Dye degradation

  • 文章类型: Journal Article
    背景:氧化锌(ZnO)纳米颗粒用于环境净化的效率受到其对紫外线(UV)光和快速电荷载流子复合的依赖的限制。已经提出碳掺杂通过潜在地增强可见光吸收和电荷分离来解决这些挑战。
    目的:本研究旨在介绍一种小说,碳掺杂ZnO(C-Z)纳米粒子的单步合成法,利用硝酸锌六水合物和糠醛在氮气气氛下的分解来提高可见光下的光催化活性。
    方法:合成了一系列C-Z变体(C-Z-1至C-Z-5)和未掺杂的样品(ZnO-0)。通过X射线光电子能谱(XPS)分析了糠醛对合成工艺和掺杂机理的影响,X射线衍射(XRD)和紫外可见漫反射光谱(DRS)。
    结果:XPS证实了碳在ZnO基质中的整合,和XRD表明,由于掺杂,晶格尺寸增加。DRS显示带隙变窄,表明电荷分离增强。在变体中,C-Z-3的表现明显优于其他,与未掺杂的ZnO相比,罗丹明B的光催化降解速率增加了12倍。
    结论:开发的C-Z纳米粒子的单步合成方法代表了用于生态应用的材料工程的重大进步。增强可见光下的光催化活性,如C-Z-3所示,强调了这些纳米颗粒用于环境净化的潜力。
    BACKGROUND: The efficiency of zinc oxide (ZnO) nanoparticles for environmental decontamination is limited by their reliance on ultraviolet (UV) light and rapid charge carrier recombination. Carbon doping has been proposed to address these challenges by potentially enhancing visible light absorption and charge separation.
    OBJECTIVE: This study aims to introduce a novel, single-step synthesis method for carbon-doped ZnO (C-Z) nanoparticles, leveraging the decomposition of zinc nitrate hexahydrate and furfural under a nitrogen atmosphere to improve photocatalytic activity under visible light.
    METHODS: A series of C-Z variants (C-Z-1 to C-Z-5) and an undoped sample (ZnO-0) were synthesized. The influence of furfural on the synthesis process and doping mechanism was analyzed by X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and UV-visible diffuse reflectance spectroscopy (DRS).
    RESULTS: XPS confirmed the integration of carbon within the ZnO matrix, and XRD indicated increased lattice dimensions owing to doping. DRS revealed bandgap narrowing, suggesting enhanced charge separation. Among the variants, C-Z-3 significantly outperformed the others, showing a 12-fold increase in the photocatalytic degradation rate of Rhodamine B compared to undoped ZnO.
    CONCLUSIONS: The developed single-step synthesis method for C-Z nanoparticles represents a major advancement in materials engineering for ecological applications. The enhanced photocatalytic activity under visible light, as demonstrated by C-Z-3, underscores the potential of these nanoparticles for environmental decontamination.
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  • 文章类型: Journal Article
    环境友好技术的发展对于有效解决与环境恶化有关的问题至关重要。这项工作集成了ZnO装饰的MoS2(MZ),以创建高性能的基于PVDF的PVDF/MoS2-ZnO(PMZ)杂化聚合物复合膜,用于声催化有机污染物降解。通过改变比例确定了MZ的有效协同组合,使用不同的结构评估其对PVDF的影响,形态学,和声催化性能。通过降解罗丹明B(RhB)染料,PMZ膜表现出非常有效的声催化特性,降解效率为97.23%,而PVDF仅降解17.7%。MoS2和ZnO的结合减少了电子-空穴复合并提高了声催化降解性能。此外,一个理想的压电PVDF聚合物与MZ增强极化,以改善氧化还原过程和染料降解,最终提高降解效率。由于存在活性氧,在使用异丙醇(IPA)和对苯醌(BQ)时,RhB的降解效率降低。这表明活性物质·O2-和·OH是利用PMZ2膜降解RhB的主要原因。PMZ膜表现出改进的可重用性,而基本上不降低其催化活性。ZnO在MoS2上的优异修饰和MZ在PVDF聚合物膜中的有效整合导致改善的降解性能。
    The development of environmentally friendly technology is vital to effectively address the issues related to environmental deterioration. This work integrates ZnO-decorated MoS2 (MZ) to create a high-performing PVDF-based PVDF/MoS2-ZnO (PMZ) hybrid polymer composite film for sonocatalytic organic pollutant degradation. An efficient synergistic combination of MZ was identified by altering the ratio, and its influence on PVDF was assessed using diverse structural, morphological, and sonocatalytic performances. The PMZ film demonstrated very effective sonocatalytic characteristics by degrading rhodamine B (RhB) dye with a degradation efficiency of 97.23%, whereas PVDF only degraded 17.7%. Combining MoS2 and ZnO reduces electron-hole recombination and increases the sonocatalytic degradation performance. Moreover, an ideal piezoelectric PVDF polymer with MZ enhances polarization to improve redox processes and dye degradation, ultimately increasing the degradation efficiency. The degradation efficiency of RhB was seen to decrease while employing isopropanol (IPA) and p-benzoquinone (BQ) due to the presence of reactive oxygen species. This suggests that the active species •O2- and •OH are primarily responsible for the degradation of RhB utilizing PMZ2 film. The PMZ film exhibited improved reusability without substantially decreasing its catalytic activity. The superior embellishment of ZnO onto MoS2 and effective integration of MZ into the PVDF polymer film results in improved degrading performance.
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  • 文章类型: Journal Article
    这项研究的重点是溶液燃烧方法,以检查未掺杂和掺杂的ZnO与不同浓度的Al(0.1%和0.2%)的纳米结构。利用各种物理技术来表征合成的纳米颗粒。X射线衍射(XRD)揭示了晶体材料,而扫描电子显微镜(SEM)和能量色散X射线(EDX)的发现证实了产品的粒径和Al插入ZnO晶格。傅里叶变换红外光谱(FTIR)证实在所获得的材料中存在不同的官能团。结果表明,Al掺杂的ZnO(Al-ZnO)纳米颗粒具有良好的光电子学和光致发光性能。光致发光分析表明,Al3+(0.2%)浓度的增加导致峰强度的降低和半峰全宽的增加。使用Taucs图计算带隙。该研究还强调了Zn1-xAlxO纳米结构在降解有机污染物方面的有效性,特别是在吸附孔雀石绿(MG)染料。在样本中,0.2%Al掺杂的ZnO由于其增强的吸附能力和更小的粒径而表现出优异的染料降解效率,降解过程中的多层吸附能力和化学吸附能力证明了这一点。这项研究为Al掺杂的ZnO纳米颗粒在各种环境和技术领域的潜在应用提供了有价值的见解,强调它们在有机污染物降解中的重要性。
    This study focuses on the solution combustion approach to examine the nanostructures of undoped and doped ZnO with different concentrations of Al (0.1 % and 0.2 %). Various physical techniques were utilized to characterize the synthesized nanoparticles. X-ray diffraction (XRD) revealed the crystalline materials, while scanning electron microscopy (SEM) with energy-dispersive X-ray (EDX) findings confirmed the products with particle size and the insertion of Al into the ZnO lattice. Fourier-transform infrared spectra (FTIR) confirmed the presence of different functional groups in the obtained material. The results indicate that Al-doped ZnO (Al-ZnO) nanoparticles show promising properties for optoelectronics and photoluminescence. Photoluminescence analysis indicated that an increase in Al3+ (0.2 %) concentration resulted in a decrease in peak intensity and an increase in the full width at half maximum. The band gap was calculated using the Taucs plot. The study also highlights the effectiveness of Zn1-xAlxO nanostructures in degrading organic pollutants, particularly in adsorbing Malachite Green (MG) dye. Among the samples, the 0.2 % Al-doped ZnO exhibited superior dye degradation efficiency due to its enhanced adsorption capacity and smaller particle size, as evidenced by multilayer adsorption capacity and chemisorption during the degradation process. This study provides valuable insights into the potential applications of Al-doped ZnO nanoparticles in various environmental and technological fields, emphasizing their significance in the degradation of organic pollutants.
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  • 文章类型: Journal Article
    在这项研究中,我们介绍了使用完全绿色合成方法合成金纳米粒子(AuNPs),而无需使用任何其他功能化剂,除了姜黄根提取物。优化了显著的合成参数,并研究了AuNPs在等离子体和铝(Al3+)和铬(Cr3+)离子的荧光传感等领域的适用性,还原4-硝基苯酚(4-NP),降解亚甲基蓝(MB)和甲基橙(MO)染料。使用UV-Vis光谱进行表征研究,TEM,FTIR,和XRD,揭示了AuNP主要具有球形形态和8.5nm的非常小的粒径,稳定性维持长达120天。开发的基于AuNP的等离子体传感器依赖于聚集诱导的吸收减少,随着光谱的红移。荧光传感表明,随着Al3和Cr3的浓度增加,强度呈线性增加,检测限为0.83和1.19nM,分别。测试了AuNPs在减少4-NP以及降解自来水和废水中的MB和MO染料(二元体系)中的催化活性。反应遵循伪一级动力学。这项研究强调了从姜黄根合成的AuNPs在各种环境和传感应用中的潜力。
    In this study, we present the synthesis of gold nanoparticles (AuNPs) using a completely green synthesis method without the use of any additional functionalizing agent, except dried turmeric root extract. The significant synthesis parameters were optimized, and the applicability of AuNPs was investigated in areas such as plasmonic and fluorescent sensing of aluminum (Al3⁺) and chromium (Cr3⁺) ions, reduction of 4-nitrophenol (4-NP), and degradation of methylene blue (MB) and methyl orange (MO) dyes. Characterization studies were performed using UV-Vis spectroscopy, TEM, FTIR, and XRD, revealing that the AuNPs predominantly had a spherical morphology and a very small particle size of 8.5 nm, with stability maintained up to 120 days. The developed AuNP-based plasmonic sensors relied on aggregation-induced decreases in absorption, along with a red shift in the spectra. Fluorescence sensing demonstrated a linear increase in intensity with increasing concentrations of Al3⁺ and Cr3⁺, with detection limits of 0.83 and 1.19 nM, respectively. The catalytic activities of AuNPs were tested in reducing 4-NP and degradations of MB and MO dyes (binary system) in tap water and wastewater, with the reactions following pseudo-first-order kinetics. This study highlights the potential of AuNPs synthesized from turmeric roots for various environmental and sensing applications.
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  • 文章类型: Journal Article
    在工业染料废水的认识,合成了碳量子点(CQDs)和钴锌铁氧体(CZF)纳米复合材料,用于使用氧化聚合反应制备碳量子点涂覆的钴锌铁氧体(CZF@CQDs)纳米催化剂。TEM的结果,zeta电位值,和FTIR证实高度分散的1-4nm颗粒具有CQD的~45.7mV羧基官能化表面。合成的CZF@CQDs光催化剂的结果表明,根据TEM的平均粒径为〜15nm,SEM,和XRD。光催化剂显示1.20eV的带隙,遵循完美的可见光照射。TGA和DTA揭示了纳米光催化剂的良好热稳定性。进行了VSM,CZF和CZF@CQDs的饱和磁化强度分别为42.44和36.14emu/g,分别。多点研究确定CZF@CQDs光催化剂的BET比表面积为149.87m2/g。在可见光照射下,最终的CZF@CQDs纳米光催化剂在光催化破坏反应性蓝222(RB222)和反应性黄145(RY145)染料方面表现出了显着的效率(25分钟内〜95%),以及机械稳定性和可回收性。即使在降解研究的回收之后,纳米光催化效率(~82%,第7个周期)主要维持。还研究了几个参数的影响,包括初始染料浓度,纳米光催化剂浓度,CQD内容,染料溶液的初始pH值,和反应动力学。降解研究数据遵循一级反应速率(R2>0.93)。最后,一种简单而低成本的合成方法,快速降解,CQD包覆的CZF纳米光催化剂的出色稳定性应使其成为染料废水处理的潜在光催化剂。
    In awareness of industrial dye wastewater, carbon quantum dots (CQDs) and cobalt zinc ferrite (CZF) nanocomposites were synthesised for the making of carbon quantum dots coated cobalt zinc ferrite (CZF@CQDs) nanophotocatalyst using oxidative polymerization reaction. The results of TEM, zeta potential value, and FTIR confirm highly dispersed 1-4 nm particles with the - 45.7 mV carboxylic functionalized surface of CQDs. The results of the synthesised CZF@CQDs photocatalyst showed an average particle size of ~ 15 nm according to TEM, SEM, and XRD. The photocatalyst showed a 1.20 eV band gap, which followed the perfect visible light irradiation. TGA and DTA revealed the good thermal stability of the nanophotocatalyst. VSM was carried out, and the saturation magnetisations for CZF and CZF@CQDs were 42.44 and 36.14 emu/g, respectively. A multipoint study determined the BET-specific surface area of the CZF@CQDs photocatalyst to be 149.87 m2/g. Under visible light irradiation, the final CZF@CQDs nanophotocatalyst demonstrated remarkable efficiency (~ 95% within 25 min) in the photocatalytic destruction of Reactive Blue 222 (RB 222) and Reactive Yellow 145 (RY 145) dyes, as well as mechanical stability and recyclability. Even after the recycling of the degradation study, the nanophotocatalyst efficiency (~ 82%, 7th cycles) was predominantly maintained. The effects of several parameters were also investigated, including initial dye concentration, nanophotocatalyst concentration, CQD content, initial pH of the dye solution, and reaction kinetics. Degradation study data follow the first-order reaction rate (R2 > 0.93). Finally, a simple and low-cost synthesis approach, rapid degradation, and outstanding stability of the CQD-coated CZF nanophotocatalyst should make it a potential photocatalyst for dye wastewater treatment.
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  • 文章类型: Journal Article
    GaN比大多数金属氧化物半导体在苛刻条件下光催化降解有机污染物更稳定,虽然其催化效率很难得到实质性的提高。在这项研究中,研究了GaN纳米粒子对有机染料的摩擦催化降解。通过在玻璃烧杯中使用自制特氟龙磁性旋转盘进行磁力搅拌来刺激,发现GaN纳米颗粒在罗丹明B(RhB)和甲基橙(MO)溶液中诱导可忽略的降解。令人惊讶的是,在底部带有Ti和Al2O3涂层的烧杯中,降解作用大大增强:对于Ti和Al2O3涂层,20mg/LRhB溶液的99.2%和99.8%在3小时内降解。分别,对于Ti和Al2O3涂层,在24小时内降解了20mg/LMO溶液的56%和60.2%,分别。此外,MO分子只被分解成更小的有机分子用于Ti涂层,而Al2O3涂层完全降解。这些发现对于在恶劣环境中GaN对有机污染物的催化降解以及对摩擦催化的更好理解非常重要。
    GaN is more stable than most metal oxide semiconductors for the photocatalytic degradation of organic pollutants in harsh conditions, while its catalytic efficiency has been difficult to be substantially improved. In this study, the tribocatalytic degradation of organic dyes by GaN nanoparticles has been investigated. Stimulated through magnetic stirring using homemade Teflon magnetic rotary disks in glass beakers, the GaN nanoparticles were found to induce negligible degradation in rhodamine B (RhB) and methyl orange (MO) solutions. Surprisingly, the degradation was greatly enhanced in beakers with Ti and Al2O3 coatings on their bottoms: 99.2% and 99.8% of the 20 mg/L RhB solutions were degraded in 3 h for the Ti and Al2O3 coatings, respectively, and 56% and 60.2% of the 20 mg/L MO solutions were degraded in 24 h for the Ti and Al2O3 coatings, respectively. Moreover, the MO molecules were only broken into smaller organic molecules for the Ti coating, while they were completely degraded for the Al2O3 coating. These findings are important for the catalytic degradation of organic pollutants by GaN in harsh environments and for achieving a better understanding of tribocatalysis as well.
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  • 文章类型: Journal Article
    将微观金属有机框架组装到宏观聚合物支架中以开发高度可再生的材料一直是一个有前途但具有挑战性的研究领域。在这里,与纳米纤维素(NC)共混的壳聚糖(CS)被单向转化为具有定向大孔的气凝胶,然后用咪唑甲酸酯骨架8(ZIF-8)进行生物矿化,形成分层结构的壳聚糖-纳米纤维素/沸石咪唑甲酸酯骨架8(CS-NC-ZIF-8)杂化气凝胶。结合ZIF-8显著提高了CS-NC气凝胶的杨氏模量为14.18MPa的通用性和机械强度。在气凝胶中掺入ZIF-8不仅提高了其对亚甲蓝的吸附能力,罗丹明B,酸性品红,还有甲基橙,而且还有利于从水中产生电子,在每个催化循环中90分钟内可以转移到降解>90%的孔雀石绿,并且这种能力保持至少10个连续循环。值得注意的是,杂化气凝胶在吸附阳离子染料和催化去除孔雀石绿后具有高度可再生性。凭借其简便的生产工艺,去除效率高,实惠和绿色自然,和优异的再生可行性,CS-NC-ZIF-8气凝胶是解决与染料污染水处理相关的挑战的有前途的解决方案。
    Assembling microscopic metal-organic frameworks into macroscopic polymeric scaffolds to develop highly renewable materials has been a promising yet challenging area of research. Herein, chitosan (CS) blended with nano-cellulose (NC) was unidirectionally transformed into an aerogel with oriented macropores and then biomineralized with zeolite imidazolate frameworks-8 (ZIF-8) to form a hierarchical structured chitosan-nanocellulose/zeolite imidazolate frameworks-8 (CS-NC-ZIF-8) hybrid aerogel. Incorporating ZIF-8 significantly increases the versatility and mechanical strength with a Young\'s modulus of 14.18 MPa of the CS-NC aerogel. The incorporation of ZIF-8 into the aerogel not only enhances its adsorption capacity for methylene blue, rhodamine B, acid fuchsin, and methyl orange, but also facilitates the generation of electrons from water that can be transferred to degrade > 90 % of malachite green within 90 min in each catalytic cycle, and this capability was maintained for at least 10 consecutive cycles. Remarkably, the hybrid aerogel was highly renewable after the adsorption of cationic dyes and catalytic removal of malachite green. With its facile production process, high removal efficiency, affordable and green nature, and excellent regeneration feasibility, the CS-NC-ZIF-8 aerogel stands as a promising solution for addressing challenges associated with dye-contaminated water treatment.
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  • 文章类型: Journal Article
    采用简单、绿色的溶胶-凝胶法合成了MgFe2O4@ZnAl2O4磁性纳米复合材料,在可见光照射下,它们的光催化效率朝着活性蓝222(RB222)染料的降解方向发展。充分表征所制备的纳米复合材料。SEM和TEM图像显示所产生的纳米复合材料的球形形态,平均尺寸为20-25nm。样品的XRD图谱显示成功合成了微晶尺寸为13nm的MgFe2O4@ZnAl2O4MNC。使用VSM检查纳米复合材料的饱和磁化强度(Ms),表示值为6.59emu/g。Hc和Mr值的不存在证实了纳米颗粒的超顺磁性。此外,利用BET分析计算表面积为78.109m2/g,通过DRS分析确定带隙为1.88eV。光催化,光解,和吸附性能进行了研究,结果表明光降解活性高于其他。这些结果证实了MgFe2O4@ZnAl2O4MNCs与可见光辐照对有机染料降解的协同作用。结果表明,96%的RB222染料在10min内快速降解,TOC去除率约为59%。此外,自由基清除剂还澄清了RB222染料的光降解。
    MgFe2O4@ZnAl2O4 magnetic nanocomposites were synthesized with the easy and green sol-gel method, and their photocatalytic efficiency was followed toward degradation of reactive blue 222 (RB222) dye under visible light irradiation. Prepared nanocomposites were fully characterized. The SEM and TEM images revealed the spherical morphology of the produced nanocomposites, with average size of 20-25 nm. The XRD pattern of sample exhibited the successful synthesis of the MgFe2O4@ZnAl2O4 MNCs with crystallite size 13 nm. The saturation magnetization (Ms) of the nanocomposites was examined using VSM, indicating a value of 6.59 emu/g. The absence of Hc and Mr values confirms the superparamagnetic nature of the nanoparticles. In addition, the surface area was calculated to be 78.109 m2/g utilizing BET analysis, and the band gap was determined to be 1.88 eV by DRS analysis. The photocatalytic, photolysis, and adsorption performance were investigated and result shown photodegradation activity was higher than others. These results confirm the synergetic effect between the MgFe2O4@ZnAl2O4 MNCs and visible light irradiation to degradation of organic dye. The results indicate that rapid degradation of 96% of RB222 dye occurred in just 10 min, with a TOC removal rate of approximately 59%. Furthermore, radical scavenger agents also clarified photodegradation of RB222 dye.
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  • 文章类型: Journal Article
    工业染料降解涉及染料分解的几个过程,理想情况下是无害的产品。亚甲基蓝(MB)是纺织工业中最常用的染料之一,并且在常规工业过程中释放到水中。这些放电导致人类和动物产生恶毒的性质。药物也从各种制药行业排放到水体中。在这两种情况下,在目前的工作中,通过溶液燃烧技术,使用柑橘的水性果皮提取物实现了钙掺杂氧化锌纳米颗粒(Ca掺杂ZnONPs)的绿色合成。结构,形态学,并利用XRD研究了合成的Ca掺杂ZnONPs的光学性质,FTIR,SEM,EDX,和紫外可见光谱。制备的NP在可见光照射下对MB染料进行光催化降解,显示~95%的染料降解。合成的Ca掺杂ZnONP也用于吸附替硝唑(TDZ),一种硝基咪唑抗生素,从水样。对于选择性吸附TDZ〜96.2%,观察到NPs的优异吸附能力。发现药物TDZ具有伪二级动力学。催化剂再循环证明了其可重复性;连续使用三次后,染料的去除率高达92%。因此,使用废柑橘皮提取物,合成了多功能Ca掺杂ZnONPs,保持有效的吸附潜力和光催化能力,可作为环境修复的有效材料。
    Industrial dye degradation involves several processes by which dyes are broken down, ideally into innocuous products. Methylene blue (MB) is one of the most commonly employed dyes in the textile industry and is released into water in routine industry processes. These discharges lead to creating a nocuous nature for humans and animals. Drugs are also discharged into water bodies from various pharmaceutical industries. In these two contexts, in the present work, the green synthesis of calcium-doped zinc oxide nanoparticles (Ca-doped ZnO NPs) is achieved using the aqueous peel extract of Citrus limetta by the solution combustion technique. The structural, morphological, and optical properties of the synthesized Ca-doped ZnO NPs are investigated using XRD, FTIR, SEM, EDX, and UV-visible spectroscopy. The prepared NPs were subjected to photocatalytic degradation of MB dye under visible-light illumination, which shows ~ 95% dye degradation. The synthesized Ca-doped ZnO NPs were also employed to adsorb tinidazole (TDZ), a nitroimidazole antibiotic, from water samples. An excellent adsorptive capacity of the NPs was observed for selectively adsorbing the TDZ ~ 96.2%. The drug TDZ was found to have pseudo-second-order kinetics. The catalyst recycling proved its repeatability; removal of the dye reached up to 92% after three successive usages. Therefore, using waste Citrus limetta peel extract, the multifunctional Ca-doped ZnO NPs were synthesized, which maintained effective adsorption potential and photocatalytic abilities and could be used as an effective material for environmental remediation.
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  • 文章类型: Journal Article
    共价有机骨架(COF)的成型,要求将不可加工的COF粉末转换为具有附加功能的适用架构,仍然是一个挑战。使用预电纺聚合物纤维作为牺牲模板,在这里,我们报告了COF中空纤维形式的结构的绿色合成,其内层是过氧化物酶样氧化铁纳米颗粒作为催化材料。与过氧化物酶样原始氧化铁纳米颗粒相比,这些COF中空纤维由于其通过高级氧化过程的过氧化物酶样活性而表现出更高的结晶紫催化分解。此外,作为一种潜在的吸附剂,中空COF纤维具有显著的有效吸附能力和对水中有机溶剂和油的去除效率。由于它们的磁性,COF中空纤维可以很容易地回收,并且对于催化染料降解和从水中除去有机溶剂都表现出高的回收稳定性。
    The shaping of covalent organic frameworks (COFs) from non-processible powder forms into applicable architectures with additional functionality remains a challenge. Using pre-electrospun polymer fibers as a sacrificial template, herein, we report a green synthesis of an architecture in the form of COF hollow fibers with an inner layer of peroxidase-like iron oxide nanoparticles as a catalytic material. When compared to peroxidase-like pristine iron oxide nanoparticles, these COF hollow fibers demonstrate higher catalytic breakdown of crystal violet due to their peroxidase-like activity via advanced oxidation process. Furthermore, as a potential adsorbent, hollow COF fibers exhibit significantly effective adsorption capacity and removal efficiency of organic solvent and oil from water. Because of their magnetic nature, COF hollow fibers can be easily recovered and have exhibited high recycling stability for both catalytic dye degradation and organic solvent removal from water.
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