalyst, electrochemical deposition, platinic acid, dihydrogen hexahydroxyplatinate(IV).


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1. Introduction Electrochemical deposition of metals has been previously reported as a potential method to prepare electrocatalysts on the nanoscale.1–28 The ability of these methods to control nucleation density and morphology has proven it to be an important advantage for preparing electrocatalyst layers as the catalytic activity is strongly dependent on the size of the nanoparticles and their distribution within the catalyst layer.

In particular, the catalyst layers in proton exchange

membrane (PEM) fuel cells require Pt nanoparticles a few nanometers in size, highly dispersed throughout the catalyst layer. Electrochemical methods for producing Pt nanoparticles have been proposed that utilize either constant current/potential or pulse current/potential methods.4–24,28 While it is possible to produce Pt particles of the appropriate size using these methods, electrodes produced via direct electrodeposition do not perform at the same level as electrodes produced by Pt incorporation (as is done for commercially available fuel cell electrodes). One possible explanation for the lack of performance is poisoning of the catalyst layer by Cl− ions.29 Most of the Pt electrochemical deposition studies have utilized a plating solution containing chloroplatinic acid (H2PtCl6) in an acid electrolyte.2,3,7–27 According to Feltham et al.,30 the electrochemical deposition of Pt from H2PtCl6 and their corresponding standard reduction potentials31 are as follows: PtIVCl62− + 2 e− → PtIICl42− + 2 Cl− PtIVCl62− + 4 e− → Pt0 + 6 Cl−

E° = 0.529 VAg/AgCl

(i)


(ii)


(iii)

and/or PtIICl42− + 2 e− → Pt0 + 4 Cl−

The cathodic processes that take place at the electrode-solution interface include the formation of Cl– ions within the vicinity of the electrodeposited Pt nanoparticle. Studies have shown that Cl– ions can have a poisoning effect on Pt electrocatalysts. The presence of Cl– ions: (1) results in


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adsorption of Cl– ions onto Pt, blocking the active sites32–34, (2) reducing further deposition of Pt from the H2PtCl6 plating solution35, and (3) increase the rate of Pt degradation29,36–38. Thus, alternative Pt plating solutions are necessary to overcome the negative impact of Cl– ions on Pt nanoparticle electrocatalysis. In this study, we report the electrochemical deposition of Pt nanoparticles from platinic acid, H2[Pt(OH)6], using pulse potential deposition (PPD). Deposition from the H2[Pt(OH)6] plating solution resulted in the formation of Pt nanoparticles free from the deleterious effects of Cl–. By controlling the deposition parameters such as pH, pulse potential, pulse width and duty cycle we were able to produce Pt nanoparticles with well-defined size, morphology and density from H2[Pt(OH)6].

Finally, we show that Pt nanoparticles produced via electrodeposition from

H2[Pt(OH)6] can be utilized as electrocatalysts for fuel cell electrodes. We show that our PPD technique can create catalyst layers with ideal morphology and significantly reduced platinum loading relative to commercially-available electrodes. 2. Experimental Methods The following chemicals were used in this study: dihydrogen hexahydroxyplatinate(IV) H2[Pt(OH)6] or platinic acid (Aldrich, 99.99 %), H2SO4 (EMD, 95.0 - 98.0 %), trace metal grade H2SO4 (Fischer Scientific, 99 %), trace metal grade HNO3 (Fischer Scientific, 99 %), isopropanol (Fischer Scientific, 99.9 %), ethanol (Gold Shield Chemical Company, 200 proof), Nafion® solution (Dupont®, 5 wt %), and deionized water. Pt nanoparticles were electrochemically deposited onto fluorine doped tin oxide, FTO (Pilkington Glass Company, TEC-8), by reduction from the H2[Pt(OH)6] plating solution using the three-electrode electrochemical cell shown in Figure 1. The planar dimensions and the consistency of the FTO electrode surface allowed the study Pt nanoparticles deposited from H2Pt(OH)6 to be easily characterized with SEM and CV than on the amorphous carbon surface


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(Vulcan XC-72R) of a gas diffusion electrode (Fuel Cell Store, Inc., ELAT 1200 W). The cell consisted of a FTO working electrode, platinum mesh counter electrode (Alfa Aesar, 99.9999%), and Ag|AgCl|KCl(sat.) reference electrode (0.197 V vs. SHE). The potential of the working electrode was computer-controlled by a potentiostat (Princeton Applied Research, VSP model) using EC-Lab software. All potentials are reported in reference to the Ag|AgCl|KCl(sat.) reference electrode unless stated otherwise. The cell depicted in Fig. 1 was designed to expose a 1 cm2 geometric area of FTO or other planar electrode surface to the plating solution. The distance between the reference electrode and working electrode was fixed to approximately two times the outer diameter of the tip of the Luggin capillary to ensure the solution resistance was minimal. The H2[Pt(OH)6] plating solution was refreshed every 6 hr. All electrochemical experiments were performed under ambient conditions unless stated otherwise.

Figure 1. Schematic representation of the electrochemical cell. The surface area of the deposited Pt nanoparticles was determined using hydrogen adsorption/desorption cyclic voltammetry in the electrochemical cell shown in Fig. 1. The cyclic voltammograms were recorded from − 0.20 V to 1.20 V in 0.5 M H2SO4 electrolyte solution that


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was deaerated with argon.

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The electrochemical surface area (ESA) and the specific

electrochemical surface area (SSA) were calculated from the hydrogen adsorption/desorption waves using standard methods39–41. The ESA and SSA are defined by Equation 1 and 2, respectively:

ESA(cm 2 ) =

QH 210 µ C cm -2

SSA(cm 2g-1 ) =

(1)

QH 210 µ C cm -2 × m Pt

(2)

where QH is the average charge of hydrogen adsorbed on (or desorbed from) the Pt surface determined by integrating the curves from 0.2 V to − 0.2 V, the value of 210 µC cm-2 is the charge of a single hydrogen atom adsorbed on a single Pt atom assuming a monolayer coverage of atomic H on the Pt surface, and mPt is the mass of Pt deposited on the working electrode surface.39 Scanning electron microscopy, SEM (FEI Company, XL-30), and transmission electron microscopy, TEM (FEI Company, T20), were utilized to determine the size and morphology of Pt nanoparticles on the electrode surface. The mass of the deposited Pt nanoparticles was determined by inductively coupled plasma-atomic emission spectroscopy, ICP-AES (Thermo iCAP 6300 model). The deposited Pt nanoparticles were removed from the electrode surface by digestion in ~ 15 g of 20 v/v % aqua regia at 60 °C for 48 h.

3. Results and Discussion The half-reactions that take place during electrochemical deposition of Pt from H2[Pt(OH)6] at the electrode-solution interface are as follows: Cathodic Reactions:


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H2[Pt(OH)6] (cr) + 4 H+ (aq) + 4 e− → Pt (s) + 6 H2O (l)

E° = 0.928 VAg/AgCl42,43

(iv)

and/or 2 H+(aq) + 2 e− → H2 (g)

E° = − 0.197 VAg/AgCl

(v)

Anodic Reaction: 4 H+ (aq) + O2 (g) + 4 e− → 2 H2O (l)


(vi)

Cyclic voltammetry was used to analyze the electrodeposition of Pt nanoparticles from a 5.0 mM H2[Pt(OH)6] + 1.0 M H2SO4 argon-saturated plating solution at a FTO surface during the initial stages of Pt nucleation and growth as seen in Figure 2. The 1st and 2nd sweep of the cyclic voltammograms shown in Fig. 2 were recorded from 0.68 V to − 0.25 V at 10 mV s-1 on FTO. The onset of cathodic current at approximately ~ 0.50 V and subsequent reduction peak (P1) at 0.059 V was attributed to the reduction of H2[Pt(OH)6] to Pt [Reaction (iv)], in agreement with the reduction peak for the [Pt(OH)6]2-/Pt0 redox couple in acidic media.44–48

Figure 2. Cyclic voltammogram recorded on FTO at 10 mV s-1 for Ar-saturated 5.0 mM H2[Pt(OH)6] + 1.0 M H2SO4 plating solution. The 1st sweep is the solid line and 2nd sweep is the dashed line. Inset shows the 1st sweep of a cyclic voltammogram recorded from FTO immersed in 1.0 M H2SO4 at 10 mV s-1. Inset is a cyclic voltammogram recorded in 1.0 M H2SO4.


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The asymmetric shape of peak P1 was attributed to the competition between Pt reduction and H2 evolution as depicted in Reactions (iv) and (v), respectively. The significant increase in cathodic current at peak H1 was a result of hydrogen ions adsorption at the Pt/FTO surface followed by H2 evolution. The peak H2 during the anodic sweep was assigned to the oxidation and desorption of H+ ions from the surface of Pt/FTO. The electrochemical response from hydrogen atoms adsorbing and desorbing on a Pt surface, peaks H1 and H2 respectively, was similar to that observed for a clean Pt surface immersed in H2SO4.39 The 2nd sweep in Fig. 2 (dashed line) shows that the cathodic peak (P1) shifted to a higher potential. The shift of peak P1 (0.059 V) to P2 (0.196 V) from the 1st sweep to the 2nd sweep was due to the presence of Pt nanoparticles on the FTO surface (from the initial sweep), which provide additional sites for Pt reduction during the second sweep. The nucleation and growth of Pt established during the 1st sweep creates a more favorable surface for deposition of Pt than bare FTO.49,50 The increased current at peak H2 during the 2nd anodic sweep was also due to the presence of Pt on the FTO surface, which allowed more hydrogen adsorption and evolution. The shift of peak P1 and the higher current observed for peak H2 indicates growth of the Pt nanoparticles with increased deposition time, and suggests a diffusion-limited process. This hypothesis was tested by probing the dependence of peak P1 on the scan rate. The cyclic voltammograms and scanning electron micrographs (SEM) in Figures 3 and 4 respectively, illustrate the dependence of the scan rate (υ) on peak current, potential at peak current, and particle morphology on a bare FTO surface. The waves of Fig. 3(a) clearly show the shift to higher potential of the peak (P1) with decreasing scan rate, which indicates that formation of Pt nanoparticles [Reaction (iv)] is irreversible.40,51 In addition, the peak current decreased with decreasing scan rate. A plot of the peak current as a function of the square root of the scan rate is


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presented in Fig. 3(b). A linear relationship was clearly observed for the peak current and the square root of the scan rate, which indicates that Reaction (iv) is diffusion-limited.40,52–55

Figure 3. (a) Cyclic voltammograms of the 1st cathodic sweep of an FTO electrode immersed in Ar-saturated 5.0 mM H2[Pt(OH)6] + 1.0 M H2SO4 plating solution collected at various scan rates (e.g. 1, 10, 50 , and 200 mV s-1 respectively) and (b) a plot of the peak current (ip) as a function of the square root of the scan rate (υ1/2). Initially, we used the potential profile shown in Fig. 4(a) to reduce Pt from a 5.0 mM H2[Pt(OH)6] + 1.0 M H2SO4 plating solution. The SEM images of Fig. 4 show the dependence of the particle morphology on the deposition potential (Edep). In each image the total deposition time was kept constant at 30 min (tdep). Using a potential Edep of 165.3 mV, near the onset of the cathodic current shown in Fig. 3(a), resulted in Pt nanoparticles with a spherical morphology [see the image of Fig. 4(b)]. The density of particles was 1.75 × 109 particles cm−2 and the average particle diameter was 198.7 nm. It was possible to reduce the size of the nanoparticles by increasing the deposition potential. The relationship between deposition overpotential and critical


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radius of a nanoparticle is expressed by the electrochemical version of the Kelvin equation:13,15,56,57

rc =

2γ Vm ze 0 η

(3)

where rc is the critical radius, γ is the specific surface energy, Vm is the atomic volume in the crystal, z is the number of elementary charges eo, and |η| is the overpotential (|η|= |Edep – E°Pt(IV)/Pt(0)| ; E°Pt(IV)/Pt(0) = 0.928 VAg/AgCl) According to Eq. (3), when |η| is increased, (Edep 0.100 A cm-2 at 0.6 and 0.5 V. The most important piece of data gleaned from Table 2 was that the electrodeposited fuel cell contained 40 % of Pt loading relative to the control fuel cell. As a result, the electrodeposited fuel cell generated a gravimetric power of 538.8 W g-1 compared to 234.4 W g-1 generated by the control fuel cell at a fixed current density of 0.200 A cm-2.

Table 2. Summary of Pt content and fuel cell performance obtained from ICP-AES analysis and i-V polarization curves.

Electrode

Pt content (mg cm-2)

i @ 0.7 V (A cm-2)a

i @ 0.6 V (A cm-2)a

i @ 0.5 V (A cm-2)a

Pg @ 0.200 A cm-2 (W g-1)b

ETEK

0.5546

0.117

0.300

0.441

234.4

OPPD

0.2190

0.087

0.190

0.324

538.8

a

i, current density; bPg, gravimetric power

4. Conclusions We have shown that electrochemical deposition of Pt nanoparticles is possible from a H2[Pt(OH)6] plating solution. Using a PPD technique it was possible to produce nanometer-scale Pt particles on both planar and three-dimensional substrates. It was found that the optimum pulse parameters for electrodeposition were Eon/Eoff of −/+ 1.0 V, ton of 3 ms, pH of 1.0, and a duty cycle of 50 %. Using these pulse parameters we produced fuel cell electrodes from H2[Pt(OH)6] with an average particle size of 2.46 nm and a narrow size distribution. We showed that


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electrodes produced using our PPD technique had i-V performance close to that of commercial electrodes with 40 % of the Pt loading. Furthermore, our electrodeposited electrodes generated more than twice the gravimetric power density than the commercial electrodes. Finally, our electrodeposition methods are easily scaled up to produce very large are electrodes.

Acknowledgment

This work was funded by the National Science Foundation (Grant no. CHE-1213950). SEM, TEM, and ICP-AES characterization made use of the MRL Shared Experimental Facilities supported by the MRSEC Program of the National Science Foundation (Grant No. DMR 1121053); a member of the NSF-funded Materials Research Facilities Network (www.mrfn.org). Finally, we would like to recognize Ryan Lindeborg and AJ Swoboda for their participation in the early stages of this project.

References


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(1)

Page 28 of 37

Taylor, E. J.; Anderson, E. B.; Vilambi, N. R. K. Preparation of High-Platinum-

Utilization Gas Diffusion Electrodes for Proton-Exchange-Membrane Fuel Cells. J. Electrochem. Soc. 1992, 139, L45–L46. (2)

Ye, J.-H.; Fedkiw, P. S. Electrodeposition of High-surface Area Platinum in a Well

Adherent Nafion Film on Glassy Carbon. Electrochimica Acta 1996, 41, 221–231. (3)

Guo, D.-J.; Li, H.-L. High Dispersion and Electrocatalytic Properties of Pt Nanoparticles

on SWNT Bundles. J. Electroanal. Chem. 2004, 573, 197–202. (4)

Thompson, S. D.; Jordan, L. R.; Shukla, A. K.; Forsyth, M. Platinum Electrodeposition

from H3Pt(SO3)2OH Solutions. J. Electroanal. Chem. 2001, 515, 61–70. (5)

Verbrugge, M. W. Selective Electrodeposition of Catalyst within Membrane-Electrode

Structures. J. Electrochem. Soc. 1994, 141, 46–53. (6)

Kim, S.; Park, S.-J. Electrical Signal Effect on Electrochemical Activities of Metal

Catalysts Electrically Deposited on Carbon Nanotubes. Electrochimica Acta 2008, 53, 4082– 4088. (7)

Yasin, H. M.; Denuault, G.; Pletcher, D. Studies of the Electrodeposition of Platinum

Metal from a Hexachloroplatinic Acid Bath. J. Electroanal. Chem. 2009, 633, 327–332. (8)

Miyake, M.; Ueda, T.; Hirato, T. Potentiostatic Electrodeposition of Pt Nanoparticles on

Carbon Black. J. Electrochem. Soc. 2011, 158, D590–D593. (9)

Ayyadurai, S. M.; Choi, Y.-S.; Ganesan, P.; Kumaraguru, S. P.; Popov, B. N. Novel

PEMFC Cathodes Prepared by Pulse Deposition. J. Electrochem. Soc. 2007, 154, B1063–B1073.


28

Page 29 of 37

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(10) Antoine, O.; Durand, R. In Situ Electrochemical Deposition of Pt Nanoparticles on Carbon and Inside Nafion. Electrochem. Solid-State Lett. 2001, 4, A55–A58. (11) Kim, H.; Popov, B. N. Development of Novel Method for Preparation of PEMFC Electrodes. Electrochem. Solid-State Lett. 2004, 7, A71–A74. (12) Gloaguen, F.; Le´ger, J.-M.; Lamy, C. Electrocatalytic Oxidation of Methanol on Platinum Nanoparticles Electrodeposited onto Porous Carbon Substrates. J. Appl. Electrochem. 1997, 27, 1052–1060. (13) Löffler, M.-S.; Groß, B.; Natter, H.; Hempelmann, R.; Krajewski, T.; Divisek, J. Synthesis and Characterization of Catalyst Layers for Direct Methanol Fuel Cell Applications. Phys. Chem. Chem. Phys. 2001, 3, 333–336. (14) Thompson, S. D.; Jordan, L. R.; Forsyth, M. Platinum Electrodeposition for Polymer Electrolyte Membrane Fuel Cells. Electrochimica Acta 2001, 46, 1657–1663. (15) Natter, H.; Hempelmann, R. Tailor-made Nanomaterials Designed by Electrochemical Methods. Electrochimica Acta 2003, 49, 51–61. (16) Kim, H.; Subramanian, N. P.; Popov, B. N. Preparation of PEM Fuel Cell Electrodes using Pulse Electrodeposition. J. Power Sources 2004, 138, 14–24. (17) Bennett, J. A.; Show, Y.; Wang, S.; Swain, G. M. Pulsed Galvanostatic Deposition of Pt Particles on Microcrystalline and Nanocrystalline Diamond Thin-Film Electrodes I. Characterization of As-Deposited Metal/Diamond Surfaces. J. Electrochem. Soc. 2005, 152, E184–E192.


29


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 30 of 37

(18) Paoletti, C.; Cemmi, A.; Giorgi, L.; Giorgi, R.; Pilloni, L.; Serra, E.; Pasquali, M. Electro-deposition on Carbon Black and Carbon Nanotubes of Pt Nanostructured Catalysts for Methanol Oxidation. J. Power Sources 2008, 183, 84–91. (19) Li, J.; Ye, F.; Chen, L.; Wang, T.; Li, J.; Wang, X. A study on Novel Pulse Preparation and Electrocatalytic Activities of Pt/C-Nafion Electrodes for Proton Exchange Membrane Fuel Cell. J. Power Sources 2009, 186, 320–327. (20) Chou, J.; Jayaraman, S.; Ranasinghe, A. D.; McFarland, E. W.; Buratto, S. K.; Metiu, H. Efficient Electrocatalyst Utilization: Electrochemical Deposition of Pt Nanoparticles Using Nafion Membrane as a Template. J. Phys. Chem. B 2006, 110, 7119–7121. (21) Shimazu, K.; Uosaki, K.; Kita, H.; Nodasaka, Y. Structure of Pt Microparticles Dispersed Electrochemically onto Glassy Carbon Electrodes: Examination with the Scanning Tunneling Microscope and the Scanning Electron Microscope. J. Electroanal. Chem. Interfacial Electrochem. 1988, 256, 481–487. (22) Shimazu, K.; Weisshaar, D.; Kuwana, T. Electrochemical Dispersion of Pt Microparticles on Glassy Carbon Electrodes. J. Electroanal. Chem. Interfacial Electrochem. 1987, 223, 223– 234. (23) Hogarth, M. P.; Munk, J.; Shukla, A. K.; Hamnett, A. Performance of Carbon-cloth Bound Porous-carbon Electrodes Containing an Electrodeposited Platinum Catalyst Towards the Electrooxidation of Methanol in Sulphuric Acid Electrolyte. J. Appl. Electrochem. 1994, 24, 85– 88.


30

Page 31 of 37

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(24) Choi, K. H.; Kim, H. S.; Lee, T. H. Electrode Fabrication for Proton Exchange Membrane Fuel Cells by Pulse Electrodeposition. J. Power Sources 1998, 75, 230–235. (25) González-González, I.; Fachini, E. R.; Scibioh, M. A.; Tryk, D. A.; Tague, M.; Abruña, H. D.; Cabrera, C. R. Facet-Selective Platinum Electrodeposition at Free-standing Polycrystalline Boron-Doped Diamond Films. Langmuir 2009, 25, 10329–10336. (26) Lupu, S.; Lakard, B.; Hihn, J.-Y.; Dejeu, J. Novel in situ Electrochemical Deposition of Platinum Nanoparticles by Sinusoidal Voltages on Conducting Polymer Films. Synth. Met. 2012, 162, 193–198. (27) Itaya, K.; Takahashi, H.; Uchida, I. Electrodeposition of Pt Ultramicroparticles in Nafion Films on Glassy Carbon Electrodes. J. Electroanal. Chem. Interfacial Electrochem. 1986, 208, 373–382. (28) Lindeborg, R.; Swoboda, A.; Burk, J.; Buratto, S. Optimization of Platinum Nanoparticles For Proton Exchange Membrane Fuel Cells using Pulse Electrochemical Deposition. Harv. Undergrad. Res. J. 2013, 6, 9–15. (29) Matsuoka, K.; Sakamoto, S.; Nakato, K.; Hamada, A.; Itoh, Y. Degradation of Polymer Electrolyte Fuel Cells Under the Existence of Anion Species. J. Power Sources 2008, 179, 560– 565. (30) Feltham, A. M.; Spiro, M. Platinized Platinum Electrodes. Chem. Rev. 1971, 71, 177– 193. (31) Bard, A. J.; Parsons, R.; Jordan, J. Standard Potentials in Aqueous Solution; 1st ed.; CRC Press, 1985.


31


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 32 of 37

(32) Stamenkovic, V.; M. Markovic, N.; Ross Jr., P. N. Structure-relationships in Electrocatalysis: Oxygen Reduction and Hydrogen Oxidation Reactions on Pt(111) and Pt(100) in Solutions Containing Chloride Ions. J. Electroanal. Chem. 2001, 500, 44–51. (33) Schmidt, T. J.; Paulus, U. A.; Gasteiger, H. A.; Behm, R. J. The Oxygen Reduction Reaction on a Pt/carbon Fuel Cell Catalyst in the Presence of Chloride Anions. J. Electroanal. Chem. 2001, 508, 41–47. (34) Lane, R. F.; Hubbard, A. T. Electrochemistry of Chemisorbed Molecules. III. Determination of the Oxidation State of Halides Chemisorbed on Platinum. Reactivity and Catalytic Properties of Adsorbed Species. J. Phys. Chem. 1975, 79, 808–815. (35) Lu, G.; Zangari, G. Electrodeposition of Platinum on Highly Oriented Pyrolytic Graphite. Part I: Electrochemical Characterization. J. Phys. Chem. B 2005, 109, 7998–8007. (36) Yadav, A. P.; Nishikata, A.; Tsuru, T. Effect of Halogen Ions on Platinum Dissolution Under Potential Cycling in 0.5 M H2SO4 Solution. Electrochimica Acta 2007, 52, 7444–7452. (37) Ofstad, A. B.; Thomassen, M. S.; de la Fuente, J. L. G.; Seland, F.; Moller-Holst, S.; Sunde, S. Assessment of Platinum Dissolution from a Pt/C Fuel Cell Catalyst: An Electrochemical Quartz Crystal Microbalance Study. J. Electrochem. Soc. 2010, 157, B621– B627. (38) Mitsushima, S.; Koizumi, Y.; Uzuka, S.; Ota, K.-I. Dissolution of Platinum in Acidic Media. Electrochimica Acta 2008, 54, 455–460. (39) Electroanalytical Chemistry: A Series of Advances, Vol. 9; Bard, A. J., Ed.; Dekker, Marcel Inc, 1976.


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(40) Bard, A. J.; Faulkner, L. R. Electrochemical Methods: Fundamentals and Applications; Wiley, 2001. (41) Kissinger, P. T.; Heineman, W. R. Laboratory Techniques in Electroanalytical Chem 2nd Edition; CRC Press, 1996. (42) Nagano, Y. Standard Enthalpy of Formation of Platinic Acid. J. Chem. Thermodyn. 2002, 34, 1745–1750. (43) Nagano, Y.; Miyazaki, Y. Standard Gibbs Energy of Formation of Platinic Acid H2Pt(OH)6 in the Crystalline State. J. Chem. Thermodyn. 2002, 34, 409–412. (44) Burke, L. D.; Borodzinski, J. J.; O’Dwyer, K. J. Multilayer Oxide Growth on Platinum Under Potential Cycling Conditions—I. Sulphuric Acid Solution. Electrochimica Acta 1990, 35, 967–973. (45) Burke, L. D.; O’sullivan, J. F. The Stability of Hydrous Oxide Films on Platinum. J. Appl. Electrochem. 1991, 21, 151–157. (46) Burke, L. D.; Buckley, D. T. The Complex Nature of Hydrous Oxide Film Behaviour on Platinum. J. Electroanal. Chem. 1996, 405, 101–109. (47) Burke, L. D.; Murphy, M. M. Effect of Solution pH on Hydrous Oxide Growth and Reduction on Polycrystalline Platinum. J. Electroanal. Chem. Interfacial Electrochem. 1991, 305, 301–312. (48) Burke, L. D.; Buckley, D. T. Anomalous Stability of Acid-grown Hydrous Platinum Oxide Films in Aqueous Media. J. Electroanal. Chem. 1994, 366, 239–251.


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(49) Sheridan, E.; Hjelm, J.; Forster, R. J. Electrodeposition of Gold Nanoparticles on Fluorine-doped Tin Oxide: Control of Particle Density and Size Distribution. J. Electroanal. Chem. 2007, 608, 1–7. (50) Oskam, G.; Long, J. G.; Natarajan, A.; Searson, P. C. Electrochemical Deposition of Metals onto Silicon. J. Phys. Appl. Phys. 1998, 31, 1927. (51) Nicholson, R. S. Theory and Application of Cyclic Voltammetry for Measurement of Electrode Reaction Kinetics. Anal. Chem. 1965, 37, 1351–1355. (52) Sevcik, A. Oscillographic Polarography with Periodical Triangular Voltage. Collect. Czechoslov. Chem. Commun. 1948, 13, 349–377. (53) Randles, J. E. B. A Cathode Ray Polarograph. Part II.—The Current-voltage Curves. Trans. Faraday Soc. 1948, 44, 327–338. (54) Mentar, L.; Khelladi, M. R.; Azizi, A.; Kahoul, A. Effect of Potential on the Early Stages of Nucleation and Growth During Cobalt Electrocrystallization in Sulfate Medium onto FTO Surface. Mater. Lett. 2010, 64, 2403–2406. (55) Nicholson, R. S.; Shain, I. Theory of Stationary Electrode Polarography. Single Scan and Cyclic Methods Applied to Reversible, Irreversible, and Kinetic Systems. Anal. Chem. 1964, 36, 706–723. (56) Budevski, E. B.; Staikov, G. T.; Lorenz, W. J. Electrochemical Phase Formation and Growth: An Introduction to the Initial Stages of Metal Deposition; John Wiley & Sons, 2008. (57) Budevski, E.; Staikov, G.; Lorenz, W. J. Electrocrystallization: Nucleation and Growth Phenomena. Electrochimica Acta 2000, 45, 2559–2574.


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Page 35 of 37

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(58) Milchev, A.; Heerman, L. Electrochemical Nucleation and Growth of Nano- and Microparticles: Some Theoretical and Experimental Aspects. Electrochimica Acta 2003, 48, 2903–2913. (59) Yu, J.; Fujita, T.; Inoue, A.; Sakurai, T.; Chen, M. Electrochemical Synthesis of Palladium Nanostructures with Controllable Morphology. Nanotechnology 2010, 21, 085601. (60) Markov, I.; Boynov, A.; Toschev, S. Screening Action and Growth Kinetics of Electrodeposited Mercury Droplets. Electrochimica Acta 1973, 18, 377–384. (61) Markov, I.; Toschev, S. Growth Kinetics and Screening Action of Mercury Droplets Electrodeposited from Dilute Solutions of Electrolyte. Electrodepos. Surf. Treat. 1975, 3, 385– 397. (62) Markov, I. Saturation Nucleus Density in the Electrodeposition of Metals onto Inert Electrodes I. Theory. Thin Solid Films 1976, 35, 11–20. (63) Markov, I.; Stoycheva, E. Saturation Nucleus Density in the Electrodeposition of Metals onto Inert Electrodes II. Experimental. Thin Solid Films 1976, 35, 21–35. (64) Tsakova, V.; Milchev, A. Spatial Distribution of Electrochemically Deposited Clusters: A Simulation Study. J. Electroanal. Chem. 1998, 451, 211–218. (65) Gunawardena, G.; Hills, G.; Montenegro, I.; Scharifker, B. Electrochemical Nucleation: Part I. General Considerations. J. Electroanal. Chem. Interfacial Electrochem. 1982, 138, 225– 239. (66) Scharifker, B.; Hills, G. Theoretical and Experimental Studies of Multiple Nucleation. Electrochimica Acta 1983, 28, 879–889.


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(67) Hyde, M. E.; Compton, R. G. A Review of the Analysis of Multiple Nucleation with Diffusion Controlled Growth. J. Electroanal. Chem. 2003, 549, 1–12. (68) Budevski, E.; Staikov, G.; Lorenz, W. J. Electrocrystallization: Nucleation and Growth Phenomena. Electrochimica Acta 2000, 45, 2559–2574. (69) Ranasinghe, A. D. Part I: In situ Pulse Electrochemical Deposition of Platinum Nanoparticles for Efficient Catalyst Utilization in Fuel Cells. Part II: Fabrication and Characterization of Polyelectrolyte-quantum Dot Hybrid Structures using Layer-by-layer Self Assembly. Ph.D., University of California, Santa Barbara: United States -- California, 2007. (70) O’Dea, J. R. Probing Ion Conducting Domains and Localizing Catalysts in Proton Exchange Membrane Fuel Cells. Ph.D., University of California, Santa Barbara: United States -California, 2010. (71) Colón-Mercado, H. R.; Kim, H.; Popov, B. N. Durability Study of Pt3Ni1 Catalysts as Cathode in PEM Fuel Cells. Electrochem. Commun. 2004, 6, 795–799.

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Electrodeposition of Pt Nanoparticle Catalysts from H2Pt(OH)6 and

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