Interfacial OOH* mediated Fe(II) regeneration on the single atom Co-N-C catalyst for efficient Fenton-like processes.

Fe(II) regeneration is decisive for highly efficient H2O2-based Fenton-like processes, but the role of cobalt-containing reactive sites in promoting Fe(II) regeneration was overlooked. Herein, a single atom Co-N-C catalyst was employed in Fe(II)/H2O2 system to promote the degradation of diverse organic contaminants. The EPR and quenching experiments indicated Co-N-C significantly enhanced the generation of superoxide species, and accelerated hydroxyl radical generation for pollutant degradation. The electrochemical and surface composition analyses demonstrated the enhanced H2O2 activation and Fe(III)/Fe(II) recycling on the catalyst. Furthermore, in-situ Raman characterization with shell-isolated gold nanoparticles was employed to visualize the interfacial reactive intermediates and their time-resolved interaction. The accumulation of interfacial CoOOH* was confirmed when Co-N-C activated H2O2 alone, but it rapidly transformed into FeOOH* upon Fe(II) addition. Besides, the temporal variation of OOH* intermediates and the relative intensity of Co(III)-O and Co(IV)=O peaks depicted the dynamic interaction of reactive intermediates along the H2O2 consumption. With this basis, we proposed a mechanism of interfacial OOH* mediated Fe(II) regeneration, which overcame the kinetical limitation of Fe(II)/H2O2 system. Therefore, this study provided a primary effort to elucidate the overlooked role of interfacial CoOOH* in the Fenton-like processes, which may inspire the design of more efficient catalysts.

Boosting the singlet oxygen production from H2O2 activation with highly dispersed Co-N-graphene for pollutant removal.

Singlet oxygen (1O2) is a promising reactive species for the selective degradation of organic pollutants. However, it is difficult to generate 1O2 from H2O2 activation with high efficiency and selectivity. In this work, a graphene-supported highly dispersed cobalt catalyst with abundant Co-N x active sites (Co-N-graphene) was synthesized for activating H2O2. The Co-N-graphene catalyzed H2O2 reaction system selectively catalyzed 1O2 production associated with the superoxide radical (O2˙-) as the critical intermediate, as proven by scavenger experiments, electron spin resonance (ESR) spin trapping and a kinetic solvent isotope effect study. This resulted in excellent degradation efficiency towards the model organic pollutant methylene blue (MB), with an outstanding pseudo-first-order kinetic rate constant of 0.432 min-1 (g Lcatalyst -1)-1 under optimal reaction conditions (C H2O2 = 400 mM, initial pH = 9). Furthermore, this Co-N-graphene catalyst enabled strong synergy with HCO3 - in accelerating MB degradation, whereas the scavenger experiment implied that the synergy herein differed significantly from the current Co2+-HCO3 - reaction system, in which contribution of O2˙- was only validated with a Co-N-graphene catalyst. Therefore, this work developed a novel catalyst for boosting 1O2 production from H2O2 activation and will extend the inventory of catalysts for advanced oxidation processes.