Formaldehyde Ambient-Temperature Decomposition over Pd/Mn₃O₄-MnO Driven by Active Sites' Self-Tandem Catalysis

The widespread presence of formaldehyde (HCHO) pollutant has aroused significant environmental and health concerns. The catalytic oxidation of HCHO into CO₂ and H₂O at ambient temperature is regarded as one of the most efficacious and environmentally friendly approaches; to achieve this, however, accelerating the intermediate formate species formation and decomposition remains an ongoing obstacle. Herein, a unique tandem catalytic system with outstanding performance in low-temperature HCHO oxidation is proposed on well-structured Pd/Mn₃O₄-MnO catalysts possessing bifunctional catalytic centers. Notably, the optimized tandem catalyst achieves complete oxidation of 100 ppm of HCHO at just 18 °C, much better than the Pd/Mn₃O₄ (30%) and Pd/MnO (27%) counterparts as well as other physical tandem catalysts. The operando analyses and physical tandem investigations reveal that HCHO is primarily activated to gaseous HCOOH on the surface of Pd/Mn₃O₄ and subsequently converted to H₂CO₃ on the Pd/MnO component for deep decomposition. Theoretical studies disclose that Pd/Mn₃O₄ exhibits a favorable reaction energy barrier for the HCHO → HCOOH step compared to Pd/MnO; while conversely, the HCOOH → H₂CO₃ step is more facilely accomplished over Pd/MnO. Furthermore, the nanoscale intimacy between two components enhances the mobility of lattice oxygen, thereby facilitating interfacial reconstruction and promoting interaction between active sites of Pd/Mn₃O₄ and Pd/MnO in local vicinity, which further benefits sustained HCHO tandem catalytic oxidation. The tandem catalysis demonstrated in this work provides a generalizable platform for the future design of well-defined functional catalysts for oxidation reactions.