Electroanalytical Methods

in Electrocatalyst Research
Presentation by: Loredana Protesescu Dai Wenyang Gediminas Mikutis

Analytical Strategy

06.12.1011

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Contents
1. Fuel cells: introduction
Introduction General types PEFCs: current challenges Hydrogen as a fuel source Principle Pt nanoprticle production

2. Electrocatalyst

3. Surface area determination (Q1) 4. Study of kinetics (Q2)

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Fuel cell: a principle

Catalyst

Source: http://ljplus.ru/img4/a/r/artykul/Fuel-Cell-scheme.jpg

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Fuel cell types

Solid Oxide FC Molten Carbonate FC Alkaline FC Phosphoric Acid FC Polymer Electrolyte FC

A nice comparison of the cells: http://www1.eere.energy.gov/hydrogenandfuelcells/fuelcells/pdfs/fc_comparison_chart.pdf Source: http://www.doitpoms.ac.uk/tlplib/fuel-cells/figures/fuelcell_types_sml.png

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Why fuel cells?

Conversion process Solar cells Internal combustion engine World electricity generation avg.1 Gas turbine (combined cycle) Fuel Cells
* Hydrogen production not considered

Efficiency 10-15% (40%) 16-20% 33% 40-60%

Environmental impact None CO, CO2, NOx, SOx CO2, NOx, Sox, radioactive, etc. CO2

40-60% (85%)* None*

Hydrogen as a fuel
Energy independence High energy density

Quiet Cheap? Ideal for:

Portable applications (battery substitution) Automotive industry On-site power for hospitals, banks, airports, schools, etc.

Source: 1) http://www.iea.org/stats/balancetable.asp?COUNTRY_CODE=29

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Applications

Source: http://stuorgs.oakland.edu/upload/images/IAHE/Potential%20Applications%20For%20Fuel%20Cells.png

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Hydrogen production
Steam reforming (from gas) CH4 + H2O CO + 3 H2

CO + H2O CO2 + H2
Partial oxidation (from oil) CnHm + n/2 O2 n CO + m/2 H2 Ex.: C6H12 + 6 O2 6 CO + 6 H2 Coal gasification (from coal) 3C (i.e.,coal) + O2 + H2O H2 + 3CO CO + H2O CO2 + H2
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Hydrogen production
Steam reforming, partial oxidation, coal gasification (from fossil fuels) CH4 + H2O CO + 3 H2 CnHm + n/2 O2 n CO + m/2 H2 3C(i.e.,coal) + O2 + H2O H2 + 3CO CO + H2O CO2 + H2 Sulfur-iodine cycle1 Photobiological water splitting (by algae)3 Photocatalytic water splitting2

Sources: 1) Walters & Wade (2002);

2) Maeda & Domen (2010); 3) Melis & Happe (2001)

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Hydrogen storage

Carbon Nanotubes

Metal-organic frameworks

Source: http://www1.eere.energy.gov/hydrogenandfuelcells/storage/basics.html

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Polymer Electrolyte Fuel Cells (PEFCs)

Nafion membrane

Anode: H2 2H+ + 2eE = 0 V

Cathode: O2 + 2H+ + 2e- H2O E = 1.229 V

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Source: http://stuorgs.oakland.edu/upload/images/IAHE/Pem%20Fuel%20Cell%20Diagram.png

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PEFCs Challenges
Catalyst efficiency (O2 reduction) Durability
Catalyst performance (CO poisoning) Membrane decay

Cost
Catalyst Membrane H2 production, delivery

Setup

Water and air management Temperature management

Supply chain infrastructure (H2)

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Electrocatalyst

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Increasing the activity of the electrocatalyst and minimize the cost?

Pt-black catalyst

Pt-alloy catalyst

Carbon supported Pt/Pt-alloy catalyst

Pt/Pt-alloy nano-scale catalyst Alloy formation and proper surface chemical composition A controlled surface structure Smaller size for preferred single crystal face

Source: 1) Sung et al. (2002); 2) Schmidt et al. (2003); 3)Wang et al. (2011)

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Nanoparticle synthesis and electrocatalytic activity

Chemical methods Impregnation methods

Colloidal methods Co sputtered methods

Sources: 1) Lee et al. (2002)

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Most important process parameters: Temperature profile (adjustable by quenching rate) Residence time Concentration of precursors

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Particle size

Why nanomaterials?

Surface area
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Techniques to determine the catalyst surface area ex-situ

BET Cyclic Voltammetry CO Striping Voltammetry

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BET Theory
BET has been developed In 1938, by Stephen Brunauer, Paul Hugh Emmett, and Edward Teller. Theory on multilayer adsorption with the following hypotheses: Gas molecules physically adsorb on a solid in layers infinitely There is no interaction between each adsorption layer The Langmuir theory can be applied to each layer
N: Avogadros number

s: Adsorption cross section of the adsorbing species

V: molar volume of adsorbate gas a: mass of adsorbent (in g)
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Cyclic Voltammetry

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Rotating disc electrode (RDE)

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Cyclic voltammograms

Starting from P in clockwise direction: No Faradaic reaction zone Plateau: formation of monolayer of oxide Oxygen evolution from oxidation of water: After inversion: break of the layer of oxide No Faradaic reaction zone Reduction of H+ :
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Techniques to determine the catalyst surface area in-situ

Cyclic Voltammetry
CO Striping Voltammetry

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Cyclic voltammograms

Source: Gasteiger et al. (2003)

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CO Striping Voltammetry
Operates under the same principle as Cyclic Voltammetry One side of the fuel cell is supplied with CO plus inert gas, humidified H2 is fed to the other side CO stripping peak potential can provide information on the composition of an unsupported metal alloy surface

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Combined In-situ Methods

Combined Voltammetry and X-ray Diffraction Combined Voltammetry and EPR Spectroscopy Combined Voltammetry and Light Microscopy Combined Voltammetry and UV/Vis spectroscopy Combined Voltammetry and AFM

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Strategy to study kinetics

A. Ex-situ:
1. Thin-film rotating ring-disk electrode (TF-RRDE)
Screening new catalysts. Obtain half-reaction rates, study side reactions (ex. H2O2, CO resistance)

B. In-situ:
1. Gas electrodes in half-cell configuration
kinetics studies of gas reactants under controlled mass transport conditions and at various temperatures (mechanism of oxygen reduction) Obtain rate-determining step, electrode potentials, diffusion/charge transfer parameters, surface area Obtain different contributions to losses Obtain various kinetic parameters (e.g. cell resistance as a fct. of current density), mechanism elucidation.
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2.

Cyclic voltammetry (CV)

3.
4.

Electrochemical Impedance Spectroscopy (EIS)

Subscale fuel cell test station

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Ex-situ: Thin-film rotating ring-disk electrode

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Ex-situ: Thin-film rotating ring-disk electrode

Molar percentage of H2O2 detected on the ring electrode

Suggested O2 reduction mechanism

ORR current density vs. disk potential

Source: Schmidt et al. (2003)

Diffusion-corrected Tafel plot for ORR (oxygen reduction reaction) in H2SO4 and HClO4 (dashed) 28

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In-situ: Gas electrodes in half-cell configuration

Source: Paulus et al. (2001)

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In-situ: Electrochemical Impedance Spectroscopy (EIS)

Advantages
Measurements can be made under real-world fuel cell operating conditions Multiple parameters can be determined from a single experiment. Relatively simple electrical measurement that can be automated. Can verify reaction models, and characterize bulk and interfacial properties of the system Measurement is non-intrusive does not substantially remove or disturb the system from its operating condition. A high precision measurement the data signal can be averaged over time to improve the signal to noise

Source: Wu et al. (2008)

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References
1. 2. 3. 4. 5. 6. 7. Maeda, K. & Domen, K. Photocatalytic Water Splitting: Recent Progress and Future Challenges. J. Phys. Chem. Lett. 1, 2655-2661 (2010). Melis, A. & Happe, T. Hydrogen Production. Green Algae as a Source of Energy. Plant Physiology 127, 740 -748 (2001). Scholz, F., Electroanalytical Methods. 2010, New York: Springer. Okada, T., et al., Electrochemical Methods for Catalyst Evaluation in Fuel Cells and Solar Cells in Molecular Catalysts for Energy Conversion. 2009, Springer Berlin Heidelberg. p. 67-102. Wu, J., et al., Diagnostic tools in PEM fuel cell research: Part I Electrochemical techniques. International Journal of Hydrogen Energy, 2008. 33(6): p. 1735-1746. Schmidt, T.J., et al., Rotating Thin-Film Method for Supported Catalysts, in Handbook of Fuel Cells: Fundamental, Technology, and Applications. Volume 2: Electrocatalysis. 2003, John Wiley & Sons: Chichester. p. 316-333. Gasteiger, H.A., et al., Beginning of Life MEA Performance - Efficiency Loss Contributions, in Handbook of Fuel Cells - Fundamentals, Technology and Applications. Volume 3: Fuel Cell Technology and Applications, Part 1, W. Vielstich, H.A. Gasteiger, and A. Lamm, Editors. 2003, John Wiley & Sons: Chichester. p. 593-610. Lee, S.-A.,et al. Nanoparticule Synthesis and Electrocatalytiv Activity of Pt alloy for Direct Methanol Fuel cells, Journal of the Electrochemical Society, 149, A1299 (2002)

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Questions?

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