Cyclodextrin-functionalized Fe3O4@TiO2: reusable, magnetic nanoparticles for photocatalytic degradation of endocrine-disrupting chemicals in water supplies.
TL;DR: Water-dispersible, photocatalytic Fe3O4@TiO2 core-shell magnetic nanoparticles have been prepared by anchoring cyclodextrin cavities to the TiO2 shell, and their ability to capture and photocatallytically destroy endocrine-disrupting chemicals, bisphenol A and dibutyl phthalate, present in water, has been demonstrated.
Abstract: Water-dispersible, photocatalytic Fe3O4@TiO2 core–shell magnetic nanoparticles have been prepared by anchoring cyclodextrin cavities to the TiO2 shell, and their ability to capture and photocatalytically destroy endocrine-disrupting chemicals, bisphenol A and dibutyl phthalate, present in water, has been demonstrated. The functionalized nanoparticles can be magnetically separated from the dispersion after photocatalysis and hence reused. Each component of the cyclodextrin-functionalized Fe3O4@TiO2 core–shell nanoparticle has a crucial role in its functioning. The tethered cyclodextrins are responsible for the aqueous dispersibility of the nanoparticles and their hydrophobic cavities for the capture of the organic pollutants that may be present in water samples. The amorphous TiO2 shell is the photocatalyst for the degradation and mineralization of the organics, bisphenol A and dibutyl phthalate, under UV illumination, and the magnetism associated with the 9 nm crystalline Fe3O4 core allows for the magneti...
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TL;DR: The latest synthesis methods and recent progress in the photocatalytic applications of magnetic iron oxide-semiconductor composite nanomaterials are reviewed, and the problems and challenges still need to be resolved and development strategies are discussed.
Abstract: Photocatalytic degradation of toxic organic pollutants is a challenging tasks in ecological and environmental protection. Recent research shows that the magnetic iron oxide–semiconductor composite photocatalytic system can effectively break through the bottleneck of single-component semiconductor oxides with low activity under visible light and the challenging recycling of the photocatalyst from the final products. With high reactivity in visible light, magnetic iron oxide–semiconductors can be exploited as an important magnetic recovery photocatalyst (MRP) with a bright future. On this regard, various composite structures, the charge-transfer mechanism and outstanding properties of magnetic iron oxide–semiconductor composite nanomaterials are sketched. The latest synthesis methods and recent progress in the photocatalytic applications of magnetic iron oxide–semiconductor composite nanomaterials are reviewed. The problems and challenges still need to be resolved and development strategies are discussed.
439 citations
TL;DR: A yolk-shell Co3O4@metal-organic frameworks (MOFs) nanoreactor via a facile method to accommodate sulfate radical-based advanced oxidation processes (SR-AOPs) into its interior cavity is proposed and a new opportunity for improved environmental remediation is elucidated.
Abstract: We here first proposed a yolk-shell Co3O4@metal-organic frameworks (MOFs) nanoreactor via a facile method to accommodate sulfate radical-based advanced oxidation processes (SR-AOPs) into its interior cavity. The mesoporous and adsorptive MOFs shells allow the rapid diffusion of reactant molecules to the encapsulated Co3O4 active sites, and the confined high instantaneous concentration of reactants in the local void space is anticipated to facilitate the SR-AOPs. As a proof of concept, the nanoreactor was fully characterized and applied for catalytic degradation of 4-chlorophenol (4-CP) in the presence of peroxymonosulfate (PMS). The enhancement of SR-AOPs in the nanoreactor is demonstrated by the result that degradation efficiency of 4-CP reached almost 100% within 60 min by using the yolk-shell Co3O4@MOFs catalysts as compared to only 59.6% under the same conditions for bare Co3O4 NPs. Furthermore, the applicability of this nanoreactor used in SR-AOPs was systematically investigated in terms of effect of reaction parameters and identification of intermediates and primary radical as well as mineralization of the reaction and stability of the composite. The findings of this study elucidated a new opportunity for improved environmental remediation.
424 citations
TL;DR: In this article, a facile, reproducible, and template-free strategy to prepare g-C3N4-Fe3O4 nanocomposites by an in situ growth mechanism was demonstrated.
Abstract: Herein we demonstrate a facile, reproducible, and template-free strategy to prepare g-C3N4–Fe3O4 nanocomposites by an in situ growth mechanism. The results indicate that monodisperse Fe3O4 nanoparticles with diameters as small as 8 nm are uniformly deposited on g-C3N4 sheets, and as a result, aggregation of the Fe3O4 nanoparticles is effectively prevented. The as-prepared g-C3N4–Fe3O4 nanocomposites exhibit significantly enhanced photocatalytic activity for the degradation of rhodamine B under visible-light irradiation. Interestingly, the g-C3N4–Fe3O4 nanocomposites showed good recyclability without loss of apparent photocatalytic activity even after six cycles, and more importantly, g-C3N4–Fe3O4 could be recovered magnetically. The high performance of the g-C3N4–Fe3O4 photocatalysts is due to a synergistic effect including the large surface-exposure area, high visible-light-absorption efficiency, and enhanced charge-separation properties. In addition, the superparamagnetic behavior of the as-prepared g-C...
352 citations
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TL;DR: The slow pace of hazardous waste remediation at military installations around the world is causing a serious delay in conversion of many of these facilities to civilian uses as discussed by the authors, which is a serious problem.
Abstract: The civilian, commercial, and defense sectors of most advanced industrialized nations are faced with a tremendous set of environmental problems related to the remediation of hazardous wastes, contaminated groundwaters, and the control of toxic air contaminants. For example, the slow pace of hazardous waste remediation at military installations around the world is causing a serious delay in conversion of many of these facilities to civilian uses. Over the last 10 years problems related to hazardous waste remediation have emerged as a high national and international priority.
17,188 citations
"Cyclodextrin-functionalized Fe3O4@T..." refers background in this paper
...treating wastewaters.(7) Separation is important not just from a reusability perspective but also to...
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TL;DR: In this article, the authors focus on interfacial processes and summarize some of the operating principles of heterogeneous photocatalysis systems, including the electron transfer and energy transfer processes in photocatalytic reactions.
Abstract: In 1972, Fujishima and Honda discovered the photocatalytic splitting of water on TiO{sub 2} electrodes. This event marked the beginning of a new era in heterogeneous photocatalysis. Since then, research efforts in understanding the fundamental processes and in enhancing the photocatalytic efficiency of TiO{sub 2} have come from extensive research performed by chemists, physicists, and chemical engineers. Such studies are often related to energy renewal and energy storage. In recent years, applications to environmental cleanup have been one of the most active areas in heterogeneous photocatalysis. This is inspired by the potential application of TiO{sub 2}-based photocatalysts for the total destruction of organic compounds in polluted air and wastewaters. There exists a vast body of literature dealing with the electron transfer and energy transfer processes in photocatalytic reactions. A detailed description of these processes is beyond the scope of this review. Here, the authors tend to focus on interfacial processes and to summarize some of the operating principles of heterogeneous photocatalysis. In section 2, the authors first look at the electronic excitation processes in a molecule and in a semiconductor substrate. The electronic interaction between the adsorbate molecule and the catalyst substrate is discussed in terms of the catalyzed ormore » sensitized photoreactions. In section 3, thermal and photocatalytic studies on TiO{sub 2} are summarized with emphasis on the common characteristics and fundamental principles of the TiO{sub 2}-based photocatalysis systems. In section 4, they address the research effort in the electronic modification of the semiconductor catalysts and its effect on the photocatalytic efficiency. Several representative examples will be presented including the Schottky barrier formation and modification at metal-semiconductor interfaces. Some concluding remarks and future research directions will be given in the final section. 160 refs.« less
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3,257 citations
TL;DR: Bisphenol A (CAS 85-05-7) is "slightly to moderately" toxic and has low potential for bioaccumulation in aquatic organisms, with most levels nondetected.
1,601 citations
"Cyclodextrin-functionalized Fe3O4@T..." refers background in this paper
...biological behavior similar to that of natural and synthetic estrogens with steroidal structures.(14,15)...
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TL;DR: It is shown that magnetic exchange coupling induced at the interface between ferromagnetic and antiferromagnetic systems can provide an extra source of anisotropy, leading to magnetization stability.
Abstract: Interest in magnetic nanoparticles has increased in the past few years by virtue of their potential for applications in fields such as ultrahigh-density recording and medicine. Most applications rely on the magnetic order of the nanoparticles being stable with time. However, with decreasing particle size the magnetic anisotropy energy per particle responsible for holding the magnetic moment along certain directions becomes comparable to the thermal energy. When this happens, the thermal fluctuations induce random flipping of the magnetic moment with time, and the nanoparticles lose their stable magnetic order and become superparamagnetic. Thus, the demand for further miniaturization comes into conflict with the superparamagnetism caused by the reduction of the anisotropy energy per particle: this constitutes the so-called 'superparamagnetic limit' in recording media. Here we show that magnetic exchange coupling induced at the interface between ferromagnetic and antiferromagnetic systems can provide an extra source of anisotropy, leading to magnetization stability. We demonstrate this principle for ferromagnetic cobalt nanoparticles of about 4 nm in diameter that are embedded in either a paramagnetic or an antiferromagnetic matrix. Whereas the cobalt cores lose their magnetic moment at 10 K in the first system, they remain ferromagnetic up to about 290 K in the second. This behaviour is ascribed to the specific way ferromagnetic nanoparticles couple to an antiferromagnetic matrix.
1,459 citations
"Cyclodextrin-functionalized Fe3O4@T..." refers background in this paper
...field leads to higher blocking temperatures, TB, and coercive fields, Hc, as compared to particles where such fields are absent.(33) The exchange-bias field, He, is defined as the offset of the Page 15 of 34...
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