ABSTRACT
The photoelectrochemical (PEC) performance of bismuth vanadate (BiVO4) suffers from sluggish charge mobility and substantial charge recombination losses due to its intrinsic defect. To rectify the problem, we developed a novel approach to prepare an n-n+ type II BVOac-BVOal homojunction with staggered band alignment. This architecture involves a built-in electric field that facilitating the electron-hole separation at the BVOac/BVOal interface. As a result, the BVOac-BVOal homojunction shows superior photocurrent density up to 3.6 mA/cm2 at 1.23 V vs. reversible hydrogen electrode (RHE) with 0.1 M sodium sulfite as the hole scavenger, which is 3 times higher than that of the single-layer BiVO4 photoanode. Unlike the previous efforts that modifying the PEC performance of BiVO4 photoanodes through incorporating heteroatoms, the highly-efficient BVOac-BVOal homojunction was achieved without incorporating any heteroatoms in this work. The remarkable PEC activity of the BVOac-BVOal homojunction highlights the tremendous importance of reducing the charge recombination rate at the interface by constructing the homojunction and offers an effective strategy to form the heteroatoms-free BiVO4 thin film as an efficient photoanode material for practical PEC applications.
ABSTRACT
To improve the photoelectrochemical (PEC) performance of photocatalysts, the doping strategy through covalent functionalization is often adopted to adjust material electronic structures. By contrast, this work demonstrates that the noncovalent interaction in the case of iodinated graphitic carbon nitride (g-CN) film can also enhance the PEC performance. Through a facile synthesis method of rapid thermal vapor condensation (RTVC), the prepared iodinated g-CN film shows a significantly improved photocurrent density (38.9 µA cm-2 ), three times that of pure g-CN film (13.0 µA cm-2 ) at 1.23 V versus reversible hydrogen electrode. Computations reveal that the noncovalent attachment of iodine anion (I- ) on g-CN plays a crucial role in modulating the bandgap states and broadening of the visible-light absorption range as well as the charge carrier separation with the photo-induced hole confined to I- and electron to g-CN film. The fully filled valence orbitals (4d10 5s2 5p6 ) of I- determine its noncovalent attachment on the g-CN film and so do the iodine species of I3 - , I5 - , etc. This work offers a favorable synthesis method to achieve efficient doping through noncovalent charge transfer between thin film and certain dopants and provides a useful modification strategy for the establishment of multi-channel transportation of charge carriers in general photocatalysts.