Department of Eco-Environment, Hebei University, No. 180 Wusi Dong Road, Lian Chi District, Baoding City, Hebei Province, 071002, China.
College of Chemistry and Materials Science, Hebei University, No. 180 Wusi Dong Road, Lian Chi District, Baoding City, Hebei Province, 071002, China; Engineering Technology Research Center for Flame Retardant Materials and Processing Technology of Hebei Province, Key Laboratory of Analytical Science and Technology of Hebei Province, Hebei University, No. 180 Wusi Dong Road, Lian Chi District, Baoding City, Hebei Province, 071002, China.
Water Res. 2023 Sep 1;243:120314. doi: 10.1016/j.watres.2023.120314. Epub 2023 Jul 5.
Microplastics (MPs) and pesticides are becoming an intractable environmental issue due to their wide spreading and non-degradable nature, posing serious threat to ecosystem and human health. To settle such dilemma, this work reasonably designed a superhydrophobic MOF-based coated sponge (ODSOSS/TiO/Ni-MOF/PDA@Sponge) through the combination of an environmentally friendly in-situ supersaturated coprecipitation and polysesiloxane modification method. Among them, (I) the introduction of polydopamine (PDA) not only improves the adhesion between coatings and sponge, but also enhances the growth of MOF structure through complexation. (II) The obtained Ni-MOF shows large-area microscale anthemy structure with multilayered flaky texture, forming heterogeneously hierarchical structure with the deposited TiO nanoparticles, which promotes photodegradation ability of TiO owing to great specific surface area of Ni-MOF. (III) The high specific large area Ni-MOF supplies sufficient action sites for linkage of PDA and polysesiloxane molecules with unique nanocage-like structure, thus further greatly increasing adsorption force for various pollutants. (IV) The superhydrophobicity protect the porous channels of MOF from contamination of various absorbed pollutants, while TiO nanoparticles effectively photodegrade the absorbed organic pollutants, endowing the sponge superior recyclability. The superhydrophobic sponge selectively rapidly and synchronously adsorbs various MPs (maintained almost 100% after 60 cycles) and pesticides (adsorption rates 71.6%-95.1%) from high-salinity water. The large-area sponge (9 cm × 6 cm × 1 cm) simultaneously removes almost 100% MPs (40 mg/L), Sudan Ⅲ (10 mg/L), kerosene (30 mL/L), and four pesticides (10 mg/L) within 1 min. Particularly, four pesticides are quickly photocatalytic degraded by the coated sponge. The free radical capture trials show that hydroxyl radicals (·OH) are the main active species of pesticide degradation. Furthermore, we reveal the negative centers where pesticide molecules are most vulnerable to ·OH attack, on basis of the charge distribution and molecular electrostatic potential (MEP) analysis. The adsorption mechanisms are carefully clarified through theoretical calculation and experimental data. This work not only provide an effective superhydrophobic candidate for MPs and pesticides removal in a broad applicable scope (especially in high-salinity wastewater), but also opens a new strategy for environmental remediation.
由于微塑料(MPs)和农药广泛分布且不可降解,它们正成为一个棘手的环境问题,对生态系统和人类健康构成严重威胁。为了解决这一困境,本工作通过结合环保的原位过饱和共沉淀和聚硅氧烷改性方法,合理设计了一种超疏水 MOF 基涂层海绵(ODSOSS/TiO/Ni-MOF/PDA@Sponge)。其中:(I)引入聚多巴胺(PDA)不仅提高了涂层与海绵的附着力,还通过配位作用增强了 MOF 结构的生长。(II)所得到的 Ni-MOF 具有大面积的微尺度葱状结构和多层片状纹理,与沉积的 TiO 纳米颗粒形成非均相的分层结构,由于 Ni-MOF 的比表面积较大,从而促进了 TiO 的光降解能力。(III)高比表面积的大 Ni-MOF 为 PDA 和聚硅氧烷分子的连接提供了充足的作用位点,这些分子具有独特的纳米笼状结构,从而进一步大大增加了对各种污染物的吸附力。(IV)超疏水性防止多孔 MOF 通道受到各种被吸附污染物的污染,而 TiO 纳米颗粒则有效地光降解了被吸附的有机污染物,赋予了海绵优异的可回收性。超疏水海绵从高盐水中选择性、快速且同步地吸附各种 MPs(经过 60 次循环后保持近 100%)和农药(吸附率 71.6%-95.1%)。大面积海绵(9 cm×6 cm×1 cm)在 1 分钟内几乎同时去除了 100%的 MPs(40 mg/L)、苏丹红Ⅲ(10 mg/L)、煤油(30 mL/L)和四种农药(10 mg/L)。特别地,四种农药被涂覆的海绵迅速光催化降解。自由基捕获试验表明,羟基自由基(·OH)是农药降解的主要活性物质。此外,我们基于电荷分布和分子静电势(MEP)分析,揭示了农药分子最易受到·OH攻击的负电荷中心。通过理论计算和实验数据,详细阐明了吸附机制。这项工作不仅为 MPs 和农药在广泛应用范围内(特别是在高盐废水中)的去除提供了一种有效的超疏水候选物,而且为环境修复开辟了一条新的策略。