Description:
<jats:title>Abstract</jats:title><jats:p>Given its favorable physical and chemical properties, Bismuth vanadate (BiVO<jats:sub>4</jats:sub>) is a commonly studied metal oxide semiconductor for photocatalytic applications. However, BiVO<jats:sub>4</jats:sub> shows a high recombination rate of photogenerated charges and limited charge transport capacity, which can be addressed by doping it with tungsten. To develop a highly efficient tungsten‐doped BiVO<jats:sub>4</jats:sub>‐based (W‐BiVO<jats:sub>4</jats:sub>) photocatalyst, it is necessary to control the dopant content, crystal structure, and morphology. These properties are, in turn, governed by the synthesis conditions. This work describes a pioneering method of microwave‐assisted reflux synthesis of W‐BiVO<jats:sub>4</jats:sub>, using ethanol as solvent and polyvinyl pyrrolidone (PVP) as a capping agent. Thus, it is possible to perform the synthesis procedure in only 30 min at 78°C, obtaining extremely regular monoclinic W‐BiVO<jats:sub>4</jats:sub> nanosquares. Furthermore, the experiments showed that the most efficient photocatalyst contains 3% tungsten as the dopant. Moreover, the direct oxidation of rhodamine B by the photogenerated holes plays a crucial role in the degradation mechanism. Finally, we observed that although the addition of PVP promotes control of the morphology, it results in a poorly efficient material. This low efficiency may be related to the formation of a polymeric coating on the surface of the catalyst or to a high amount of oxygen defects. Finally, we show that the unique interaction of microwaves with the species present in the reaction media influences nanoparticle growth.</jats:p>