Electrode Surface Heating with Organic Films Improves CO2 Reduction Kinetics on Copper.

Management of the electrode surface temperature is an understudied aspect of (photo)electrode reactor design for complex reactions, such as CO2 reduction. In this work, we study the impact of local electrode heating on electrochemical reduction of CO2 reduction. Using the ferri/ferrocyanide open circuit voltage as a reporter of the effective reaction temperature, we reveal how the interplay of surface heating and convective cooling presents an opportunity for cooptimizing mass transport and thermal assistance of electrochemical reactions, where we focus on reduction of CO2 to carbon-coupled (C2+) products. The introduction of an organic coating on the electrode surface facilitates well-behaved electrode kinetics with near-ambient bulk electrolyte temperature. This approach helps to probe the fundamentals of thermal effects in electrochemical reactions, as demonstrated through Bayesian inference of Tafel kinetic parameters from a suite of high throughput experiments, which reveal a decrease in overpotential for C2+ products by 0.1 V on polycrystalline copper via 60 °C surface heating.

Ammonium Formate as a Safe, Energy-Dense Electrochemical Fuel Ionic Liquid.

While solid and liquid energy carriers are advantageous due to their high energy density, many do not meet the efficiency requirements to outperform hydrogen. In this work, we investigate ammonium formate as an energy carrier. It can be produced economically via a simple reaction of ammonia and formic acid, and it is safe to transport and store because it is solid under ambient conditions. We demonstrate an electrochemical cell that decomposes ammonium formate at 105 °C, where it is an ionic liquid. Here, hydrogen evolves at the cathode and formate oxidizes at the anode, both with ca. 100% Faradaic efficiency. Under the operating conditions, ammonia evaporates before it can oxidize; a second, modular device such as an ammonia fuel cell or combustion engine is necessary for complete oxidation. Overall, this system represents an alternative class of electrochemical fuel ionic liquids where the electrolyte is majority fuel, and it results in a modular release of hydrogen with potentially zero net-carbon emissions.

In situ electrochemical generation of nitric oxide for neuronal modulation.

Understanding the function of nitric oxide, a lipophilic messenger in physiological processes across nervous, cardiovascular and immune systems, is currently impeded by the dearth of tools to deliver this gaseous molecule in situ to specific cells. To address this need, we have developed iron sulfide nanoclusters that catalyse nitric oxide generation from benign sodium nitrite in the presence of modest electric fields. Locally generated nitric oxide activates the nitric oxide-sensitive cation channel, transient receptor potential vanilloid family member 1 (TRPV1), and the latency of TRPV1-mediated Ca2+ responses can be controlled by varying the applied voltage. Integrating these electrocatalytic nanoclusters with multimaterial fibres allows nitric oxide-mediated neuronal interrogation in vivo. The in situ generation of nitric oxide in the ventral tegmental area with the electrocatalytic fibres evoked neuronal excitation in the targeted brain region and its excitatory projections. This nitric oxide generation platform may advance mechanistic studies of the role of nitric oxide in the nervous system and other organs.