In this work, a new effective and relatively stable heterogeneous catalyst of Metal-Organic Framework Co3(BTC)2·12H2O (Co-BTC) has been synthesized and tested to activate peroxymonosulfate (PMS) for removal of refractory dibutyl phthalate (DBP). Co-BTC(A) and Co-BTC(B) were synthesized by different methods, which resulted in different activity towards PMS. The results indicated that Co-BTC(A) showed better performance on DBP degradation. The highest degradation rate of 100% was obtained within 30 min. The initial pH showed respective level on DBP degradation with a rank of 5.0 > 2.75 > 9.0 > 7.0 > 11.0 in PMS/Co-BTC(A) system. No remarkable reduction of DBP was observed in the catalytic activity of Co-BTC(A) at 2nd run as demonstrated by recycling. However, the DBP degradation efficiency decreased by 8.26%, 10.9% and 25.6% in the 3rd, 4th, and 5th runs, respectively. The loss of active catalytic sites of Co(II) from Co-BTC(A) is responsible for the activity decay. Sulfate radicals (SO4−•) and hydroxyl radicals (•OH) were found at pH 2.75. Here, we propose the possible mechanism for activation of PMS by Co-BTC(A), which is involved in homogeneous and heterogeneous reactions in the solutions and the surface of Co-BTC(A), respectively.
This work was supported by National Natural Science Foundation of China (No. 51208206), Guangdong Provincial Department of Science (No. 2012A032300015), Fundamental Research Funds for the Central Universities (2013ZZ0031).
- Activation mechanism
- Cobalt metal-organic frameworks
- Dibutyl phthalate