Abstract
Oriented external electric fields are now emerging as "smart effectors" of chemical changes. The key challenges in experimentally studying electrostatic catalysis are (i) controlling the orientation of fields along the reaction axis and (ii) finely adjusting the magnitudes of electrostatic stimuli. Surface models provide a versatile platform for addressing the direction of electric fields with respect to reactants and balancing the trade-off between the solubility of charged species and the intensity of electric fields. In this mini-review, we present the recent advances that have been investigated of the electrostatic effect on the chemical reaction on the monolayer-functionalized silicon surfaces. We mainly focus on elucidating the mediator/catalysis role of static electric fields induced from either solid/liquid electric double layers at electrode/electrolyte interfaces or space charges in the semiconductors, indicating the electrostatic aspects is of great significance in the semiconductor electrochemistry, redox electroactivity, and chemical bonding. Herein, the functionalization of silicon surfaces allows scientists to explore electrostatic catalysis from nanoscale to mesoscale; most importantly, it provides glimpses of the wide-ranging potentials of oriented electric fields for switching on/off the macroscale synthetic organic electrochemistry and living radical polymerization.