铁铜催化剂非均相Fenton降解苯酚及机制研究

通过浸渍法制备了负载于活性炭(AC)上的金属催化剂Fe/AC、Cu/AC和Fe-Cu/AC,并通过X射线衍射(XRD)、物理吸附仪及X射线光电子能谱(XPS)对其进行了表征.研究了非均相Fenton反应催化H2O2降解苯酚废水的工艺参数,并通过中间产物分析和电子自旋共振谱(ESR)探讨了过程反应机制.实验表明,Cu/AC催化剂中铜主要以CuO形式存在,Fe/AC中铁以多价态形式存在,以无定形形态分散于活性炭中.Fe/AC、Cu/AC和Fe-Cu/AC催化过氧化氢降解苯酚60 min内降解率分别达到96.7%、77.5%和99%;Cu/AC和Fe-Cu/AC催化剂中活性组分铜和铁有一定溶出,而Fe/AC中活性组分铁溶出很少,苯酚降解主要是以非均相催化为主,同时在三轮循环实验后的苯酚降解率仍然高达93%以上,显示了良好的催化稳定性.在优化条件pH=3、T=303 K及初始H2O2为4.38 mmol.L-1下,Fe/AC催化过氧化氢对苯酚和TOC去除率分别达到97%和53%,没有催化剂时苯酚几乎不降解.ESR结果表明Fe/AC催化过氧化氢产生了羟基自由基,证明苯酚降解是以羟基自由基氧化为主;通过高效液相色谱(HPLC)检测苯酚降解中间产物主要有邻苯二酚、对苯二酚和对苯醌,推测苯酚降解途径主要为邻位和对位的羟基取代反应.

Degradation of Phenol with a Fe/Cu-Catalytic Heterogeneous-Fenton Process

The catalysts of Fe/AC, Cu/AC and Fe-Cu/AC with active carbon as support were prepared by a wet impregnation method, and were characterized using X-ray diffraction (XRD), nitrogen adsorption and X-ray photoelectron spectroscopy (XPS) measurements; the catalytic heterogeneous-Fenton processes of phenol degradation with these catalysts were also investigated, and the degradation mechanism was discussed with analysis of intermediate products and electron spin resonance (ESR) measurement. The results showed that the active component states varied in different catalysts; CuO was the main state of Cu in Cu/AC and Fe exhibited various valence states in Fe/AC. The degradation rate of phenol with Fe/AC, Cu/AC and Fe-Cu/AC as catalyst in the initial 60 min reached 96.7%, 77.5% and 99%, respectively; the dissolution of a little active-component metal was found in Cu/AC and Fe-Cu/AC, but little Fe in Fe/AC was dissolved; the degradation of phenol was performed by heterogeneous Fe/AC instead of dissolved Fe, and the degradation rate was above 93% after Fe/AC was used for three cycle runs, showing a stable catalytic activity. Under the optimum conditions of pH=3, T=303 K, and 4.38 mmol·L^-1 H₂O₂, the removal of phenol and TOC in the Fe/AC-catalytic Fenton process could reach 97% and 53%, respectively, while little phenol was degraded without catalyst. The ESR results indicated that hydroxyl radical was produced in the catalytic decomposition of H₂O₂ with Fe/AC as catalyst, demonstrating that the degradation of phenol mainly followed an oxidation pathway of hydroxyl radical; intermediates such as hydroquinone, p-benzenequinone and catechol were obtained, and the results showed thatortho- and para-substitution reaction by hydroxyl might be the main mechanism of phenol oxidation.