Robust route to H₂O₂ and H₂ via intermediate water splitting enabled by capitalizing on minimum vanadium-doped piezocatalysts

H₂O₂ is an environmentally friendly chemical for a wide range of water treatments. The industrial production of H₂O₂ is an anthraquinone oxidation process, which, however, consumes extensive energy and produces pollution. Here we report a green and sustainable piezocatalytic intermediate water splitting process to simultaneously obtain H₂O₂ and H₂ using single crystal vanadium (V)-doped NaNbO₃ (V-NaNbO₃) nanocubes as catalysts. The introduction of V improves the specific surface area and active sites of NaNbO₃. Notably, V-NaNbO₃ piezocatalysts of 10 mg exhibit 3.1-fold higher piezocatalytic efficiency than the same catalysts of 50 mg, as more piezocatalysts lead to higher probability of aggregation. The aggregation causes reducing active sites and decreased built-in electric field due to the neutralization between different nano-catalysts. Remarkably, piezocatalytic H₂O₂ and H₂ production rates of V-NaNbO₃ (10 mol%) nanocubes (102.6 and 346.2 μmol·g⁻¹·h⁻¹, respectively) are increased by 2.2 and 4.6 times compared to the as-prepared pristine NaNbO₃ counterparts, respectively. This improved catalytic efficiency is attributed to the promoted piezo-response and more active sites of NaNbO₃ catalysts after V doping, as uncovered by piezo-response force microscopy (PFM) and density functional theory (DFT) simulation. More importantly, our DFT results illustrate that inducing V could reduce the dynamic barrier of water dissociation over NaNbO₃, thus enhancing the yield of H₂O₂ and H₂. This facile yet robust piezocatalytic route using minimal amounts of catalysts to obtain H₂O₂ and H₂ may stand out as a promising candidate for environmental applications and water splitting.