UIC Final Report

REU 2004 Summer Program

The Engineering of Pt/Carbon Catalyst Preparation

For application on Proton Exchange Fuel Cell Membrane
(PEFCM)

Student’s Name: Jaime O Robles

Advisor: John R. Regalbuto

Catalysis Laboratory
University of Illinois at Chicago
Progress Report
 This paper will deal with the strong electrostatic adsorption (SEA) method
used for catalyst preparation of Platinum on carbon supports for use in proton
exchange fuel cell membranes (PEFCM). The main objective is to optimize
dispersion and loading of Pt on carbon supports. Characterization results, of the
Pt/Carbon catalyst, prepared via the SEA will suggest that the SEA is the suitable
technique. Furthermore, the key variables will be identified and optimized in order
to obtain the conditions at which to prepare the catalyst.

Introduction

The proton exchange fuel cell membrane has become the dominant fuel cell due
to its advantages in power, low operating temperature, and low CO2 emission [1]. Fuel
cell technology is a promising, but futuristic nonetheless. Like every innovation ever
presented, fuel cells have their pros and cons. Fuel quality and storage are the main
concerns that need to be addressed before commercializing this new technology. The
research focuses on the two electrodes, composed of Platinum on carbon-coded film,
found in the PEFCM.
The Pt/carbon-coded electrodes demand a high dispersion, high weight percent of
platinum on carbon to enhance its efficiency, although economically speaking this
process in not sound. Due to its low operating temperature-80 degrees Celsius-such high
weight percentage specifications can be used. At the catalysis laboratory, the main focus
of the research is to use high and low surface area carbon supports in order to comply
with the high dispersion, high weight percent demands. Table 1 shows the different
carbons used, for experimentation, along with their important characteristics.
Furthermore, an in depth characterization process is to be conducted using: Scanning
Transmission Electron Microscope (STEM images provided by the Research Resource
Center at the University of Illinois at Chicago), Extended X-ray Absorption Fine
Structure imaging at Argonne National Laboratory.
The characterization process will provide the results needed to understand the
chemistry taking place. Ideally, the EXAFS will provide the dispersion and weight
loading; STEM images will provide pictorial evidence and estimated particle size.
Ultimately, the results will show that the strong electrostatic adsorption method is the
supreme method to meet the demands of high dispersion high weight percent Pt/carbon
catalyst.
Table 1: Carbons used for impregnation experiments.

Company Surface Area

Carbon name Type
Name (m^2/g)
Ketjen Black
Akzon Nobel cabon black 795
EC 300 J
Ketjen Black
Akzon Nobel cabon black 1415
EC 600 J
Black Pearls
Cabot cabon black 1475
2000

Ensaco 350 Erachem cabon black 795

The Proton Exchange Membrane Fuel Cell (PEMFC)

How do Fuel Cells work? Fuel cells are electrochemical converter devices that
convert hydrogen and oxygen into water, producing electricity and heat in the process.
First hydrogen is fed to the fuel cell via a reformer or stored high pressure hydrogen.
The hydrogen comes into contact with the anode where the chemistry between the two
allows for the separation of the two electrons from the hydrogen atom. The electrons are
conducted by the anode to an external electric circuit where electricity is produced.
Meanwhile, the hydrogen cations are conducted through the electrolyte to the cathode
where they meet with the oxygen gas and the free electrons to produce water and heat.
Such a single procedure generates approximately .7 volts, and therefore the use of fuel
stacks is in order. Fuel stacks are composed of single fuel cells combined in series or
parallel. The PEMFC operates at a low temperature, usually at 176 degrees Fahrenheit
(80 degrees Celsius) [2].
Figure1 shows a composite sketch of a PEMFC along with a half reaction of each
electrode, which is composed of four basic elements [3].

Figure 1: Shows the four basic elements A)

A) Anode B) Cathode
C) Electrolyte and D) Catalyst
The PEMFC consists of four basic elements [3]:

Anode: The cathode is the first element the Hydrogen comes into contact with. This
element is the negative terminal, which serves various functions. It has the dispersed
catalyst (Pt) that enables it to react with the hydrogen being fed. Once
the hydrogen is disassociated from its electrons, the cathode conducts the electrons to an
external circuit which produces the electricity.

Cathode: The anode is the positively charged terminal, which

Conducts the electrons from the external circuit to meet with the hydrogen cations and
oxygen to form the water molecules. This reaction, or combination, is allowed through
the dispersed platinum.

Electrolyte: This element is also known as the Proton Exchange Membrane. The
PEM is a special solution or specially treated material that only conducts
positively charged ions.

Catalyst: The catalyst is usually made of platinum particles dispersed in carbon

material. It allows for the reactions between hydrogen and oxygen. The platinum
catalyst always faces the PEM.

The PEMFC has had applications in the automobile industry. In the 1990s
Ballard, a leader in fuel cell manufacturing, put its fuel cells into a series of prototype
buses that ran on compressed hydrogen. In the late 1990s fuel cell powered buses were
put onto the streets of Chicago and Vancouver. Today, fuel cells are common in space
flights, transportation, portable power and large power generators, among other
applications [4].

Point of zero charge (PZC) experiment - 11 point PZC measurment

The point of zero charge, or PZC, can be said to be the first step in catalyst
preparation. It is a very important parameter used to determine the pH range at which the
impregnation step should be carried out. The point of zero charge is defined as being the
pH at which the surface charge of the carbon is neutral.
The PZC experiment is carried out by contacting the different carbons with, pH
adjusted, deinoized water. An eleven point PZC measurement is the most common
experiment used to obtain the PZC. The eleven pH points used are
1,2,3,4,5,6,9,10,11,12,13. The carbon is weight out for each pH sample. The weight of
\the carbon depends on the surface area, surface loading, and volume of sample bottle. A
sample calculation is given by equation (1). Finally, the carbon is added to each sample
bottle, which contains the deionized water at different pHs, and shaken for an hour. The
pH is measured and recorded as final pH. Table 2 illustrates the PZC results for some of
the carbons used for a surface loading of 10,000 m^2/L and a volume of 50mL bottles.
The surface areas are unique to each carbon and are given in Table 2.
  m2 
 ( )
 * m 3
L 
( Surface _ Loading ) * (Volume)
M carbon = [=]  (1)
Surface _ Area m2
grams

Table 2: Point of zero charge results.

g of
Carbon Volume (m^3) SA (m^2/g) SL (m^2/L) carbon PZC
needed
Ketjen Black EC
0.050 795 10000 0.629 9.4
300 J
Ketjen Black EC
0.050 1415 10000 0.353 9.5
600 J
Black Pearls
0.050 1475 10000 0.339 9.5
2000

After the final pH is measure a strong buffering effect is evident at pHs 4,5,6 and 9, as
shown by Table 3 and Figure 2 for Ketjen black EC 300J and Ketjen black EC 600J.
At this final pH the PZC can be read off of Figure 3, mainly, for the 300J and 600J the
PZC are 9.4, 9.5, respectively.

Table 3: pH measurements for Ketjen 300J and Ketjen 600J.

KETJEN BLACK EC 300 J KETJEN BLACK EC 600 J

pH(final-1hr. pH(final-1hr.
pH(initial) pH(initial)
Contact) Contact)
1.06 1.06 1.05 1.07
1.97 2.07 1.97 2.04
3.05 7.72 3.01 7.93
4.01 8.90 3.90 9.03
4.89 9.44 4.90 9.26
5.86 9.51 5.77 9.44
9.12 9.84 9.15 9.77
10.18 10.28 9.98 10.27
11.07 11.06 10.99 10.99
11.88 11.87 11.89 11.89
13.05 13.03 12.88 12.85
 11-point pH PZC measerument
14
13
12
11
10
9
pH final

8
7
6
5
4
3 KETJEN BLACK ED 300 J
2
1
0
0 2 4 6 8 10 12 14
pH initial

(A)

11 point PZC measurment

14
13
12
11
10
9
pH final

8
7
6
5 KETJEN BLACK ED 600 J
4
3
2
1
0
0 2 4 6 8 10 12 14
pH initial

(B)

Figure 3: (A) Ketjen 300J PZC measurement graph (B) Ketjen 600J PZC measurement
graph.
Molecular Adsorption on Carbon Surfaces

The molecular adsorption concept is adopted and used in the SEA synthesis
technique. The SEA adsorption technique can be described as having a substrate and
adsorbate with two modes of adsorption: physical adsorption (Physisorption) and
chemical adsorption (chemisorption) [5]. The substrates are the different carbons used
(see Table 1), where as the adsorbate used is hydrogen hexachloroplatinate (IV) (H2Cl6Pt
obtained from Alrich chemical company). The main difference between physisorption
and chemicsorption is the nature of the bonding between the molecules and surface. In
physical adsorption there is no significant redistribution of electron density between the
substrate (carbons) and the adsorbate (CPA). In chemical adsorption a chemical bond is
formed between the adsorbate and substrate [5].
The catalyst preparation process has three main steps, CPA preparation,
Impregnation, and reduction. The SEA synthesis technique is a physical adsorption
process.

Revised Physical Adsorption model (RPA)

Before preparing a catalyst the revised physical adsorption model (RPA)

important to understand. Figure 2 illustrates a simple RPA model, where an in depth
theoretical RPA model was omitted for simplification purposes.

[PtCl6]-2
pH<PZC
OH2+
K1

PZC OH

pH>PZC K2

[(NH3)4Pt]+2
O-
Figure 4: Revised Physical Adsorption Model (Spieker and Regalbuto, CES 56, 2001,
3491, Hao and Regalbuto, JCIS, 267, 2003, 259 [6]).
Figure 2 shows an electrostatic interaction between the carbon support and Platinum
complexes. Mainly, if the carbon surface is positively charge an anionic Pt complex is
needed, i.e. CPA ([PtCl6]2-. Furthermore, if the carbon surface is negatively charge a
cationic Pt complex is needed, i.e. PTA ([(NH3)4Pt]2+). For the research at hand, CPA
was the target complex used for the impregnation step do to the high PZC recorded for
each carbon used. Because of its characteristics, CPA has a 48 hour preparation process,
which will be discuss shortly.

CPA preparation

In reference readings by Regalbuto and blank [7], the optimized concentration, at

which to run the impregnation step, of CPA was found to be 200ppm. The preparation
process begins by diluting CPA stock solution to the 200ppm needed. Next, an initial pH
is needed that will shift down to the target pH of 2.8. Ideally, the initial pH for 200ppm
CPA solution is 4.18, which will shift, after 48 hours, to 2.8. It is important to note that
CPA solution should be exposed to light during the 48 hour shift. This is the first of three
steps for the adsorption experiment.

The Strong Electrostatic Adsorption Method – Wet Impregnation

The strong electrostatic adsorption (SEA) method, the second of three steps, has
become a trademark at the catalysis laboratory at the University of Illinois at Chicago
lead by Professor John R. Regalbuto. The PZC data suggests that the CPA pH range
should be adjusted, after 48 hours, from 1 to 7. Once the CPA pH range is obtained, the
adsorption experiment is carried out. Mainly, the amount of carbon needed for each pH
point is calculated using equation (1). Next, the carbon is added to a designated volume
of CPA (usually 50mL bottles). The carbon support and CPA are allowed to contact for
an hour, where most of the Pt uptake takes place. Before contact, a 5mL sample of the
200ppm CPA is extracted to measure its exact concentration with the Inductively Couple
Plasma machine (to see whether its ~200ppm). After 1 hour contact, 5mL of the slurry is
filtrated and used to measure its concentration. The difference in concentration,
concentration before contact – concentration after contact, is recorded as uptake. Figure
5 suggests that a pH from 2 to 3 be used to obtain the optimum Pt uptake.
Using the data provided in Figure 5, the adsorption experiments, for the carbons
given in Table 1, where conducted at pHs ranging from 2 to 3. These experiments will
pin point, more accurately, a CPA pH that will yield an optimum Pt uptake. Figure 6
shows the results obtained for the SEA experiments conducted for the carbons given in
Table 1. It is important to note that the results given in both Figure 5 and 6, both have
carbons with high PZC values, both conducted at surface loadings of 500 m^2/L, and
both with CPA concentration of 200ppm.
 200
SX4 1Hr pzc=7.5
180

160 SX 1Hr pzc=8.0

140 SX2 1Hr pzc=8.5

Uptake (ppm

120
Vulcan 1Hr
100 pzc=8.6
Ensaco 250 1Hr
80 pzc=8.8
ensaco 350 1Hr
60
pzc=9.8
40

20

0
0 5 10 15
pH

Figure 5: pH vs. Uptake (ppm) from Xianghong Hao Thesis defense (2004).
SL=500m^2/L, 200ppm CPA.
180

160

140

120
Uptake (ppm)

100 EC 300J

EC 600J
80
Black Pearls
60
Umicore Ensaco 350

40 GE Ensaco 350

20

0
1.6 1.8 2 2.2 2.4 2.6 2.8 3 3.2 3.4 3.6 3.8 4 4.2
pH final

Figure 6: pH vs. Uptake (ppm) SL=500m^2/L, 200ppm CPA.

Figure 7 show the weight percent of each carbon used for the SEA experiments. The
weight percent ranges from 20% to 30%.

Weight percent of Pt on carbon

35

30

25

20
Pt Wt%

15

10

0
Ketjen Black EC 300J Ketjen Black EC 600J Black Pearls Ensaco 350
Carbon

Figure 7: Pt wt% of different carbons (SL=500m^2/L, 200ppm CPA).

Reduction of Pt/Carbon catalyst with H2

The reduction process reduces the Pt ligands attached to the carbon surface to
elemental Platinum. After the impregnation step, Platinum is found to be in its oxidation
state of +4, meaning that other species are present at the surface (i.e. Cl and OH). The
reduction process is started by purging the catalyst sample in He at room temperature for
30 minutes. Next, Hydrogen gas is reacted with the catalyst for 1.5 hours. At the
beginning, the temperature is ramped by 5ºC per minute until reaching 200ºC. This
process usually takes about 30 minutes, the rest of the time, 1 hour, the reaction takes
place. Finally, after 1.5 hours of reaction, the sample is cooled to room temperature in
He bath. After the reduction process, the catalyst is ready to be characterized via STEM
and EXAFS.

STEM characterization

STEM imaging will give a rough estimate of the Pt particle size as well as a
pictorial representation of the Pt/Carbon Catalyst dispersion. From Figure 8, it can bee
seen that the Pt particles are roughly 10-20 Å and highly dispersed. The EXAFS results
will yield a numerical dispersion value.
Figure 8: Ketjen EC 600JC, S.A. = 1415 m^2/g, 30 wt% Pt/C, ave. particle size 10-20 Å.

Extended X-ray Absorption Fine Structure

The EXAFS were conducted at Argonne National Laboratory under Dr. Jeff
Miller’s supervision. The results obtained are promising and can be depicted from Figure
9. Mainly, Pt-Pt bonds are close, which can be seen through the small intense peaks.
Futhermore, results obtained by Dr. Miller’s fits shows that the estimated dispersion of
the Pt is ~ 90%, as can be seen from Table 4.
 Magnitude of FT [k3*Chi(k)]
Pt-Pt
0.2

Pt Higher
0.1 Shells

0 2 4 6

R [Å]

Figure 9: Timcal Timrex Wet impregnation EXAFS results.

EXAFS Fits Pt/Carbon

June 04
Sample Scatter CN R, Å DWF (x103) Eo, eV Est. Disp.
ctmrex WI Pt-Pt 4.7 2.74 1.0 -3.8 0.9

Table 4: Timcal Timrex Wet impregnation numerical value fits.

S.L SA CPA CPA

Method m^2/L (m^2/g) pH concetration PZC
Point of zero
795
charge 1000 - - -
SEA 500 - 200 200 8 to 9

Table 5: Optimized parameter for the SEA synthesis method and PZC experiments.
Conclusion

The research allowed for the identification of key variables shown in Table 5.
The optimization of these variables is vital to the catalyst preparation steps. The ideal
conditions at which to run the preparation of the catalyst are given in Table 5 as well,
primarily, use high PZC carbons, prepare CPA solution at a final pH of 2.8, surface
loading at 500 m^2/L, and CPA concentration of 200ppm. Using the conditions
presented, one can obtain important results like those given by the STEM and EXAFS.
In closing, I would like to thank the National Science Foundation for fuding the
research, the University of Illinois at Chicago, Professor John R. Regalbuto, and Dr. Jeff
Miller.
 References

[1] S. Giddey, F.T. Ciacchi, S.P.S. Badwal, V. Zelizko, J.H. Edwards, G.J. Duffy,
Elsevier Solid State Ionics 152 (2000) 363.
[2] Nice, K. (2000). How Fuel Cell Works. Retrieved July 23, 2003 from the
World Wide Web: http://science.howstuffworks.com/fuel-cell.htm
[3] Marshall, M. (1999). The Proton Exchange Membrane Fuel Cell.
Retrieved July 23, 2004 from the World Wide Web:
http://www.humboldt.edu/~serc/animation.html
[4]A. B. Stambouli, E. Traversa, J. Renewable & Sustainable Energy Reviews.
6 (2002) 297-306
[5] Nix, Roger (2003). Adsorption of Molecules on Surfaces.
Retrieved July 23, 2004 from the World Wide Web:
http://www.chem.gmw.ac.uk/surfaces/scc
[6] X. Hao, W.A. Spieker, J.R. Regalbuto, Journal of Colloid and Interface Science
267 (2003) 259