Hubei Key Lab of Biomass Resource Chemistry and Environmental Biotechnology, School of Resources and Environmental Science, Wuhan University, Wuhan 430079, China.
State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, National Center for Magnetic Resonance in Wuhan, Wuhan Institute of Physics and Mathematics, Innovation Academy for Precision Measurement Science and Technology, Chinese Academy of Sciences, Wuhan 430071, China.
Molecules. 2023 Jan 6;28(2):607. doi: 10.3390/molecules28020607.
Pyrite has been used in photo-Fenton reactions for the degradation of pollutants, but the application of photo-Fenton processes with extra HO in real water/wastewater treatment has still been limited by the economic cost of HO and artificial light sources. Herein, citric acid (CA) and simulated/natural sunlight are used to develop a pyrite-based photo-Fenton system (pyrite-CA-light) in situ generating HO through the enhanced activation of molecular oxygen. The degradation of pharmaceuticals and personal care products (PPCPs), especially acetaminophen (APAP) as the main target pollutant, in the pyrite-CA-light system was investigated. The effects of influencing factors such as various organic acids, APAP concentration, pH, pyrite dosage, CA concentration and co-existing anions (HCO, Cl, NO, SO and HPO) were examined. At a pyrite dosage of 0.1 g L, CA concentration of 0.6 mM and an initial pH of 6.0, the degradation efficiency of APAP (30 μM) was 99.1% within 30 min under the irradiation of xenon lamp (70 W, λ ≥ 350 nm). Almost the same high efficiency of APAP degradation (93.9%) in the system was achieved under natural sunlight irradiation (ca. 650 W m). The scavenging experiments revealed that the dominant active species for degrading APAP was hydroxyl radical (HO). Moreover, a quantitative structural-activity relationship (QSAR) model for pseudo-first-order rate constants () was established with a high significance (R = 0.932, = 0.001) by using three descriptors: octanol-water partition coefficient (logow), dissociation constant (pK) and highest occupied molecular orbital (HOMO). This work provides an innovative strategy of the photo-Fenton process for the degradation of PPCPs using natural minerals and ordinary carboxylic acid under sunlight.
黄铁矿已被用于光芬顿反应中以降解污染物，但在实际水/废水中应用额外的 HO 的光芬顿工艺仍然受到 HO 和人工光源的经济成本限制。在此，使用柠檬酸 (CA) 和模拟/自然光来开发一种基于黄铁矿的光芬顿系统（黄铁矿-CA-光），通过增强分子氧的活化原位生成 HO。研究了黄铁矿-CA-光系统中药物和个人护理产品（PPCPs），特别是作为主要目标污染物的扑热息痛（APAP）的降解。考察了各种有机酸、APAP 浓度、pH 值、黄铁矿用量、CA 浓度和共存阴离子（HCO、Cl、NO、SO 和 HPO）等影响因素的影响。在黄铁矿用量为 0.1 g L、CA 浓度为 0.6 mM 和初始 pH 值为 6.0 的条件下，在氙灯（70 W，λ≥350nm）照射下，30μMAPAP（30μM）的降解效率在 30min 内达到 99.1%。在自然光照射下（约 650 W m），该系统对 APAP 具有几乎相同的高效降解（93.9%）。猝灭实验表明，降解 APAP 的主要活性物质是羟基自由基 (HO)。此外，通过使用三个描述符：辛醇-水分配系数 (logow)、离解常数 (pK) 和最高占据分子轨道 (HOMO)，建立了一个具有高显著性的准一级速率常数 () 的定量结构-活性关系 (QSAR) 模型（R = 0.932， = 0.001）。这项工作为使用天然矿物质和普通羧酸在阳光下降解 PPCPs 提供了一种光芬顿工艺的创新策略。
