Green synthesized conditions impacting on the reactivity of Fe NPs for the degradation of malachite green

doi:10.1016/j.saa.2014.08.116

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy

Volume 137, 25 February 2015, Pages 154-159

https://doi.org/10.1016/j.saa.2014.08.116 Get rights and content

Highlights

•
Impact of synthesized conditions on the reactivity of Fe NPs was studied.
•
Fe NPs were used for the degradation of MG.
•
90.56% of MG was removed using Fe NPs.
•
Fe NPs were characterized by various techniques.

Abstract

This study investigates green tea extract synthesized conditions impacting on the reactivity of iron nanoparticles (Fe NPs) used for the degradation of malachite green (MG), including the volume ratio of Fe²⁺ and tea extract, the solution pH and temperature. Results indicated that the reactivity of Fe NPs increased with higher temperature, but fell with increasing pH and the volume ratio of Fe²⁺ and tea extract. Scanning electron microscope (SEM), energy-dispersive spectrometer (EDS), Fourier transform infrared spectroscope (FTIR) and X-ray diffraction (XRD) indicated that Fe NPs were spherical in shape, their diameter was 70–80 nm and they were mainly composed of iron oxide nanoparticles. UV–visible (UV–vis) indicated that reactivity of Fe NPs used in degradation of MG significantly depended on the synthesized conditions of Fe NPs. This was due to their impact on the reactivity and morphology of Fe NPs. Finally, degradation of MG showed that 90.56% of MG was removed using Fe NPs.

Graphical abstract

Introduction

Nanoscale zero-valent iron (nZVI) has received extensive attention in environmental remediation and water treatment due to its large specific surface area and high reaction activity [1]. The physicochemical properties of nZVI and its reductive capacity encourage its application in the rapid decontamination of many aqueous pollutants [2], [3]. Chemical methods have successfully been utilized to produce nZVI nanoparticles. However, the drawbacks include chemical substances such as NaBH₄, organic solvents, stabilizing and dispersing agents being toxic and expensive [1]. Therefore, the development of clean, biocompatible, non-toxic and eco-friendly synthesized methods for nanoparticles is required. The green synthesis of nanoparticles has nanotechnology potential using plant extracts as reducing agents and capping agents. It is superior to other methods because it is simple, cost-effective, and relatively reproducible and often results in more stable materials [4].

Presently, there are only a few studies on the synthesis of iron nanoparticles (Fe NPs) using plant extracts [4], [5], [6], [7], [8], [9]. Fe NPs were produced using extracts of green tea leaves and then applied as a Fenton-like catalyst for decolorization of aqueous solutions containing methylene blue (MB) and methyl orange (MO) dyes [5]. The results indicated fast removal of the dyes with the kinetic data of MB following a second order removal rate, whereas those of MO were fitted to a first order removal rate. The membranes containing reactive nanoparticles (Fe and Fe/Pd) immobilized in a polymer film [polyacrylic acid (PAA)-coated polyvinylidene fluoride (PVDF) membrane] were prepared with the use of tea extract [6]. The membrane-supported nanoparticles were used to degrade a common and highly important pollutant, trichloroethylene (TCE). However, no study has documented the synthesized conditions impacting on the formation of Fe NP using green extracts and its reactivity. In addition, the morphology of Fe NPs can dramatically affect their reactivity, which significantly depends on synthesized conditions such as the reducing and capping agents, temperature and solution pH [4].

Recently, Fe NPs were synthesized using tea extracts for the purpose of degrading malachite green [10], [11], where the best degradation of malachite green (MG) was Fe NPs synthesized by green tea extracts. However, the synthetic conditions impacting the morphology and reactivity of Fe NPs are still unclear. As a consequent study, this report describes a reliable green synthesis of Fe NPs using green tea extract as the reducing and capping agent. To understand the synthesized conditions affecting the formation of Fe NPs and their reactivity for degrading MG, experimental factors such as the volume ratio of Fe²⁺ and tea extract, temperature, and pH were studied. The synthesized Fe NPs were characterized by a variety of methods, including scanning electron microscope (SEM), energy-dispersive spectrometer (EDS), X-ray diffraction (XRD), and Fourier-transform infrared (FTIR) spectroscopy. Finally, the degradation pathway of MG by Fe NPs was proposed.

Section snippets

Synthesis of Fe NPs

The synthesis of Fe NPs using green tea extracts is described below. The initial concentrations of 60.0 g/L green tea extracts were prepared by adding 60 g green tea into 1 L deionized water and heating them at 353 K for 1 h in water bath. Then these extracts were vacuum-filtered after cooling to the room temperature and 0.10 mg/L FeSO₄ solution was added to the tea extracts at different volume ratios for volume ratios. The Fe NPs were formed when black Fe NPs were observed in the solution mixed Fe

The synthesized conditions for Fe NPs and their degradation of MG

The reactivity of Fe NPs was highly sensitive to the synthesis conditions and the reduction rate is kinetically dominated by experimental parameters [4]. Therefore, as discussed in the following sections, the influences of experimental parameters such as the volume ratio of Fe²⁺ and tea extract, temperature, and pH were systematically investigated. These features provide valuable insights into the morphology and reactivity of Fe NPs dominating kinetically as a result of these factors.

Since

Conclusion

In this study the impacts of synthesized conditions on the reactivity of Fe NPs and their application in the degradation of malachite green were investigated. It concluded that the ratio of Fe²⁺and tea extract, the solution pH and temperature influenced the reactivity of Fe NPs. The optimized conditions included the ratio 1:1 of Fe²⁺and green tea extract and pH at 6.0 and 318 K and 90.56% with an initial concentration of 50 mg/L MG being removed. Various techniques were used for the

Acknowledgment

This research was supported by a Fujian “Minjiang Fellowship” Grant from Fujian Normal University.

References (21)

R.A. Crane et al.
Nanoscale zero-valent iron: future prospects for an emerging water treatment technology
J. Hazard. Mater.
(2012)
X. Zhang et al.
2,4,6-Trinitrotoluene reduction kinetics in aqueous solution using nanoscale zero-valent iron
J. Hazard. Mater.
(2009)
X. Zhang et al.
Characterizations of kaolinite supported nanoscale zero-valent iron used to remove Pb²⁺ from aqueous solution
Water Res.
(2011)
T. Shahwan et al.
Green synthesis of iron nanoparticles and their application as a Fenton-like catalyst for the degradation of aqueous cationic and anionic dyes
Chem. Eng. J.
(2011)
V. Smuleac et al.
Green synthesis of Fe and Fe/Pd bimetallic nanoparticles in membranes for reductive degradation of chlorinated organics
J. Membr. Sci.
(2011)
Y. Kuang et al.
Heterogeneous Fenton-like oxidation of monochlorobenzene using green synthesis of iron nanoparticles
J. Colloid Interface Sci.
(2013)
O.V. Kharissova et al.
The greener synthesis of nanoparticles
Trends Biotechnol.
(2013)
L.L. Huang et al.
Synthesis of iron-based nanoparticles using oolong tea extract for the degradation of malachite green
Spectrochim. Acta Part A Mol. Biomol. Spectrosc.
(2014)
L.L. Huang et al.
Green synthesis of iron nanoparticles by various tea extracts: comparative study of the reactivity
Spectrochim. Acta Part A Mol. Biomol. Spectrosc.
(2014)
Z. Chen et al.
Removal of methyl orange from aqueous solution using bentonite-supported nanoscale zero-valent iron
J. Colloid Interface Sci.
(2011)

There are more references available in the full text version of this article.

Cited by (100)

Brownfield-related studies in the context of climate change: A comprehensive review and future prospects
2024, Heliyon
The global climate change events are expected to augment the vulnerability of persistent organic pollutants within the global brownfield areas to a certain extent, consequently heightening the risk crises faced by these brownfields amidst the backdrop of global environmental changes. However, studies addressing brownfield risks from the perspective of climate change have received limited attention. Nonetheless, the detrimental consequences of brownfield risks are intrinsically linked to strategies for mitigating and adapting to sustainable urban development, emphasizing the critical importance of their far-reaching implications. This relevance extends to concerns about environmental quality, safety, health risks, and the efficacy of chosen regeneration strategies, including potential secondary pollution risks. This comprehensive review systematically surveys pertinent articles published between 1998 and 2023. A selective analysis was conducted on 133 articles chosen for their thematic relevance. The findings reveal that: (1) Under the backdrop of the climate change process, brownfield restoration is necessitated to provide scientific and precise guidance. The integration of brownfield considerations with the dynamics of climate change has progressively evolved into a unified framework, gradually shaping a research paradigm characterized by “comprehensive + multi-scale + quantitative” methodologies; (2) Research themes coalesce into five prominent clusters: “Aggregation of Brownfield Problem Analysis”, “Precision Enhancement of Brownfield Identification through Information Technology”, “Diversification of Brownfield Reutilization Assessment”, “Process-Oriented Approaches to Brownfield Restoration Strategies”, and “Expansion of Ecological Service Functions in Brownfield Contexts”; (3) Application methodologies encompass five key facets: “Temporal and Spatial Distribution Patterns of Pollutants”, “Mechanisms and Correlations of Pollution Effects”, “Evaluation of Pollution Risks”, “Assessment of Brownfield Restoration Strategies”, and “Integration of Brownfield Regeneration with Spatial Planning”. Future brownfield research from the climate change perspective is poised to reflect characteristics such as “High-Precision Prediction, Comprehensive Dimensionality, Full-Cycle Evaluation, Low-Risk Exposure, and Commitment to Sustainable Development”.
Enhanced photocatalytic activity of magnetite/titanate (Fe<inf>3</inf>O<inf>4</inf>/TiO<inf>2</inf>) nanocomposite for methylene blue dye degradation under direct sunlight
2024, Optical Materials
In this study, we have presented findings on the structural, optical, morphological, magnetic and photocatalytic characteristics of magnetite/TiO₂ nanocomposite (Fe₃O₄/TiO₂ NCs) for the degradation of methylene blue (MB) dye under sunlight. The NCs were synthesized using a facile hydrothermal technique and subsequently subjected to analysis using several characterization methods, including XRD, Raman spectroscopy, SEM, UV–Vis and VSM. XRD analysis revealed that the as-prepared sample exhibited a high level of crystallinity, accompanied by a smaller crystallite size. The structural defects in the crystal system and the presence of impurities in the as-prepared sample can be analysed using Raman spectroscopy. Morphological studies represent the synthesized Fe₃O₄/TiO₂ NCs are evenly arranged and are spherical in shape. The average particle size was determined through the utilization of image J software, yielding a measurement of 31 nm. UV–Vis spectrum shows the absorbance peak and the energy bandgap was calculated. The NCs, in their initial state, demonstrated a degradation efficiency exceeding 97% for MB dye under sunlight within duration of 40 min. The Fe₃O₄/TiO₂ NCs possess the capability of effortless separation from the dye solution facilitated by an external magnet.
Recent trends in phyto-mediated iron-based nanomaterials for environmental remediation and biomedical applications
2024, Inorganic Chemistry Communications
Advancements in nanoscience and nanotechnology have significantly impacted the widespread integration of iron-based nanomaterials across various domains of scientific investigation, research institutions, and industrial sectors. The intrinsic properties exhibited by iron oxide nanoparticles, such as their biocompatibility, low toxicity, catalytic behaviors, and versatility in engaging in various reaction pathways, have positioned these nanoparticles as highly promising candidates for a wide range of biomedical uses. The substantial financial outlays associated with reagents, equipment, and potential environmental risks linked to the physical and chemical methodologies utilized in synthesizing iron-based nanomaterials have presented a significant hurdle. In order to address the challenges mentioned earlier, which pertain to the mitigation of environmental consequences and the cost-efficient synthesis of nanomaterials possessing desired properties and effectiveness, this comprehensive review seeks to gather substantial knowledge from recent advancements in the manufacturing, analysis, and utilization of iron-based nanomaterials using biological methods. This endeavor will draw upon previous scientific investigations to comprehensively understand the subject matter. The use of botanical extracts in producing iron-based nanomaterials is gaining recognition for their capacity to reduce and stabilize these materials during manufacturing efficiently. Moreover, employing botanical extracts for biologically synthesizing iron-based nanomaterials offers multiple advantages. The advantages of this approach encompass its simplicity, cost-effectiveness, environmental sustainability, and lower energy requirements compared to traditional physical and chemical synthesis techniques. Therefore, this comprehensive analysis provides a thorough overview of the optimal conditions and characterization techniques for synthesizing iron-based nanomaterials with various organic extracts. This paper presents a comprehensive analysis of the applications of iron-based nanoparticles derived from the soil as therapeutic agents for antibacterial and anticancer purposes. Furthermore, a comprehensive investigation is conducted to assess the effectiveness of iron-based nanomaterials in purifying contaminated effluents containing dyes and other hazardous compounds.
Green synthesis of iron nanoparticles: Sources and multifarious biotechnological applications
2023, International Journal of Biological Macromolecules
Green synthesis of iron nanoparticles is a highly fascinating research area and has gained importance due to reliable, sustainable and ecofriendly protocol for synthesizing nanoparticles, along with the easy availability of plant materials and their pharmacological significance. As an alternate to physical and chemical synthesis, the biological materials, like microorganisms and plants are considered to be less costly and environment-friendly. Iron nanoparticles with diverse morphology and size have been synthesized using biological extracts. Microbial (bacteria, fungi, algae etc.) and plant extracts have been employed in green synthesis of iron nanoparticles due to the presence of various metabolites and biomolecules. Physical and biochemical properties of biologically synthesized iron nanoparticles are superior to that are synthesized using physical and chemical agents. Iron nanoparticles have magnetic property with thermal and electrical conductivity. Iron nanoparticles below a certain size (generally 10–20 nm), can exhibit a unique form of magnetism called superparamagnetism. They are non-toxic and highly dispersible with targeted delivery, which are suitable for efficient drug delivery to the target. Green synthesized iron nanoparticles have been explored for multifarious biotechnological applications. These iron nanoparticles exhibited antimicrobial and anticancerous properties. Iron nanoparticles adversely affect the cell viability, division and metabolic activity. Iron nanoparticles have been used in the purification and immobilization of various enzymes/proteins. Iron nanoparticles have shown potential in bioremediation of various organic and inorganic pollutants. This review describes various biological sources used in the green synthesis of iron nanoparticles and their potential applications in biotechnology, diagnostics and mitigation of environmental pollutants.
Nano-size plastics inhibited Cr(VI) species transformation during facilitated transport of green synthesized nano-iron in the presence of oxyanions
2023, Journal of Hazardous Materials
Remediating hexavalent chromium (Cr(VI))-contaminated soils using green synthesized nano-iron (g-nZVI), which merits high reactivity, low cost, and environmental friendliness, has attracted significant attention. However, the broad existence of nano plastics (NPs) could adsorb Cr(VI) and subsequently influence in situ remediation of Cr(VI)-contaminated soil by g-nZVI. To clarify this issue and improve the remediation efficiency, we investigated the co-transport between Cr(VI) and g-nZVI coexisting with sulfonyl-amino-modified nano plastics (SANPs) in water-saturated sand media in the presence of oxyanions (i.e., phosphate and sulfate) at environmentally relevant conditions. This study found that SANPs inhibited the Cr(VI) reduction to Cr(III) (i.e., Cr₂O₃) by g-nZVI, attributed to nZVI-SANPs hetero-aggregates and Cr(VI) adsorption on SANPs. Notably, “nZVI-[SANPs•••Cr(III)]” agglomerate happened via complexation of [–NH₃•••Cr(III)] between Cr(III) from Cr(VI) reduced by g-nZVI and amino group on SANPs. Further, the co-presence of phosphate (stronger adsorption on SANPs than g-nZVI) remarkably suppressed Cr(VI) reduction. Then, it promoted the co-transport of Cr(VI) with nZVI-SANPs hetero-aggregates, which could potentially threaten underground water. Fundamentally, sulfate would instead concentrate on SANPs, hardly impacting the reactions between Cr(VI) and g-nZVI. Overall, our findings provide crucial insights into understanding the Cr(VI) species transformation during co-transport with g-nZVI in ubiquitous complexed soil environments (i.e., containing oxyanions) contaminated by SANPs.
Enhanced activity of Fe/Mn nanoparticles using a response surface methodology and mechanism for removing oxytetracycline and copper ion
2023, Chemosphere
As feed additives, oxytetracycline (OTC) and copper ion (Cu(II)) are often detected in livestock and poultry farming wastewater. To address this issue, firstly, the synthesis conditions of Fe/Mn nanoparticles (Fe/Mn NPs) were initially optimized using a response surface methodology (RSM) to yield highly active Fe/Mn NPs, where the application of RSM significantly increased the Fe/Mn NPs’ efficiency in removing co-contamination OTC and Cu(II),respectively, from 45.8 to 86.2% and 14.9–67.2%. Secondly, scanning electron microscope and Nitrogen adsorption-desorption isotherms results showed that Fe/Mn NPs were composed of elliptic particles between 20 and 40 nm, a specific surface area of 59.5 m² g⁻¹, and a mean pore diameter of 5.27 nm. Fourier infrared spectrometer and X-ray photoelectron spectroscopy analysis revealed that amino, carboxyl and hydroxyl functional groups existed on the surface. Zeta potential indicated that Fe/Mn NPs maintained a high negative charge density between pH 1 and 11. These surface properties possessed by the green synthesized Fe/Mn NPs resulted in high adsorption efficiency for co-contamination OTC and Cu(II). Based on this, a removal mechanism based on a combination of complex-bridging effect, pore-filling, hydrogen bonding, surface complexation, ion exchange and electrostatic attraction was proposed. Finally, the assessment of Fe/Mn NPs used in swine wastewater demonstrated that both 99.9% OTC and 55.6% Cu(II) were removed.

View all citing articles on Scopus

View full text

Green synthesized conditions impacting on the reactivity of Fe NPs for the degradation of malachite green

Highlights

Abstract

Graphical abstract

Introduction

Section snippets

Synthesis of Fe NPs

The synthesized conditions for Fe NPs and their degradation of MG

Conclusion

Acknowledgment

J. Hazard. Mater.

J. Hazard. Mater.

Water Res.

Chem. Eng. J.

J. Membr. Sci.

J. Colloid Interface Sci.

Trends Biotechnol.

Spectrochim. Acta Part A Mol. Biomol. Spectrosc.

Spectrochim. Acta Part A Mol. Biomol. Spectrosc.

J. Colloid Interface Sci.