Transition Metal and Metal-Nx Codoped MOF-Derived Fenton-Like Catalysts: A Comparative Study on Single Atoms and Nanoparticles.

To deal with the ever-growing toxic benzene-derived compounds in the water system, extensive efforts have been dedicated for catalytic degradation of pollutants. However, the activities and efficiencies of the transition metal-based nanoparticles or single-atom sites are still ambiguous in Fenton-like reactions. Herein, to compare the Fenton-like catalytic efficiencies of the nanoparticles and single atoms, the free-standing nanofibrous catalyst comprising Co nanocrystals and Co-Nx codoped carbon nanotubes (CNTs) or bare Co-Nx doped CNTs is fabricated. It is noteworthy that all these nanofibrous catalysts exhibit efficient activities, mesoporous structures, and conductive carbon networks, which allow a feasible validation of the catalytic effects. Benefiting from the maximized atomic utilization, the atomic Co-Nx centers exhibit much higher reaction kinetic constant (κ = 0.157 min-1 ) and mass activity toward the degradation of bisphenol A, far exceeding the Co nanocrystals (κ = 0.082 min-1 ). However, for the volume activities, the single-atom catalyst does not show apparent advantages compared to the nanocrystal-based catalyst. Overall, this work not only provides a viable pathway for comparing Fenton-like catalytic effects of transition metal-based nanoparticles or single atoms but also opens up a new avenue for developing prominent catalysts for organic pollutants' degradation.