Abstract: In recent years, the enrichment of refractory pollutants in water has caused numerous environmental issues, which cannot be treated effectively by traditional water treatment process. Advanced oxidation techniques are recognized to be the most effective method to degrade refractory pollutants. An emerging advanced oxidation technique based on sulfate radical (SO4-·) generated from activating PMS catalyzed by heterogeneous catalysts (transition metal oxide) has been developed to degrade the refractory pollutants in wastewater. Compared with traditional advanced oxidation technique, the new technique features wider adaptability range of pH, stronger oxidizability under neutral conditions and longer half-life of free radicals. Besides, it overcomes the secondary pollution problem of metal ions in homogeneous catalytic system as well as their difficulty in recycling. This newly developed advanced oxidation technique has been drawn tremendous attention from scholars of environmental fields and are expected to provides new ideas and methods for removing refractory water pollutants like antibiotics and hormones etc. Nevertheless, due to the reduction of active sites, heterogeneous catalysis presents lower catalytic efficiency than that of homogeneous catalysis, with poor catalytic stability and poor recyclability as well. This urges intensive research endeavors to seek new transition metal oxide catalysts and modify existing catalysts for PMS activation, aiming at improving catalytic efficiency and recyclability of catalysts while exploiting economic and environmental advantages of heterogeneous catalysis. Impressive strides have been made in researches of heterogeneous transition metals for PMS activation in recent years, which greatly contribute to its practical application. In many transition metals, the oxides of cobalt, iron, and manganese have been proved to have catalytic activity on PMS activation. Cobalt oxides were studied first since cobalt ions show the strongest activation ability for PMS. Subsequently, the oxides of iron and manganese have gradually become the substitutes for cobalt oxides due to their environmental friendliness and cheapness. Research works in the past five years have established new methods to overcome the bottleneck of low catalytic efficiency and poor catalytic stability, which introduce various new materials like nanostructured carbon, mesoporous materials, metal organic frameworks in the preparation of catalysts to modify the transition metals oxides and result in an increased electron transfer speed and an enhanced chemical stability. Moreover, researchers also have demonstrated that binary composite materials containning two transition metal catalytic cores exhibit improvements in both catalytic efficiency and stability. The research progress and synthesis of Co-based, Mn-based and Fe-based monobasic catalysts are introduced in this article. The present researches of binary composite catalysts are reviewed. Finally, the current existing shortcomings and the prospects of this newly developed technique are discussed. There are reasons to believe that heterogeneous catalysis of PMS activation by transition metal oxide has a bright future in degradation of refractory pollutants in wastewater.
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