Enhanced Photoelectrochemical Water Oxidation on BiVO4 Photoanodes Functionalized by Bimetallic Dicyanamide Molecular Catalysts

A novel hybrid structure of bimetallic dicyanamide decorated BiVO4 is developed via a simple method to accelerate interfacial water oxidation kinetics. Two types of bimetallic dicyanamides, CoNi(dca)2 and CoFe(dca)2, are coated on BiVO4 photoanodes and are found to exhibit far more enhanced PEC performance than Co(dca)2 or Ni(dca)2 as cocatalysts. The successful deposition of metal dicyanamides on BiVO4 photoanodes is confirmed by physical characterizations including X-ray photoelectron spectroscopy (XPS). The optimized Co0.9Ni0.1(dca)2/BiVO4 photoanode exhibits the highest photocurrent density of 2.58 mA/cm2 at 1.23 V vs. RHE under 100 mW/cm2 AM 1.5 G irradiation, which is 2.5 times that of bare BiVO4. The substantial enhancement of PEC performance can be ascribed to the advantageous interfacial charge transfer and improved charge injection efficiencies. This work presents a feasible strategy using different types of bimetallic dicyanamides to design a modified BiVO4-based photoanode system for enhanced water oxidation efficiency.