Corrosive Resistance of Graphene Support in Catalysts with Pt Nanoparticles

Dr. Alan Lane, Brian Carr, Dylan Nichols, Wei Li Dept. of Chemical and Biological Engineering Contact: Dylan Nichols, djnichols@crimson.ua.edu, (205) 394-3850 Brian Carr, btcarr@crimson.ua.edu, (504) 606-8890

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Introduction
Background: A serious barrier to commercialization of PEM fuel cells is electrocatalytic oxidation of the carbon black support for the Pt catalyst at the cathode. Graphene, a new carbon support for the Pt catalyst, is expected to show a greater resistance to corrosion than traditional carbon black. Two main reasons: 1. Carbon support corrosion Two main proposed pathways for the carbon support corrosion: C + 2H2O = CO2 + 4H+ + 4e , 25 C, 0.207 V vs. SHE C + H2O = CO + 2H+ + 2e, 25 C, 0.518 V vs. SHE 2. Pt dissolution Pt = Pt2+ + 2e Pt + H2O = PtO + 2H+ + 2e PtO + 2H+ = Pt2+ + H2O Objective: Study the carbon black support corrosion and Pt oxidation/reduction with DEMS spectra. Then, compare those findings to the DEMS spectra for graphene support corrosion

Past Results and Discussion

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Past Results and Discussion

3. DEMS spectra interpretation 3.1 CO2 signal (Figure 1: c) Maximum I at 100 mV: C reacts with hydrogen peroxide. Maximum II (peak II) at 600 mV: COsurf oxidized to CO2. Maximum III (peak III) at 900 mV: carbon surface oxides groups oxidized to CO2. Maximum IV (peak IV) at 1400 mV: C directly oxidized to CO2. Maximum V at 750 mV (cathodic scan): removal of [O] or [OH] from Pt and transfer to carbon surface to help to produce CO2 . 3.2 H2 signal Peak at 100 mV: hydrogen desorption from HOPD (Figure 1: c and Figure 2) Two kinds of H in 100 400 mV Underpotential deposition H, HUPD, (main part) Overpotential deposition H, HOPD, (small part) Mechanism Only HOPD contributes to this peak Hydrogen evolution reaction (HER) Pt + H+ + e = Pt-HOPD Pt-HOPD + Pt-HOPD = 2Pt + H2 Or Pt-HOPD + H+ + e = Pt + H2 The size of H2 peak is very small compared to the electrochemical surface area from CV. HER has positive temperature effect.
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Past Results and Discussion

3.2 H2 signal (continued) H2 Plateau: (Figure 1: c and Figure 2) Starts around 0.9 V (anodic scan), where the Pt begins to be oxidized; ends around 0.8 V (cathodic scan), where the PtOx reduction ends. This matches that in CV. One advantage of DEMS is that it can resolve the currents of Pt oxidation and C oxidation, which cannot in CV. PtOx has low hydrogen oxidation catalytic effect so as to increase the hydrogen signal.

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Summary and Future Work

1. DEMS is a powerful tool to investigate the carbon support corrosion, Pt oxidation/reduction and their interplay during electrocatalyst degradation in the cathode of PEMFC, by correlating the products and probe gases changes to specific potentials. 2. This investigation will be extended to carbene to ascertain its increased stability and resistance to corrosion relative to carbon black.

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Experiment
Differential Electrochemical Mass Spectrometry: DEMS is a combination of cyclic voltammetry and mass spectrometry. In this DEMS experiment, the effluent from the fuel cell cathode was analyzed in real time by an online mass spectrometer to detect CO2 as the cell potential was cycled from 0.05 to 1.4 V by an electrochemical potentiostat. Humidified hydrogen and helium were fed to the cathode and anode, respectively. The MS data was coupled with the results from cyclic voltammetry to relate oxidative peaks at various potentials to the oxidation of either the hydrogen fuel, platinum catalyst, or the support.

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Acknowledgements
Special thanks to Xia Xu, Dan Armstrong, and the MINT Center. Past results curtsy of Dr. Alan Lane and Wei Li.

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Fig. 1: Pt/C cathode DEMS spectra: (a) CV; (b) locate the potentials; (c) DEMS spectra of H2 and CO2; and (d) DEMS spectra of H2 and O2

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Fig. 2: Hydrogen MS spectra peaks

Fig. 3: MS spectra for C, Pt and Pt/C cathodes: (a) H2 MS spectra and (b) CO2 MS spectra

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