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A microcalorimeter for measuring heat effects of electrochemical reactions with submonolayer conversions
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View: Figures


Image of FIG. 1.
FIG. 1.

Schematic of the cell. The thin WE is mounted directly onto the free-standing pyroelectric detector foil. Thermal contact is established by removing the air in between electrode and detector foil (RE: reference electrode and CE: counter electrode).

Image of FIG. 2.
FIG. 2.

Sketch of the electronic circuit. The pyrolectric signal is collected at the backside of the metallized PVDF foil, referenced to the WE. The electrochemical cell current is measured at the CE. The cell can be electrically switched off by the computer controlled ocp-switch (RE: reference electrode and CE: counter electrode).

Image of FIG. 3.
FIG. 3.

Temperature response of the electrode-sensor assembly to a 10 ms laser pulse of ≈5 mW. Pulse start and end are indicated by dashed lines. The inset shows the temperature transient up to .

Image of FIG. 4.
FIG. 4.

Temperature response to laser pulses with varying pulse duration but identical total energy. (a) 2.5, 5, and 10 ms pulses, around per pulse. (b) 10, 20, and 40 ms, around per pulse.

Image of FIG. 5.
FIG. 5.

Potential , temperature , and electrochemical current transients upon pulsed Ag dissolution (a) and deposition (b) onto around 300 ML thick Ag layer on Au. (, Au foil, supported by thick Si). Before the potential pulse, the cell potential was set to the equilibrium potential . At the potential was stepped 5 mV positive (a) or negative (b). After 10 ms the cell current was forced to 0 by opening the ocp-switch.

Image of FIG. 6.
FIG. 6.

Temperature change, measured 10 ms after the beginning of the potential pulse for different electrochemical conversion, i.e., electrochemical charge density upon deposition or dissolution of Ag in . Prior to the experiments, around 300 ML Ag were deposited onto the Au electrode. For comparison the electrochemical conversion is also given in ML of Ag, assuming one transferred elementary charge per Ag atom in a Ag(111) surface. Triangles: data measured potentiostatically with constant amplitude potential pulses. Circles: data measured galvanostatically, i.e., with constant current during the deposition or dissolution pulse. The inset shows a closeup for low conversions.

Image of FIG. 7.
FIG. 7.

Temperature change normalized to the electrochemical conversion, measured with 10 ms potential pulses for the Fe(II)/Fe(III) electron transfer reaction in (diamonds) and the ion transfer reaction in (triangles: potentiostatic pulses; circles: galvanostatic pulses). The right axis was obtained by calibration of the calorimeter with the help of literature data (see text).


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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: A microcalorimeter for measuring heat effects of electrochemical reactions with submonolayer conversions