Search

[Display omitted] Metal-organic polymers (MOPs) can enhance the photoelectrochemical (PEC) water oxidation performance of BiVO 4 photoanodes, but their PEC mechanisms have yet to be comprehended. In this work, we constructed an active and stable composite photoelectrode by overlaying a uniform MOP on the BiVO 4 surface using Fe2+ as the metal ions and 2,5-dihydroxyterephthalic acid (DHTA) as ligand. Such modification on the BiVO 4 surface yielded a core-shell structure that could effectively enhance the PEC water oxidation activity of the BiVO 4 photoanode. Our intensity-modulated photocurrent spectroscopy analysis revealed that the MOP overlayer could concurrently reduce the surface charge recombination rate constant (k sr) and enhance the charge transfer rate constant (k tr), thus accelerating water oxidation activity. These phenomena can be ascribed to the passivation of the surface that inhibits the recombination of the charge carrier and the MOP catalytic layer that improves the hole transfer. Our rate law analysis also demonstrated that the MOP coverage shifted the reaction order of the BiVO 4 photoanode from the third-order to the first-order, resulting in a more favorable rate-determining step where only one hole accumulation is required to overcome water oxidation. This work provides new insights into the reaction mechanism of MOP-modified semiconductor photoanodes. [ABSTRACT FROM AUTHOR]

[Display omitted] • Enhanced photoelectrochemical water oxidation on Bi 2 WO 6 photoanodes by heterojunction and facet-engineering. • The heterojunction of WO 3 /Bi 2 WO 6 improved charge separation and transfer. • Crystalline {2 0 0} and {1 3 1} orientations on WO 3 /Bi 2 WO 6 and Bi 2 WO 6 films, respectively. • A 1st-order and a 2nd-order charge reaction kinetics were discovered on {2 0 0} and {1 3 1} facets, respectively. Charge separation and transfer kinetics play a significant role in photocatalytic water oxidation, which is sensitive to the crystal facets. Herein, the bismuth tungstate (Bi 2 WO 6) films were used as a model photoanode to investigate how the photogenerated charges react on {1 3 1} and {2 0 0} facets under constantly applied bias in a photoelectrochemical (PEC) cell. On the WO 3 electron transport layer, the Bi 2 WO 6 films have a {2 0 0} orientation while possessing a {1 3 1} orientation on the fluorine-doped tin oxide substrate. It is discovered that {2 0 0} facets on the WO 3 /Bi 2 WO 6 heterojunction display a low overpotential of PEC water oxidation, showing a 1st-order reaction behavior and faster charge transfer rate constant. Differently, water oxidation on the {1 3 1} facet on Bi 2 WO 6 displays a 2nd-order reaction behavior. Further, density functional theory calculations were applied to demonstrate how the rate-determining step and the major formed intermediate correlate with the charge accumulation and reaction orders. The findings of this work shed fundamental light on how to rationally design and precisely modulate surface charge density and reaction kinetics for efficient (photo)electrocatalysts. [ABSTRACT FROM AUTHOR]