On the Temperature Sensitivity of Electrochemical Reaction Thermodynamics

Abstract

Herein, we report a method to estimate the thermodynamic potentials of electrochemical reactions at different temperatures. We use a two-term Taylor series approximation of thermodynamic potential as a function of temperature, and we calculate the temperature sensitivity for a family of twenty seven known half reactions. We further analyze pairs of cathode and anode half-cells to pinpoint optimal voltage matches and discuss implications of changes in temperature on overall cell voltages. Using these observations, we look forward to increased interest in temperature and idealized half-reaction pairing as experimental choices for the optimization of electrochemical processes.

High-throughput parallel testing of ten photoelectrochemical cells for water splitting: case study on the effects of temperature in hematite photoanodes

“…3(b), right axis). The comparable decrease of the equilibrium potential of OER with temperature accounting for the shift of the hydrogen reference electrode (−1.73 mV K −1 ) 64,65 supports the previously reported hypothesis that the surface states follow a Nernstian behavior. 41…”

“…61 As a performance metric, ABPE has been found to have a number of issues when assessing photoelectrochemical devices under electrical bias. 62,63 Nevertheless, ABPE can be a useful tool for comparing the performance of a given material subjected to different operating conditions, although care must be taken as ABPE values should not be compared with other reports for different materials or devices. is the standard equilibrium potential of the oxygen evolution reaction (OER) at 25 °C (1.23 V vs. RHE), is the standard entropy of the OER, is the standard entropy of the hydrogen evolution reaction (HER) to account for the shift of the hydrogen reference electrode with temperature, z is the number of moles of electrons transferred in the half reaction per moles of reactant, F is the Faraday constant , 64,65 T the average cell temperature, T ° is the standard temperature (25 °C), E app is the applied potential, G LED is the total average irradiance from the blue LED (384 W m −2 ). The apparent photon conversion efficiency (PCE) is obtained as the product of photocurrent and photovoltage over the LED total irradiance (eqn (4)).…”

“…eq is the standard equilibrium potential of the oxygen evolution reaction (OER) at 25 °C (1.23 V vs. RHE), Ds OER is the standard entropy of the OER, Ds HER is the standard entropy of the hydrogen evolution reaction (HER) to account for the shi of the hydrogen reference electrode with temperature, z is the number of moles of electrons transferred in the half reaction per moles of reactant, F is the Faraday constant ððDs 64,65 T the average cell temperature, T°is the standard temperature (25 °C), E app is the applied potential, G LED is the total average irradiance from the blue LED (384 W m −2 ). The apparent photon conversion efficiency (PCE) is obtained as the product of photocurrent and photovoltage over the LED total irradiance (eqn (4)).…”

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“…Electrochemical cell potential can be affected by several factors, such as temperature, concentration, and pressure [ 38 ]. Since physical conditions are maintained the same for our experiments, changes in cell potential result from chemical composition of each solution.…”