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Standard Operating Procedure

Flame-annealing and subsequent cooling of Pt single-


crystal electrodes
Prepared by Dr. Angel Cuesta 08/01/2014

for Electrochemistry labs in Meston G68

Introductory remarks

The aim of electrochemical experiments with single-crystal electrodes is to obtained


detailed information about the structure of the electrochemical double layer and
about structure-reactivity relationships in electrochemical reactions. This obviously
requires working with very clean surfaces whose atomic structure coincides with the
nominal one and can reproducibly be re-established. In the case of Pt, this can be
achieved by annealing the crystal in the flame of a Bunsen burner (which cleans the
surface from contaminants and allows the surface atoms to attain their equilibrium
positions) followed by cooling in a reducing atmosphere (to avoid roughening of the
surface due to reaction with atmospheric oxygen). The cooling step consists of
introducing the red-hot crystal in a flask containing a N 2 + H2 atmosphere. In some
cases, good results can be obtained using a N 2 + CO atmosphere.

Preparation of the cooling atmosphere

The cooling atmosphere must be prepared in a small flask containing a small volume
of ultrapure water, with two built-in gas bubblers, an output tube with a valve, and a
glass cone with a glass stopper. The stopper must fit perfectly in the cone. One of the
bubblers is used to bubble N2 and the other to bubble H2 (or CO).

Health and Safety

Hydrogen is flammable and, at concentrations above 10-15% its reaction with


oxygen is explosive. CO is flammable and poisonous. Hence, none of these
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gases must be released into the laboratorys atmosphere. A flexible tube


connected to the flasks output tube must be used to send the gases outside the
building through a fume hood or through a window.

Only nitrogen must be continuously bubbled into the flask, which must be purged
for at least 15 min before H2 or CO are introduced. This avoids the risk of mixing
these gases with oxygen within the flask.

Hydrogen or carbon monoxide must only be introduced just before starting the
flame annealing, and H2 or CO bubbling must be stopped immediately after
finishing the cooling step, which must not take more than ca. 5 min.

The flux of hydrogen or CO must always be < 50% of the nitrogen flux. This can
be controlled by looking at the height reached by the bubbles in the corresponding
bubblers: the height in the H 2 or CO bubbler must be less than half the height in
the nitrogen bubbler.

The valve in the output tube must be kept open. Just before finishing the flame-
annealing step, the stopper must be loosed (not removed), in order to allow the
overpressure inside the flask to be released through the thin space between the
stopper and the cone. Then the valve in the output tube must be closed. These
will create an oxygen poor atmosphere around the flask opening, and will reduce
the risk of bringing oxygen into the flask when introducing the red-hot crystal.

The crystal holder must perfectly fit in the flasks cone. After annealing the crystal
in the flame during 2-3 min, the stopper must be removed and the red-hot crystal
immediately introduced in the flask. The valve in the output tube must be
immediately opened. A small flame, which will extinguish as soon as the flask is
closed by the perfectly-fitting electrode holder, might form. This is not bad, since it
will remove oxygen in the atmosphere around the opening and avoid it from
entering the flask. Gloves must never be worn.

The time required to cool the crystal down to room temperature depends on the
crystals size. For our single-crystal electrodes it is typically of 15-20 s. Once cold,
a drop of ultrapure water is attached to the electrode surface, in order to protect it
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from contamination when transferred to the electrochemical cell through the


laboratorys atmosphere.

Before taking the electrode out of the flask, the H 2 or CO bubbling must be
stopped (only the N2 bubbling must always be kept running). The flask must be
closed with the stopper once the electrode has been taken out.