1. What was the funding for this research?
This research made use of the Shared Experimental Facilities supported by the MRSEC Program of the National Science Foundation under award no.
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Hydrogen Oxidation and Evolution Reaction Kinetics on Platinum: Acid vs Alkaline Electrolytes
TL;DR: In this article, the Butler-Volmer equation was fitted to the HOR/HER exchange current densities on polycrystalline platinum and high surface area carbon-supported platinum nanoparticles using rotating disk electrode (RDE) measurements.
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Abstract: The kinetics of the hydrogen oxidation reaction (HOR) and hydrogen evolution reaction (HER) on polycrystalline platinum [Pt(pc)] and high surface area carbon-supported platinum nanoparticles (Pt/C) were studied in 0.1 M KOH using rotating disk electrode (RDE) measurements. After corrections of noncompensated solution resistance from ac impedance spectroscopy and of hydrogen mass transport in the HOR branch, the kinetic current densities were fitted to the Butler-Volmer equation using a transfer coefficient of α = 0.5, from which HOR/HER exchange current densities on Pt(pc) and Pt/C were obtained, and the HOR/HER mechanisms in alkaline solution were discussed. Unlike the HOR/HER rates on Pt electrodes in alkaline solution, the HOR/HER rates on a Pt electrode in 0.1 M HClO 4 were limited entirely by hydrogen diffusion, which renders the quantification of the HOR/HER kinetics impossible by conventional RDE measurements. The simulation of the hydrogen anode performance based on the specific exchange current densities of the HOR/HER at 80°C illustrates that in addition to the oxygen reduction reaction cell voltage loss on the cathode, the slow HOR kinetics are projected to cause significant anode potential losses in alkaline fuel cells for low platinum loadings (> 130 mV at 0.05 Mg pt /CM 2 anode and 1.5 A/cm 2 anode ), contrary to what is reported for proton exchange membrane fuel cells.
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Figures
Figure 6. Color online HOR/HER measured kinetic current densities gray solid lines on Pt/C in 0.1 M KOH at 10 mV/s and their fit to the Butler– Volmer equation Eq. 2 with = 0.5 dashed black lines : a 275 and b 314 K. The HOR/HER kinetic current densities were obtained from iRcorrected polarization curves and were corrected for hydrogen mass transport in the HOR branch using Eq. 1. The corresponding insets show the HOR/ HER polarization curves before solid black lines and after dashed red lines iR correction. 
Figure 7. Color online a HOR/HER polarization curve on Pt pc in 0.1 M HClO4 at 1600 rpm before ERDE, solid black lines and after EiR-free, dotted red lines iR correction. The inset is the Koutecky–Levich plot obtained at E = 0.1 V/RHE for the HOR at different rotation rates. b HOR/HER polarization curve on Pt pc in 0.1 M KOH at 1600 rpm before ERDE, solid black lines and after EiR-free, dotted red lines iR correction; the dashed black lines are the Nernstian diffusion overpotential calculated according to Eq. 12. The data are shown for the positive-going scans at 10 mV/s at 294 1.5 K. The x-axis potential range in b is double of that in a . 
Figure 1. Color online CVs of Pt pc at 294 1.5 K in Ar-saturated 0.1 M KOH at 50 mV/s with two different positive potential limits. The current density is referenced to the actual Pt surface area. 
Figure 8. Color online a HOR/HER specific exchange current density of Pt/C in a PEMFC at 353 K and 101 kPaabs H2 solid circles, from Ref. 12 compared to that obtained in 0.1 M KOH in this study solid squares and extrapolated to 353 K open squares . b Projected HOR overpotential vs Pt mass activity in KOH based either on 62 m2/gPt for the 46 wt % Pt/C catalyst used in this study black solid lines or on 92 m2/gPt for the 5 wt % Pt/C catalyst used in Ref. 12 gray dashed lines ; this is compared with mass activities measured on 5 wt % Pt/C in a PEMFC at 353 K red lines, from Ref. 12 . 
Figure 3. Color online HOR/HER measured kinetic current densities gray solid lines on Pt pc in 0.1 M KOH at 10 mV/s and their fit to the Butler– Volmer equation Eq. 2 with = 0.5 dashed black lines : a 275 and b 314 K. The HOR/HER kinetic current densities were obtained from iRcorrected polarization curves and are corrected for hydrogen mass transport in the HOR branch using Eq. 1. The corresponding insets show the HOR/ HER polarization curves before solid black lines and after dashed red lines iR correction. 
Figure 2. Color online a HOR/HER polarization curves positive-going scans on Pt pc at different rotation rates at 294 1.5 K. The inset shows a Koutecky–Levich plot at 0.5 V/RHE. b HOR/HER polarization curves on Pt pc at 1600 rpm at different temperatures positive-going scans . The data were collected in H2-saturated 0.1 M KOH at 10 mV/s.
Citations
In Situ Decoration of Ultrafine Ru Nanocrystals on N-Doped Graphene Tube and Their Applications as Oxygen Reduction and Hydrogen Evolution Catalyst
Barun Kumar Barman,Bidushi Sarkar,Priyadarshini Ghosh,Monalisa Ghosh,Gowravaram Mohan Rao,Karuna Kar Nanda +5 more
- 30 Sep 2019
TL;DR: In this paper, the development of significantly active and stable bifunctional catalysts toward hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR) remains a challenge.
34
Study on the catalytic performance of Pd/TiO2 electrocatalyst for hydrogen evolution reaction
Ming Nie,Ming Nie,Hai Sun,Jianming Liao,Qing Li,Zhenhong Xue,Fengjuan Xue,Feng Liu,Mingyu Wu,Tong Gao,Liumei Teng +10 more
TL;DR: In this article, Pd/TiO2 was successfully prepared by anodic oxidation and electrodeposition, and its physical properties were characterized by XRD, EDS, SEM, and XPS.
34
Catalytic Surface Specificity of Ni(OH)2 -Decorated Pt Nanocubes for the Hydrogen Evolution Reaction in an Alkaline Electrolyte.
TL;DR: In this article, a bifunctional catalytic surface of Ni(OH)2decorated Pt nanocubes was used to enhance the Volmer/Tafel coupling in an alkaline medium.
34
Strong negative nanocatalysis: oxygen reduction and hydrogen evolution at very small (2 nm) gold nanoparticles.
TL;DR: The electron transfer kinetics associated with both the reduction of oxygen and of protons to form hydrogen at gold nanoparticles are shown to display strong retardation when studied at citrate capped ultra small Gold nanoparticles.
34
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