Orbital‐Hybridization‐Driven N‐Fe‐Mo Interatomic Charge Bridges at Amorphous FeMoOx/Porous Carbon Nitride Interface Boosting Peroxymonosulfate Activation in Fenton‐like Reaction

Why It Matters

By overcoming kinetic limits of PMS activation, the approach enables more efficient, long‑duration wastewater treatment, offering a template for next‑generation catalytic materials in the water‑purification market.

Key Takeaways

• Orbital hybridization creates N‑Fe‑Mo electron highways
• >99% RhB removal in 50‑hour continuous flow
• Singlet oxygen identified as primary reactive species
• Strategy reduces Fe(III)→Fe(II) reduction barrier

Pulse Analysis

The peroxymonosulfate (PMS) based Fenton‑like process has attracted attention for degrading recalcitrant organic pollutants, yet its commercial adoption is hampered by slow Fe(III) to Fe(II) reduction and inefficient electron exchange at the catalyst surface. Conventional iron oxides rely on bulk redox chemistry, which often leads to high activation energy and limited selectivity. Recent advances in nanostructured interfaces suggest that tailoring atomic‑scale interactions can reshape the electronic landscape, thereby accelerating the generation of reactive oxygen species. In this context, orbital hybridization emerges as a powerful tool to engineer charge pathways that directly couple the oxidant to the active metal centers.

The study introduces a hybrid material where amorphous FeMoOx is intimately coupled with porous carbon nitride (pCN), forming directional N‑Fe‑Mo charge‑transfer bridges. Spectroscopic analysis and density‑functional calculations reveal that nitrogen 2p orbitals hybridize with iron 3d states, while molybdenum acts as an electron reservoir, creating a continuous “highway” for electrons to reach PMS molecules. This interfacial architecture not only lowers the Fe(III)→Fe(II) reduction barrier but also steers the reaction toward singlet oxygen (^1O2) as the dominant oxidant, improving selectivity and minimizing undesired by‑products. Performance testing demonstrated >99% removal of Rhodamine B over a 50‑hour continuous flow, treating 75 L of contaminated water without loss of activity.

The implications extend beyond a single dye‑degradation case. By proving that atomic‑scale charge‑transfer bridges can dramatically enhance PMS activation, the research opens a pathway for designing catalysts that are both highly active and durable in real‑world water‑treatment plants. Industries ranging from textile manufacturing to pharmaceutical waste management could adopt such materials to meet stricter discharge regulations while reducing chemical dosing costs. Moreover, the concept is transferable to other advanced oxidation processes, such as persulfate or electro‑Fenton systems, positioning orbital‑hybridization engineering as a strategic lever for the next generation of sustainable environmental technologies.