The reaction mechanism at the fuel cell cathode
Using density functional theory (DFT) with the B3LYP gradient-corrected
exchange–correlation functional, we systematically studied the cathode
reaction of polymer electrolyte membrane (PEM) fuel cells in gas-phase:
As catalyst material we assumed Pt, which was modeled with a cluster of
Figure 1: Motivation for choosing Pt14.13.8.
We first calculated binding structures and energetics for each
intermediate on the Pt(111) surface plane separately: O, H, O2,
H2, OH, OOH, H2O. Atomic oxygen binds most
strongly at the µ3-fcc position (77.71 kcal/mol),
while molecular O2 prefers the bridge site (11.30 kcal/mol).
Thus, OOH prefers the same geometry with one O covalently bound on top
of a Pt atom (23.85 kcal/mol). Including zero-point energy (ZPE) a
single H atom prefers the µ3-fcc over an on top site
by ˜3.2 kcal/mol, whereas molecular H2 undergoes
dissociation to two on top bound H atoms wile adsorbing on Pt. OH and
water show comparable binding structures (on top bound), but a
different type of binding. The hydroxyl radical binds covalently to one
Pt atom (47.45 kcal/mol), and water uses the remaining lone pair
orbital of its oxygen to attach to the surface atom (13.90 kcal/mol).
In order to study whole reaction pathways we calculated all possible
dissociation processes of the various intermediates on the Pt cluster.
Using all energetics we calculated heats of formation (?Hf)
and combined these with the dissociation barriers. Since on the cathode
oxygen and hydrogen catalytically reacts to water, we studied possible
reaction pathways starting with gas-phase H2 and O2.
We distinguished between two main reaction pathways:
Along the O2-Dissociation pathway oxygen adsorbs on the
surface, dissociates, and finally reacts with hydrogen to form water.
With a barrier of 31.66 kcal/mol the rate-determining step for this
mechanism is the Oad + Had --> OHad
reaction and not the dissociation of O2. Since O2
changes its adsorption structure during dissociation the dissociation
barrier is lowered to only 15.02 kcal/mol. Along the OOH-Formation
pathway adsorbed O2 first forms OOH with a surface hydrogen,
and the generates OH via O–OH dissociation, which finally reacts with
another hydrogen to water. For this mechanism the OOHad
--> OHad + Oadfcc dissociation has
the highest barrier with 17.13 kcal/mol. Thus, we propose the
OOH-Formation mechanism to be the most likely pathway for the cathode
reaction. This pathway may additionally be supported by recombination
of two adsorbed surface oxygens.
Further investigations will address the effects of solvation and the
presence of an external electric field. In this context, we will also
present first simulations using the reactive ForceField (reaxFF).
Besides the pure cathode reaction, the interface between the electrode
and the electrolyte plays an important role for structural purposes,
but also for supporting partial reaction steps.
Figure 2: Model for simulating the Electrode–Electrolyte
Interface. The central part models the bulk polymer..
We will present first moleculardynamic simulations on the electrolyte
structure close to the electrode. In the interface region we find an
increased polymer density (compared to the polymer bulk area). In
addition, the presence of the electrode surface seems to result in a
lower water content interface. The extracted water forms a water
monolayer on the surface comparable to the QM calculations for 2/3ML
coverage. For low water-content there is a direct attachment of the
polymer chains to the electrode, resulting in hydrophilic regions.
However, increasing the water-content prevents this attachment and
almost the whole polymer is separated from the electrode by the water
Personnel: Dr. Timo Jacob
This project is co-directed by Dr. Boris Merinov and Dr. Adri van Duin.