Scheme 2: Under reductive bias, diphenyliodonium polymerizes on the electrode surface to form a robust polyaromatic coating that is electronically insulating, but permeable to reactants and solvent. In our previous work, we determined organic films create hydrodynamically isolated electrode microenvironments. We hypothesized that the addition of an organic coating would protect intermediates for long enough close to the electrode surface to allow for them to equilibrate with SH electrode temperatures. While we previously investigated films based on N,N'-ethylenephenanthrolinium dibromide, herein we investigate those derived from diphenyliodonium triflate due to their increased robustness (Scheme 2). Upon the incorporation of an organic film, we observe a boost in C2+ FE and a systematic increase in activity for carbon-coupled products with temperature. In addition to the change in catalytic performance, we observe a positive shift in onset potential for carbon-coupled product formation (Figure ; Figure , Table ). The highest activity for C2+ products was observed at -1.02 V vs RHE and SH=60 °C, where we obtained a FEC2+ of 44% and a partial current density of 6.61 mA/cm 2 . With the organic coating, at ambient temperature an additional 0.1 V of overpotential is needed to obtain comparable C2+ activity, highlighting how the temperature-based improvements to electrokinetics enable operation at lower overpotentials. This activity and selectivity are beyond those observed without an organic coating, regardless of temperature. The systematic increase in electrokinetics with increasing surface temperature is more apparent in the presence of the organic coating than in its absence. This systematic improvement to C2+ activity is observed up to 60 °C, above which we suspect that the loss in improvement may be from delamination of the organic coating or the restructuring of copper. While the Butler-Volmer expression is analogous to a traditional Arrhenius rate constant expression, calculating the activation energy for an electrochemical reaction is non-trivial because any temperature dependent analysis (such as plotting log10(ik) vs 1/𝑇) will result in the calculation of a convolution of activation energy, transfer coefficient, and applied potential. Specifically, the slope on a log10(ik) vs 1/𝑇 plot is not the activation energy as it is with a thermochemical reaction, but instead is the quantity (-Ea+𝛼𝜙). Thus, to calculate the activation energy of an electrochemical reaction, a comprehensive analysis of a range of potentials and temperatures is necessary, which is seldom done due to limitations in sufficient data collection for rigorous parameter estimation procedures. As a result, we took additional data points at intermediate temperatures to better describe the transition in onset potential across temperatures and fit the resulting data to a temperature dependent Butler-Volmer model coupled with a mass-transfer limiting current (Figure ). Using the data collected from HT-ANEC at a range of temperatures and potentials with a surface film, we simultaneously calculated posterior distributions for the activation energy (Figure , See SI for discussion and derivation). The result is an activation energy for CO2 reduction of ca. 1.0 eV, differs from previously reported values (ca. 0.5 eV), because here we calculate just the activation energy, while previous analyses calculate the value of the expression (-Ea+𝛼𝜙). Note that we include all carbon-coupled products in this analysis due to their presumed common rate determining step, and therefore activation barrier. In addition to the activation energy, we can calculate practical system parameters such as the rate of change of the onset potential with changing temperature (Figure ) and the rate of change of the current with changing temperature (Figure ).