High-Density Nanosharp Microstructures Enable Efficient CO2 Electroreduction.

Conversion of CO2 to CO powered by renewable electricity not only reduces CO2 pollution but also is a means to store renewable energy via chemical production of fuels from CO. However, the kinetics of this reaction are slow due its large energetic barrier. We have recently reported CO2 reduction that is considerably enhanced via local electric field concentration at the tips of sharp gold nanostructures. The high local electric field enhances CO2 concentration at the catalytic active sites, lowering the activation barrier. Here we engineer the nucleation and growth of next-generation Au nanostructures. The electroplating overpotential was manipulated to generate an appreciably increased density of honed nanoneedles. Using this approach, we report the first application of sequential electrodeposition to increase the density of sharp tips in CO2 electroreduction. Selective regions of the primary nanoneedles are passivated using a thiol SAM (self-assembled monolayer), and then growth is concentrated atop the uncovered high-energy planes, providing new nucleation sites that ultimately lead to an increase in the density of the nanosharp structures. The two-step process leads to a new record in CO2 to CO reduction, with a geometric current density of 38 mA/cm2 at -0.4 V (vs reversible hydrogen electrode), and a 15-fold improvement over the best prior reports of electrochemical surface area (ECSA) normalized current density.