scholarly journals Oxygen Reduction Reaction on Polycrystalline Platinum: On the Activity Enhancing Effect of Polyvinylidene Difluoride

Surfaces ◽  
2019 ◽  
Vol 2 (1) ◽  
pp. 69-77
Author(s):  
Alessandro Zana ◽  
Gustav Wiberg ◽  
Matthias Arenz

There have been several reports concerning the performance improving properties of additives, such as polyvinylidene difluoride (PVDF), to the membrane or electrocatalyst layer of proton exchange membrane fuel cells (PEMFC). However, it is not clear if the observed performance enhancement is due to kinetic, mass transport, or anion blocking effects of the PVDF. In a previous investigation using a thin-film rotating disk electrode (RDE) approach (of decreased complexity as compared to membrane electrode assembly (MEA) tests), a performance increase for the oxygen reduction reaction (ORR) could be confirmed. However, even in RDE measurements, reactant mass transport in the catalyst layer cannot be neglected. Therefore, in the present study, the influence of PVDF is re-examined by coating polycrystalline bulk Pt electrodes by PVDF and measuring ORR activity. The results on polycrystalline bulk Pt indicate that the effects of PVDF on the reaction kinetics and anion adsorption are limited, and that the observed performance increase on high surface area Pt/C most likely is due to an erroneous estimation of the electrochemical active surface area (ECSA) from CO stripping and Hupd.

Author(s):  
Busra Ergul-Yilmaz ◽  
Zhiwei Yang ◽  
Assem O. Basurrah ◽  
Mike L. Perry ◽  
Kimberly S Reeves ◽  
...  

Abstract Self-supported nanocolumnar Pt:Ni thin films (TFs) with varying Pt:Ni atomic ratios and Pt mass loadings were produced on a microporous layer (MPL)-like surface composed of carbon particles by high pressure sputtering and examined as oxygen reduction reaction (ORR) electrocatalysts for polymer electrolyte membrane fuel cells. Cauliflower-like microstructures were observed from scanning electron microscopy imaging. Various Pt:Ni atomic ratios were obtained by simply changing the relative deposition power between Pt and Ni source and investigated by X-ray diffraction and quartz crystal microbalance analysis. Electrochemical characterization of the Pt:Ni-TF/MPL-like-layer/glassy-carbon samples was conducted through benchtop cyclic voltammetry and rotating disk electrode measurements. The electrochemically active surface area (ECSA) was found to be between 22-42 m2/g for different Pt:Ni atomic ratios. Lower Pt mass loadings exhibited a higher ECSA and the catalytic activity of all Pt:Ni ratios increased with the increase in Pt mass loading. The ORR activity of the Pt:Ni-TFs increased in the order of 3:1 < 1:1 < 1:3 with exhibiting a specific activity of 1781 µA/cm2 and mass activity of 0.66 A/mg for the Ni-rich film with 1:3 ratio. The catalytic performance of Pt:Ni-TFs were higher than traditional high surface area carbon supported Pt nanoparticles, elemental Pt nanorods, and Pt-Ni nanorods.


2018 ◽  
Vol 8 (10) ◽  
pp. 2672-2685 ◽  
Author(s):  
Rhiyaad Mohamed ◽  
Tobias Binninger ◽  
Patricia J. Kooyman ◽  
Armin Hoell ◽  
Emiliana Fabbri ◽  
...  

Synthesis of Sb–SnO2 supported Pt nanoparticles with an outstanding ECSA for the oxygen reduction reaction.


2011 ◽  
Vol 1311 ◽  
Author(s):  
Wisam J. Khudhayer ◽  
Nancy Kariuki ◽  
Deborah Myers ◽  
Ali Shaikh ◽  
Tansel Karabacak

ABSTRACTIn this work, we investigated the electrocatalytic oxygen reduction reaction (ORR) activity of vertically aligned, single-layer, carbon-free, and single crystal Pt nanorod arrays utilizing cyclic voltammetry (CV) and rotating-disk electrode (RDE) techniques. A glancing angle deposition (GLAD) technique was used to fabricate 200 nm long Pt nanorods, which corresponds to Pt loading of 0.16 mg/cm2, on glassy carbon (GC) electrode at a glancing angle of 85° as measured from the substrate normal. An electrode comprised of conventional carbon-supported Pt nanoparticles (Pt/C) was also prepared for comparison with the electrocatalytic ORR activity and stability of Pt nanorods. CV results showed that the Pt nanorod electrocatalyst exhibits a more positive oxide reduction peak potential compared to Pt/C, indicating that GLAD Pt nanorods are less oxophilic. In addition, a series of CV cycles in acidic electrolyte revealed that Pt nanorods are significantly more stable against electrochemically-active surface area loss than Pt/C. Moreover, room temperature RDE results demonstrated that GLAD Pt nanorods exhibit higher area-specific ORR activity than Pt/C. The enhanced electrocatalytic ORR activity of Pt nanorods is attributed to their larger crystallite size, single-crystal property, and the dominance of (110) crystal planes on the large surface area nanorods sidewalls, which has been found to be the most active plane for ORR. However, the Pt nanorods showed lower mass specific activity than the Pt/C electrocatalyst due to the large diameter of the Pt nanorods.


RSC Advances ◽  
2019 ◽  
Vol 9 (31) ◽  
pp. 17979-17987
Author(s):  
Robin Sandström ◽  
Joakim Ekspong ◽  
Eduardo Gracia-Espino ◽  
Thomas Wågberg

The oxygen reduction reaction (ORR) is efficiently facilitated platinum catalysts alloyed with Co and reveal high electrochemically active surface area via rapid microwave synthesis.


Catalysts ◽  
2021 ◽  
Vol 11 (8) ◽  
pp. 989
Author(s):  
Kan Huang ◽  
Oscar Morales-Collazo ◽  
Zhichao Chen ◽  
Tangqiumei Song ◽  
Liang Wang ◽  
...  

Ionic liquids (ILs) have been explored as a surface modification strategy to promote the oxygen reduction reaction (ORR) on Pt/C and their chemical structures were identified to have strong influence on the ORR activities. To better understand the roles of anion and cation of ILs on the catalytic reaction, two cations ([MTBD]+ and [bmim]+) were paired with three anions ([TFSI]−, [beti]−, and [C4F9SO3]−) to form various IL structures. By systematically varying the IL combinations and studying their effects on the electrochemical behaviors, such as electrochemical surface area and specific ORR activities, it was found that cation structure had a higher influence than anion, and the impact of the [MTBD]+ series was stronger than the [bmim]+ series. In addition to the investigation in the half-cell, studies were also extended to the membrane electrode assembly (MEA). Considerable performance enhancements were demonstrated in both the kinetic region and high current density region with the aid of IL. This work suggests that IL modification can provide a complementary approach to improve the performance of proton exchange membrane fuel cells.


Author(s):  
N. F. Daudt ◽  
A. Poozhikunnath ◽  
H. Yu ◽  
L. Bonville ◽  
R. Maric

Abstract Proton exchange membrane fuel cells (PEMFC) play a key role for sustainable energy; however, catalyst degradation remains one of the main challenges for competing with traditional energy technologies. The Pt/C commercially available electrocatalysts are susceptible to Pt dissolution and carbon support corrosion. In this context, we design a Pt–NbOx catalyst supported on TiN nanoparticles as an alternative electrocatalyst for the oxygen reduction reaction (ORR). The use of Pt–NbOx reduces materials’ costs by lowering the required platinum loading and improving catalyst performance. The TiN support is selected to improve support stability. The electrocatalyst is successfully synthesized by a one-step flame spray process called reactive spray deposition technology. Electrocatalyst with two different very low Pt loadings (0.032 mg cm−2 and 0.077 mg cm−2) are investigated and their performance as cathode is evaluated by the rotating disk electrode method. The new electrocatalyst based on Pt–NbOx supported on TiN has ORR performance that is comparable to the state-of-the-art Pt/C electrocatalyst. A half-wave potential of 910 mV was observed in the polarization curves, as well as a mass activity of 0.120 A∙mgPt−1 and a specific activity of 283 μA∙cmPt−2 at 0.9 V. These results demonstrate that Pt–NbOx on TiN electrocatalyst has the potential for replacing Pt/C cathode in PEMFC.


2014 ◽  
Vol 17 (2) ◽  
pp. 055-065 ◽  
Author(s):  
A. Seifitokaldani ◽  
M. Perrier ◽  
O. Savadogo

The electrochemical stability and activity of different compositions of titanium and tantalum oxy-nitride nano-catalysts were investigated for the oxygen reduction reaction (ORR). A new sol-gel method was used to produce a nano-powder mixture of Ti and Ta oxynitride from their alkoxides using urea as a nitrogen source. The precursors prepared by the sol-gel method were annealed in a N2 + 3% H2 atmosphere at determined temperatures (500, 700 and 900 °C) inside a silica tube furnace. X-ray diffraction results proved that by using this method a considerable amount of nitrogen was inserted into the catalyst structure at a relatively low temperature. Energy dispersive spectroscopy showed that the prepared catalyst should be oxidized carbonitride of titanium and/or tantalum. Heat treatment had a major effect on the onset potential by changing the crystallinity of the catalyst, so that the onset potential of titanium oxynitride increased from ca. 0.05 V to 0.65 V vs. NHE by increasing the temperature from 500 to 700 °C. Increasing the Ta concentration also led to a higher onset potential but lower ORR current. For instance, the onset potential for the ORR for tantalum oxynitride heat treated at 700 °C was ca. 0.85 V vs. NHE while this value was ca. 0.65 V vs. NHE for titanium oxynitride. However, the ORR current was 100 times smaller in tantalum oxynitride, most likely because of a low electrochemically active surface area. Electrochemical measurements suggested that an appropriate composition of titanium and tantalum was required to have both a good onset potential and ORR current by improving the catalytic activity and increasing the active surface area and electrical conductivity.


2021 ◽  
Author(s):  
Xieweiyi Ye ◽  
Yakun Xue ◽  
Kaijia Li ◽  
Wen Tang ◽  
Xiao Han ◽  
...  

Improving the activity and durability of Pt-based electrocatalysts used in the acidic oxygen reduction reaction (ORR) is a great task for the commercial applications of proton-exchange membrane fuel cells. Alloying...


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