The photoelectrocatalytic (PEC) glycerol oxidation has emerged as a promising technology for the simultaneous valorization of this biomass waste and hydrogen production. Herein, we report the enhancement of the photocatalytic (PC) activity and stability of a monoclinic WO₃ catalyst, by means of an external bias, for the selective generation of value-added C₃ products under near-neutral conditions. Glyceraldehyde and dihydroxyacetone production were increased up to 4.5 and 11.5 times, respectively, while maintaining a liquid selectivity of these C3s above 87% and a stable faradaic efficiency above 50% of the additional holes generated, in a wide potential range (0.5–2.0 V vs. RHE). Indeed, the photo- and electro-catalytic contributing effects are unravelled for the first time herein. The photoelectrocatalytic mechanisms on WO₃ and WO₃/TiO₂ are discussed, as well as the key role of the sub-stoichiometric WO_3−x content and the oxygen vacancies, which confer advantageous properties for the selective PEC valorization of glycerol.

光电催化 (PEC) 甘油氧化已成为一种有前途的技术，可同时对这种生物质废物和氢气生产进行增值。_{在此，我们报道了通过外部偏压提高单斜晶系 WO 3}催化剂的光催化 (PC) 活性和稳定性，以选择性地生成增值 C ₃近中性条件下的产品。甘油醛和二羟基丙酮的产量分别提高了 4.5 倍和 11.5 倍，同时保持这些 C3s 的液体选择性高于 87% 和稳定的法拉第效率高于 50% 产生的额外空穴，在很宽的电位范围内（0.5-2.0 V与 RHE）。实际上，光催化和电催化的贡献效应在本文中首次被揭示。_{讨论了 WO 3}和 WO ₃ /TiO ₂的光电催化机理，以及亚化学计量的 WO _3-x含量和氧空位的关键作用，它们为甘油的选择性 PEC 增值提供了有利的性质。