Promoting catalytic ozonation of phenol over graphene through nitrogenation and Co₃O₄ compositing

Catalytic ozonation is progressively becoming an attractive technique for quick water purification but efficient and stable catalysts remains elusive. Here we solvothermally synthesized highly-dispersed Co₃O₄ nanocrystals over microscale nitrogen-doping graphene (NG) nanosheets and tested it as a synthetic catalyst in the ozonation of phenol in aqueous solutions. Transmission electron microscopy, powder X-ray diffraction, Fourier transform infrared spectra and X-ray photoelectron spectroscopy were used to determine its morphology, crystallinity, elemental composition and molecular bonds, respectively. The comparative experiments confirmed the highest catalytic activity and oxidation degree (AOSC) of Co₃O₄/NG among four nanocomposites (G, NG, Co₃O₄/G, and Co₃O₄/NG). Co₃O₄/NG also has exhibited the highest degradation rate: complete conversion of a near-saturated concentration of phenol (941.1 mg/L) was achieved within 30 min under ambient conditions with only a small dosage of Co₃O₄/NG (50 mg/L) and ozone (4 mg/L, flow rate: 0.5 L/min). It also resulted in 34.6% chemical oxygen demand (COD_Cr) and 24.2% total organic carbon (TOC) reduction. In this work, graphene nanosheets not only functioned as a support for Co₃O₄ nanocrystals but also functioned as a co-catalyst for the enhancement in phenol removal efficiency. The surface nitridation and Co₃O₄ modification treatment further improved the removal rate of the phenol pollutants and brought in the higher oxidation degree. Our finding may open new perspectives for pursuing exceptional activity for catalytic ozonation reaction.