Porous Electropolymerized Films of Ruthenium Complex: Photoelectrochemical Properties and Photoelectrocatalytic Synthesis of Hydrogen Peroxide.

The photoelectrochemical cells (PECs) performing high-efficiency conversions of solar energy into both electricity and high value-added chemicals are highly desirable but rather challenging. Herein, we demonstrate that a PEC using the oxidatively electropolymerized film of a heteroleptic Ru(II) complex of [Ru(bpy)( L ) 2 ](PF 6 ) 2 Ru1 {bpy and L stand for 2,2'-bipyridine and 1-phenyl-2-(4-vinylphenyl)-1 H -imidazo[4,5- f ][1,10]phenanthroline respectively}, poly Ru1 , as a working electrode performed both efficient in situ synthesis of hydrogen peroxide and photocurrent generation/switching. Specifically, when biased at -0.4 V vs. saturated calomel electrode and illuminated with 100 mW·cm -2 white light, the PEC showed a significant cathodic photocurrent density of 9.64 μA·cm -2 . Furthermore, an increase in the concentrations of quinhydrone in the electrolyte solution enabled the photocurrent polarity to switch from cathodic to anodic, and the anodic photocurrent density reached as high as 11.4 μA·cm -2 . Interestingly, in this single-compartment PEC, the hydrogen peroxide yield reached 2.63 μmol·cm -2 in the neutral electrolyte solution. This study will serve as a guide for the design of high-efficiency metal-complex-based molecular systems performing photoelectric conversion/switching and photoelectrochemical oxygen reduction to hydrogen peroxide.