Study of Electrochemical

Catalysts in Fuel Cells

Kenichi Shimizu
Research Seminar
Nov. 8 2007

1
Study of Electrochemical Catalysts
in Fuel Cells
I. Study of catalyst effect in anodic
oxidation of organic fuels.

II. Synthesis of Pt on single-walled carbon

nanotube for cathodic reduction of
oxygen.

2
 Fuel Cells
 A system that harvests electrical
energy directly from a
spontaneous redox reaction.
 Electricity will be generated
continuously as long as fuel is
supplied.

Sutton, G.W. Direct Energy Conversion. Inter-University Electronics Series, Vol.3, NY, 1966. 3
 Fuel Cells

F + zH2O  wCO2 + vH+ + ve- + xI (E1)

yO2 + vH+ + ve-  zH2O (E2)
F + yO2  wCO2 + zH2O + xI (Ecell = E1+ E2)

Sutton, G.W. Direct Energy Conversion. Inter-University Electronics Series, Vol.3, NY, 1966. 4
 Gas Voltaic Battery (1842)

H 2  2 H   2e  G  0.0 kJ / mol H  0.0 kJ / mol

1
O2  2 H   2e   H 2 O G  237.2 kJ / mol H  285.8 kJ / mol
2
1
H 2  O2  H 2 O Grxn  237.2 kJ / mol H rxn  285.8 kJ / mol
2

Experimental design by William R. Grove

Grove, W.R. Phil. Trans. 1843, 133, 91-112. 5

 After >100 years of Nothing
 Alkaline hydroxide 9733
fuel cell was 10000

developed for 8000

Apollo mission in
# publication
6000
the 1950’s.
4000

2000

0
1981 1986 1991 1996 2001 2006

Year

Hoogers G.; Fuel cell technology handbook, CRC press, NY, 2003, pp2-1. 6
 Types of Fuel Cells Nafion®

 Solid oxide fuel cell.

 Molten carbonate fuel
cell.
 Polymer Electrolyte
Membrane (PEM) fuel
cell.
 Microbial fuel cell.
www.news.cornell.edu

Hoogers G.; Fuel cell technology handbook, CRC press, NY, 2003, 2-1.
Fuel Cell Technology. Reaching Towards Commercialization, Springer, Germany, 2006, 277-293. 7
Meier, F.; et al.; J. Membr. Sci. 2004, 241, 137.
 Polymer Electrolyte Membrane Fuel
Cell
Nafion®

Meier, F.; et al.; J. Membr. Sci. 2004, 241, 137. 8

Automotive Application of Fuel
Cell
 Zero (low) emission.
 No mechanical parts.
 Higher fuel efficiency.

GM Sequal fuel cell vehicle

http://www.fueleconomy.gov/feg/ http://www.fueleconomy.gov/feg/

9
Stationary Power Plant
 Generates little or no
air pollution.
 Sustainable fuel
source.
 Anaerobic digester gas
 Quiet.

www.fuelcellenergy.com

10
Portable power sources
 Fuel cells could supply
larger energy density
than the conventional
battery system.
http://pr.fujitsu.com/en/news/
 Very quick recharge.

http://www.physorg.com/news6542.html

11
 Limitations of Fuel Cells
 Fuel availability and storage.
 Use of Hydrogen as anode fuel
 Low power density.
 Kinetic limitations. Part 1

 High cost.
 Pt catalyst. Part 2

 Polymer electrolyte membrane.

O’Hayre, R. et al. Fuel Cell Fundamentals. John Wiley & Sons. N.Y. 2006. 12
Study of Electrochemical Catalysts
in Fuel Cells
I. Study of catalyst activity in anodic
oxidation of organic fuels.

II. Synthesis of Pt on single-walled carbon

nanotube for cathodic reduction of
oxygen.

13
 Limitations of Fuel Cells
 Fuel availability and storage.
 Use of Hydrogen as anode fuel
 Low power density.
 Kinetic limitations.
 High cost.
 Pt catalyst.
 Polymer electrolyte membrane.

O’Hayre, R. et al. Fuel Cell Fundamentals. John Wiley & Sons. N.Y. 2006. 14
 Fuel Availability and Storage
CH 3OH  H 2 O  CO2  6 H   6e  G  9.2 kJ / mole H  131.0 kJ / mol
3
O2  6 H   6e   3H 2 O G  712.1 kJ / mole H  857.4 kJ / mol
2
3
CH 3OH  O2  CO2  2 H 2 O Grxn  702.9 kJ / mol H rxn  726.4 kJ / mol
2
CH3OH Fuel Cell H2 Fuel Cell
Fuel Storage Easy Difficult
Fuel Availability High Low
Cost ($/kWh) 0.02 0.15
Efficiency (%) 97 83
Power (kW/g-Pt) 0.2 0.6
Heath, C.E.; Worsham, C.H.; The Electrochemical Oxidation of Hydrocabons in a Fuel Cell. In Fuel Cell,
Young, G.J. Ed.; Reihold Publishing Corp.: NY, 1963, Vol. 2;, pp 182. 15
 Lower power density

O’Hayre, R. et al. Fuel Cell Fundamentals. John Wiley & Sons. N.Y. 2006. 16
 Kinetic Limitations for Fuel Cells
0.8
Cell potential (V)

0.6
1 2 3

0.4

0.2

0
0 0.02 0.04 0.06 0.08 0.1
Ampere
1. Potential drop is observed due to activation energy.
2. Ohmic resistance of the cell is proportional to the applied
amperage.
3. Potential starts dropping at higher current due to mass transport.

O’Hayre, R. et al. Fuel Cell Fundamentals. John Wiley & Sons. N.Y. 2006. 17
 Basic Operation of a Fuel Cell
e- 2 e-

Air
Anode Fuel

1. Activation energy.
3
1 1 3 2. Ohmic resistance
H+
3. Mass transport.
3

Product H2O
Electrolyte
Anode e.g. Nafion® Cathode

O’Hayre, R. et al. Fuel Cell Fundamentals. John Wiley & Sons. N.Y. 2006. 18
Activation Energy
 Activation loss of cell potential is due to the
electrochemical reactions
 For hydrogen fuel cell
 Oxygen reduction at cathode.
 For fuel cells with organic fuel
 Anodic oxidation of organic fuel.

19
Activation Energy
 Activation loss of cell potential is due to the
electrochemical reactions
 For hydrogen fuel cell
 Oxygen reduction at cathode.
 For fuel cells with organic fuel
 Anodic oxidation of organic fuel.

20
Activity of Catalysts in Anodic
Oxidation
1. Methanol oxidation.
Overview of how catalysts are evaluated in anodic
oxidation using cyclic voltammetry.

2. Formic acid oxidation.

Evaluate kinetic effects of PtRu and PtBi catalysts
on anodic oxidation.

21
 1. Methanol Oxidation
CH3OH

H2O  M-OHabs+ H+ HCHO CO

HCOOH H2O  M-OHabs+ H+

CO2

Christensen, P.A. et al. J. Electroanal. Chem. 1993, 362, 207-218. 22

Cyclic Voltammetric response of
Methanol Oxidation
1.6 PtRuCNT

1.2
i /(mA)

0.8

0.4

0
0.2 0.4 0.6 0.8 1 1.2
E /(V vs. NHE)

23
 Interpretation of Forward Peak
1.6 PtRuCNT Sufficient reaction kinetics
• Deactivation of
1.2 Slow reaction kinetics catalyst surface
• Mass transport
i /(mA)

0.8

CH3OH + H2O  CO2 + 6H+ + 6e-

0.4

0
0.3 0.5 0.7 0.9 1.1
E /(V vs. NHE)
Onset potential

24
 Interpretation of Reverse Peak
1.6 PtRuCNT

Kinetically controlled reaction

1.2
Not sufficient
i /(mA)

potential
0.8 • Reviving catalyst surface
• Mass transport

0.4

CH3OH + H2O  CO2 + 6H+ + 6e-

0
0.3 0.5 0.7 0.9 1.1
E /(V vs. NHE)

Manohara, R.; Goodenough, J.B. J. Alloy. Compd. 2001, 315, 118. 25

 Guidelines for Evaluating Catalysts
using Cyclic Voltammetry
1.6
 Catalyst efficiency (if/ib). PtRuCNT

 Current density (A/cm2) 1.2

 Study of catalyst effects on

i /(mA)
an electrochemical reaction. if
0.8
 Mass activity (A/g-Pt)
ib
 Study of catalyst system. 0.4

0
300 500 700 900 1100
E /(mV vs. NHE)

Liu, Z. et al.; J. Phys. Chem. B 2004, 108, 8234. 26

 Cyclic Voltammetric Evaluation of
Catalysts in Methanol Oxidation

Mass activity

Yen, C.H.; Shimizu, K.; Lin, Y.-Y.; Bailey, F.; Cheng, I.F.; Wai, C.M.; Energy & Fuels 2007, 21, 2268. 27
2. Formic Acid Oxidation
Kinetic Effects of Carbon Nanotube
Supported Binary Metal Catalysts; PtRuCNT
and PtBiCNT

28
 Application of Formic Acid as a Fuel
Fuel Cell Formic acid Methanol Hydrogen
Efficiency (%) 95 97 83
Cost ($/kWh) -- 0.02 0.15
Fuel Storage Easy Easy Difficult
Fuel Availability High High Low
Cell Potential (V) 1.45 1.21 1.23
Fuel Crossover Low High High
Heath, C.E.; Worsham, C.H.; The Electrochemical Oxidation of Hydrocabons in a Fuel Cell. In Fuel Cell, Young,
G.J. Ed.; Reihold Publishing Corp.: NY, 1963, Vol. 2;, pp 182. 29
Kang, S.; et al.; J. Phys. Chem. B, 2006, 110, 7270.
 Fuel Crossover
H+

H+

Fuel

Air
H+
www.news.cornell.edu
H+

 DMethanol = 5 x10-6 cm2s-1. (Anode) PEM (Cathode)

 Creates short circuit.

Meier, F.; et al.; J. Membr. Sci. 2004, 241, 137.
Mauritz, K.A.; Moore, R.B.; Chem. Rev.2004, 104, 4535. 30
 Formic Acid Oxidation
 Direct electrochemical oxidation to CO2.
 Chemical pathway involves spontaneous dissociation of
formic acid to water and CO.

Rice, C.; et al.; J. Power Sources, 2003, 115, 31

229.
 Cyclic Voltammetric Response of
Formic Acid Oxidation

5 1. HCOOH  CO2 + 2e- E0 = + 0.17 V

Pt CNT
1
4 2. HCOOH  COads + H2O
4 3. H2O  OHads + H+ +e-
3
mA/cm 2

4. COads + OHads  CO2 + H+ + e-

2 1
1

-1
0.1 0.6 1.1
E /(V vs.NHE)

32
 PtRu CNT and PtBi CNT
Pt42Ru58CNT Pt38Bi62CNT

Atomic ratio of Pt:Ru is 1:1.4. 20 nm

Atomic ratio of Pt:Bi is 1:1.6.
50 nm

Image is courtesy of Clive, H. Yen.

33
 intermediate

Catalytic Effect of Ru HCOOH

Rxn 1
CO2
Rxn 2
PtRuCNT
12 5
PtCNT CO
10 4
i /(mA/cm , PtRuCNT)

i /(mA/cm , PtCNT)
8
3
6
2
2

2
4

2 1

0 0
0.1 0.3 0.5 0.7 0.9 1.1 1 M H2SO4
E /(V vs. NHE) 0.1 M HCOOH

34
Evaluation of PtRu CNT using Peak
Currents
Pt CNT mA/cm2 (1) (2) (3) (1)/(3)
5
(3) PtCNT 2.84 1.61 5.31 0.53
4
(1) PtCBc 3.72 0.99 11.3 0.33
3
i /(mA/cm 2)

PtRuCNT 11.6 N/A 8.91 1.3

2 (2)
PtRuCBc 6.05 N/A 6.01 1.0
1
C
Commercial Catalyst
0 1 M H2SO4
-1 0.1 M HCOOH

0.1 0.3 0.5 0.7 0.9 1.1

 Higher current ratio suggests
E /(V vs. NHE)
higher catalytic efficiency of
PtRu pair.

35
 intermediate

Catalytic Effect of Bi HCOOH

Rxn 1
CO2
Rxn 2
PtBiCNT 5
PtCNT CO
1.2
i /(mA/cm2, PtBiCNT)

i /(mA/cm2, PtCNT)
0.9
3
0.6
2

0.3 1

0 0
0.1 0.3 0.5 0.7 0.9 1.1 1 M H2SO4
E /(V vs. NHE) 0.1 M HCOOH

36
Evaluation of PtBi CNT using Peak
Currents
Pt CNT
5
(3) A/cm2 (1) (2) (3) (2)/(3)
4
(1) PtCNT 2.84 1.61 5.31 0.30
3
i /(mA/cm 2)

2 PtCBc 3.72 0.99 11.3 0.09

(2)
1
PtBiCNT N/A 0.73 0.52 1.4
0 1 M H2SO4
0.1 M HCOOH
-1 C
Commercial catalyst
0.1 0.3 0.5 0.7 0.9 1.1
E /(V vs. NHE)

37
 Activation Energy of Formic Acid
Oxidation
Eac (kJ/mole) CI (90%)
PtCBa 20.4 N/A
Ptb 20.9 1.6
PtCBc 21.1 2.1
PtCNT 17.5 2.5
PtRuCBc 21.0 3.9
PtRuCNT 22.2 4.3
PtBiCNT 45.5* 3.0
PtBi(III)b 42.3* 7.2
C
Commercial catalyst 90% confidence interval

a
Lovic, J.D.; et al.; J. Electroanal. Chem., 2005, 581, 294.
b
Wilson, J.R.; et al.; J. Electrochem. Soc., 1984, 2369. 38
Review of PtBiCNT
 Peak currents
 Low peak current density suggests slower
kinetics.
 Current ratio suggests high catalyst efficiency.
 Activation energy
 PtBiCNT requires the highest activation energy.
 Bi keeps Pt free from CO poisoning but
lowers overall catalytic activity.

39
 Third Body Effect

Cao, D. et.al.; J. Phys.Chem. 2005, 109, 11622. 40

 Third Body Effect
 Replace neighboring
Pt with the secondary
metal catalyst.
 Does not provide the
three Pt binding site
for CO.
 Pt stays free of CO
poisoning.

Casado-Rivera, E.; et al.; Chem. Phys. Chem. 2003, 4, 193.

Gojković, S.Lj.; et al. Electrochimica Acta 2003, 48, 3607-3614. 41
 Tafel Analysis
if kf
PtCNT Red Ox A B
ib kb
-8
β
ln l j/(A/cm )l
2

lnlj0l  Exchange current,

-12
j0;
1 M H2SO4  Equilibrium Potential,
-16
0.1 M HCOOH
Eeq;
0.1 Eeq 0.5 0.9
E (V vs. NHE)
 Tafel Slope, β;

42
 Tafel Analysis
Tafel Slope j0 Eeq
(mV/dec) (µA/cm2) (V vs. NHE)
PtCB 150 -- --
PtCNT 91 ± 9 3.6 ± 0.6 0.30 ± 0.02
PtCBc 80 ± 4 5.3 ± 1.3 0.23 ± 0.05
PtRuCNT 32 ± 5 11.8 ± 5.9 0.29 ± 0.01
PtRuCBc 39 ± 3 2.9 ± 0.6 0.26 ± 0.02
PtBiCNT 96 ± 3 4.3 ± 2.5 0.25 ± 0.07
C
Commercial catalyst ±: 90% confidence interval

Lovic, J.D.; et al.; J. Electroanal. Chem., 2005, 581, 294. 43

Conclusion of Formic Acid Oxidation
 PtRuCNT improved catalytic efficiency by
enhancing the reaction kinetics.
 No significant change in activation energies.
 Highest exchange current was observed.
intermediate
Rxn 1
HCOOH CO2
Rxn 2

CO

44
Conclusion of Formic Acid Oxidation
 Addition of Bi could suppress Pt poisoning
by CO.
 Improved current ratio (catalytic efficiency).
 Activation energy was significantly higher.
intermediate
Rxn 1
HCOOH CO2
Rxn 2

CO

45
Study of Electrochemical Catalysts
in Fuel Cells
I. Study of catalyst activity in anodic
oxidation of organic fuels.

II. Synthesis of Pt on single-walled carbon

nanotube for cathodic reduction of
oxygen.

46
Synthesis of Pt-SWNT
For Oxygen Reduction;
O2(g) + 4H+ + 4e-  2H2O(l)

47
 Catalyst Requirement
 Stable.
 Adequate electrical conductivity.
 High surface area.
 High catalytic activity.

Liebhafsky, H.A; Cairns, E.J. Fuel Cells and Fuel Batteries. John Wiley & Sons Inc., N.Y., 1968, pp384. 48
Methods of Synthesis
 Direct supercritical CO2 deposition.
 Water-in-hexane microemulsion.
 Water-in-supercritical CO2 microemulsion.
 Electro-less deposition of Pt.

49
Electro-less deposition
of Pt onto SWNT
Reduction of Pt in
2+

Methanol/Water Solution

50
Single-Walled Carbon Nanotube
 Metal impurities does
not diffract on XRD. TEM

 29 wt% Fe present.
 Hydrophobic in nature.

20 nm

51
 Pt-SWNT Synthesis
 3 to 5 mg of unpurified
SWNT.
 Methanol/Water (1:1
v/v).
 Aqueous Pt2+ salt.
 Inspired by Choi et al.

Choi, H.C.; et al. J. Am. Chem. Soc. 2002, 124, 9058. 52

 Pt-SWNT in Methanol Oxidation
Pt-SWNT (1:10 C:Pt) Commercial PtCB
0.3 0.2

i /(Amp/mg Pt)
0.2 0.1
i /(A/mg-Pt)

0.1
0.1
0.0
0.0
-0.1

-0.1 -0.1
0.1 0.3 0.5 0.7 0.9 1.1 0.1 0.3 0.5 0.7 0.9 1.1
E /(V vs. NHE) E /(V vs. NHE)

 Oxidation of 0.1M methanol in 1M sulfuric acid.

 Anodic peak current: 446 mA/mg-Pt for Pt-SWNT vs. 111 mA/mg-Pt for PtCB.
 Pt surface area: 351 cm2/mg-Pt for Pt-SWNT vs. 107 cm2/mg-Pt.

53
 Wt% Pt and % Utilization
 >90 % conversion of
Pt2+/Pt0 was obtained
Wt% Pt on Pt-SWNT

60
50.5
from UV-vis analysis.
40 34.4  50.5 wt% corresponds
24.5
20 to only 5 %
conversion.
0
1:4 1:6 1:10
C:Pt C:Pt C:Pt

54
 Spontaneous Reduction of Pt(II)

 Pt nanoparticles can be formed through reduction

of Pt2+ by alcohols.

Wang, X. et al. Nature 2005, 437, 121-124. 55

Reduction of Pt by SWNT
in aqueous solution
3 to 5 mg of SWNT
Pt2+

Shaking and ultrasonic agitation

56
 Reduction of Pt by SWNT
0.05
 Hydrogen
0
adsorption/desorption (circled
i /(mA)

-0.05 region) indicates Pt(0).

as received SWNT

-0.1
Pt-SWNT  2.8 wt% Pt in Pt-SWNT.
0 0.5 1
E /(V vs. NHE)  Deposition efficiency is 16
%.
EDS
 2200 cm2/mg-Pt.
Counts

 107 cm2/mg-Pt from the

commercial PtCB.

57
Methanol Oxidation
Pt-SWNT
5.0E-05
w/o Methanol
w/ Methanol
3.0E-05
i /(Amp)

1.0E-05

-1.0E-05

-3.0E-05
0.1 0.3 0.5 0.7 0.9 1.1
E /(V vs. NHE)

58
 Reduction of Oxygen
Pt-SWNT Commertial PtCB
0.2

i /(A/mg-Pt)
0

-0.05
-0
i /(A/mg-Pt)

-0.1
0 0.5 1
-0.2 E /(V vs. NHE)

Ep ip
-0.4
w/ Nitrogen (V) (A/mg-Pt)
w/ Oxygen
-0.6 Pt-SWNT 0.68 0.52
0 0.5 1 PtCB 0.57 0.05
E /(V vs. NHE)

59
Chronoamperometry
Commercial PtCB w/ Nitrogen
1400 Commertial PtCB w/ Oxygen
@ 600 mV
1200 Pt-SWNT w/ Nitrogen
i /(A/mg-Pt)

1000 Pt-SWNT w/ Oxygen

800
600
14 times higher catalytic activity
400
200
0
0 10 20 30
Time (s)

60
 Synthesis Pt-CB and Pt-MWNT
1 50
0
-2

i /(m A)
-50
i /(m A)

-5 -100
w/ Nitrogen
-8 -150
w/ Oxygen
-11 -200
0 0.5 1 0 0.5 1
E /(V vs. NHE) E /(V vs. NHE)

Carbon black substrate Unpurified multi-walled carbon

(80-100 mesh, 100 % carbon) nanotube (95 % purity)

 This synthetic method was applicable to other carbon

supports.

61
Conclusion for Pt-SWNT
 Direct deposition of Pt onto SWNT
without added reducing agent.
 Prepared catalyst was 14 times more
active towards O2 reduction.
 Inactive towards methanol oxidation.
 Will not be affected by methanol crossover.
 Applicable to other carbon substrates.

62
Current/Future work
 Investigate reaction mechanism for Pt-
SWNT synthesis in aqueous solution.
 Possible improvement on Pt utilization.
 Currently 16 %.
 Synthesis of bimetallic catalysts.
 Application to fuel cell.

63
 Acknowledgement
 Dr. Frank Cheng
 Dr. Chien Wai and his research group
 Clive Yen, Shaofen Wang, Byunghoon Yoon, Dinesh Thanu
 Dr. Peter Griffiths and his research group
 Dr. Garry Knerr
 Department of chemistry and office staff
 Cheng group
 Tina Noraduon, Derek Laine, Simon McAllister, Rubha Ponraj, Yu Qun Xie, and Chris Roske
 Department of Agricultural engineering for power press
 Department of Forest Product for heat press
 Tom Williams and Franklin Barely for XRD, TEM, SEM, and EDS.
 Maria Paulina Viteri Espinel

Financial support
 Electric Power Research Institute (EPRI) Innovative Small Grants Program
 Dr. and Mrs. Renfrew Summer scholarship

64
Additional References
1. Cheng, S.; Liu, H.; Logan, B.; Environ. Sci. Technol. 2006, 40,
364.
2. Zhou, L.; Gunther, S.; Imbihl, R.; J. Catal. 2005, 230,166.
3. Park, K.W.; Choi, J.H.; Sung, Y.E.; J. Phys. Chem. 2003, 107,
5851.
4. Matsumoto, T.; et al.; Chem. Comm. 2004, 840.
5. Park, K.-W.; Choi, J.-H.; sung, Y.-E.; J. Phys. Chem. 2003,
107, 5851.
6. Tang, H.; Chen, J.H.; Wang, M.Y.; Nie, L.H.; Kuang, Y.F.
Yao, S.Z.; Appl. Catal. A 2004, 275, 43.
7. Casado-Rivera, E.; Volpe, D.J.; Alden, L.; Lind, C.;
Downie, C.; Vázquez-Alvarez, T.; Angelo, A.C.D.; DiSalvo,
F.J.; Abruña, H.D.; J. Am. Chem. Soc. 2004, 126, 4043.
8. Huang, J.; Yang, H.; Huang, Q.; Tang, Y.; Lu, T.; Akins,
D.L.; J. Electrochem. Soc. 2004, 151(11), A1815.
9. Roychowdhury, C.; Matsumoto, F.; Zeldovich, V.B.;
Warren S.C.; Mutolo, P.F.; Ballesteros, M.; Wiesner, U.;
Abruña, H.D.; DiSalvo, F.J.; Chem. Mater. 2006, 18, 3365.

65