Solar-initiated photocatalytic degradation of carbamazepine on excited-state hexadecachlorophthalocyanine in the presence of peroxymonosulfate
Solar-initiated photocatalytic degradation of carbamazepine on excited-state hexadecachlorophthalocyanine in the presence of peroxymonosulfate
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DOI：
10.1016/j.cej.2017.07.172
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发表时间：
2017-12
影响因子：
15.1
通讯作者：
Lulin Wang;Wangyang Lu;D. Ni;Tiefeng Xu;Nan Li;Zhexin Zhu;Haixiang Chen;Wenxing Chen
中科院分区：
文献类型：
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作者：
Lulin Wang;Wangyang Lu;D. Ni;Tiefeng Xu;Nan Li;Zhexin Zhu;Haixiang Chen;Wenxing Chen
在环境催化领域，构建高效、稳定的催化氧化过程已引起人们的广泛关注。在太阳光激发下，以十六氯酞菁铁（FePcCl 16）和过硫酸盐（PMS）为氧化剂，建立了一种新型的太阳光催化氧化体系FePcCl 16/PMS/Sunlight.在阳光照射下，FePcCl 16的酞菁环被激发为处于激发态的FePcCl 16，其激活PMS产生自由基或高价铁（IV）-氧代中间体（Fe（IV）= O）以氧化卡马西平（CBZ）。该系统能有效降解CBZ，90 min内总有机碳去除率接近80%。FePcCl_（16）/PMS/Sunlight光催化氧化体系经20次循环后，催化活性几乎没有损失，铁元素也没有流失，是一种稳定、高效的光催化氧化体系。电子顺磁共振、气相色谱-质谱和光催化活性实验分析表明，Fe（IV）= O物种、单线态氧（1 O2）、羟基和硫酸根自由基（dotOH自由基、SO 4自由基dot−）是CBZ催化氧化的主要活性物种。密度泛函理论（DFT）计算结果表明，FePcCl 16的激发态电子云从四氮杂卟啉环和外围取代基转移到中心Fe原子及其轴向位置.通过超高效液相色谱-高分辨质谱（UPLC Synapt G2-S HDMS）分析，提出了CBZ的主要降解中间体和可能的降解途径。该研究为废水处理提供了高效的催化氧化支持。
In the field of environmental catalysis, the construction of highly efficient and stable catalytic oxidation processes has raised considerable attention. In this study, a novel solar-initiated photocatalytic oxidation system, FePcCl16/PMS/Sunlight, was established by iron hexadecachlorophthalocyanine (FePcCl16) with peroxymonosulfate (PMS) in the presence of sunlight excitation. Under sunlight irradiation, the phthalocyanine ring of the FePcCl16is motivated to FePcCl16∗in the excited state, which activates PMS to generate free radicals or high–valent iron(IV)-oxo intermediates (Fe(IV) = O) to oxidize carbamazepine (CBZ). The system could degrade CBZ effectively and total-organic-carbon removal from solution reached nearly 80% within 90 min. FePcCl16catalytic activity was almost without loss and without iron leaching after twenty recycles, indicating that the FePcCl16/PMS/Sunlight was a stable and efficient photocatalytic oxidation system. Electron paramagnetic resonance, gas chromatography-mass spectrometry and photocatalytic-activity-experiment analysis shows that Fe(IV) = O species, singlet oxygen (1O2), hydroxyl and sulfate radicals (radical dotOH, SO4radical dot−) are the main active species in the catalytic oxidation of CBZ. Density functional theory (DFT) calculations exhibits that the electronic cloud for excited state FePcCl16∗is transferred from the porphyrazine ring and peripheral substituents to the central Fe atom and its axial position. The main degradation intermediates and possible degradation pathway of CBZ were proposed by ultra-performance liquid chromatography and high-resolution mass spectrometry (UPLC Synapt G2-S HDMS). This study provides efficient catalytic oxidation support for wastewater treatment.