Herein we report a general electrochemical strategy for the Sandmeyer reaction. Using electricity as the driving force, this protocol employs a simple and inexpensive halogen source, such as NBS, CBrCl₃, CH₂I₂, CCl₄, LiCl and NaBr for the halogenation of aryl diazonium salts. In addition, we found that these electrochemical reactions could be performed using anilines as the starting material in a one-pot fashion. Furthermore, the practicality of this process was demonstrated in the multigram scale synthesis of aryl halides using highly inexpensive graphite as the electrode. A series of detailed mechanism studies have been performed, including radical clock and radical scavenger study, cyclic voltammetry analysis and in situ electron paramagnetic resonance (EPR) analysis.

As one of the most promising semiconductor oxide materials, titanium dioxide (TiO₂) absorbs UV light but not visible light. To address this limitation, the introduction of Ti³⁺ defects represents a common strategy to render TiO₂ visible-light responsive. Unfortunately, current hurdles in Ti³⁺ generation technologies impeded the widespread application of Ti³⁺ modified materials. Herein, we demonstrate a simple and mechanistically distinct approach to generating abundant surface-Ti³⁺ sites without leaving behind oxygen vacancy and sacrificing one-off electron donors. In particular, upon adsorption of organodiboron reagents onto TiO₂ nanoparticles, spontaneous electron injection from the diboron-bound O^2- site to adjacent Ti⁴⁺ site leads to an extremely stable blue surface Ti³⁺‒O^-· complex. Notably, this defect generation protocol is also applicable to other semiconductor oxides including ZnO, SnO₂, Nb₂O₅, and In₂O₃. Furthermore, the as-prepared photoelectronic device using this strategy affords 10³-fold higher visible light response and the fabricated perovskite solar cell shows an enhanced performance.