Selective photocatalytic reduction of nitric oxide to dinitrogen via bimetallic bond incorporation

[Display omitted] •Fe–O–Bi was identified as the key active site of the first rate-limiting NO adsorbate state.•N2O formation was confirmed as the rate-determining step.•BFWO is also capable of photocatalytic N2O removal.•NO linkage with Fe–O–Bi benefits intermediates formation, boosting NO removal and selectivity. In this study, we addressed the challenge of optimizing the first rate-limiting NO adsorbate state, which has received limited attention in previous research on the photoreduction of NO. We prepared BiFeWO6 (BFWO), which improved not only the NO removal rate under illumination but also the selectivity of photocatalytic NO conversion to N2. To further optimize the performance, we introduced platinum into BFWO, achieving a 57.5 % NO conversion rate with ∼80 % N2 selectivity under 425 nm light-emitting diode illumination (50 mW/cm2), which is optimal for converting NO into less harmful compounds at low concentrations. FeOBi bonds were identified as the key active sites of the first rate-limiting NO adsorbate state in BFWO through time-resolved operando infrared (IR) spectroscopy and density functional theory (DFT) analysis. The specific adsorption configuration of NO on the FeOBi group accelerated the photoreduction reaction kinetics, resulting in superior photocatalytic NO removal performance.