Zero-Valent Iron Nanoparticles for Abatement of Environmental Pollutants: Materials and Engineering Aspects

Zero-valent iron nanoparticle technology is becoming an increasingly popular choice for treatment of hazardous and toxic wastes, and for remediation of contaminated sites. In the U.S. alone, more than 20 projects have been completed since 2001. More are planned or ongoing in North America, Europe, and Asia. The diminutive size of the iron nanoparticles helps to foster effective subsurface dispersion whereas their large specific surface area corresponds to enhanced reactivity for rapid contaminant transformation. Recent innovations in nanoparticle synthesis and production have resulted in substantial cost reductions and increased availability of nanoscale zero-valent iron (nZVI) for large scale applications. In this work, methods of nZVI synthesis and characterization are highlighted. Applications of nZVI for treatment of both organic and inorganic contaminants are reviewed. Key issues related to field applications such as fate/transport and potential environmental impact are also explored.     

Enhanced reactivity of nanoscale iron particles through a vacuum annealing process

A reactivity study was undertaken to compare and assess the rate of dechlorination of chlorinated aliphatic hydrocarbons (CAHs) by annealed and non-annealed nanoscale iron particles. The current study aims to resolve the uncertainties in recently published work studying the effect of the annealing process on the reduction capability of nanoscale Fe particles. Comparison of the normalized rate constants (m²/h/L) obtained for dechlorination reactions of trichloroethene (TCE) and cis-1,2-dichloroethene (cis-1,2-DCE) indicated that annealing nanoscale Fe particles increases their reactivity ~30-fold. An electron transfer reaction mechanism for both types of nanoscale particles was found to be responsible for CAH dechlorination, rather than a reduction reaction by activated H₂ on the particle surface (i.e., hydrogenation, hydrogenolysis). Surface analysis of the particulate material using X-ray diffraction (XRD) and transmission electron microscopy (TEM) together with surface area measurement by Brunauer, Emmett, Teller (BET) indicate that the vacuum annealing process decreases the surface area and increases crystallinity. BET surface area analysis recorded a decrease in nanoscale Fe particle surface area from 19.0 to 4.8 m²/g and crystallite dimensions inside the particle increased from 8.7 to 18.2 nm as a result of annealing.     

Solid-stabilized emulsion formation using stearoyl lactylate coated iron oxide nanoparticles

Iron oxide nanoparticles can exhibit highly tunable physicochemical properties that are extremely important in applications such as catalysis, biomedicine and environmental remediation. The small size of iron oxide nanoparticles can be used to stabilize oil-in-water Pickering emulsions due to their high energy of adsorption at the interface of oil droplets in water. The objective of this work is to investigate the effect of the primary particle characteristics and stabilizing agent chemistry on the stability of oil-in-water Pickering emulsions. Iron oxide nanoparticles were synthesized by the co-precipitation method using stoichiometric amounts of Fe²⁺ and Fe³⁺ salts. Sodium stearoyl lactylate (SSL), a Food and Drug Administration approved food additive, was used to functionalize the iron oxide nanoparticles. SSL is useful in the generation of fat-in-water emulsions due to its high hydrophilic–lipophilic balance and its bilayer-forming capacity. Generation of a monolayer or a bilayer coating on the nanoparticles was controlled through systematic changes in reagent concentrations. The coated particles were then characterized using various analytical techniques to determine their size, their crystal structure and surface functionalization. The capacity of these bilayer coated nanoparticles to stabilize oil-in-water emulsions under various salt concentrations and pH values was also systematically determined using various characterization techniques. This study successfully demonstrated the ability to synthesize iron oxide nanoparticles (20–40 nm) coated with SSL in order to generate stable Pickering emulsions that were pH-responsive and resistant to significant destabilization in a saline environment, thereby lending themselves to applications in advanced oil spill recovery and remediation.     

Growth of carbon nanotubes on metal nanoparticles: a microscopic mechanism from ab initio molecular dynamics simulations

We report on ab initio molecular dynamics simulations of the early stages of single-walled carbon nanotube (SWCNT) growth on metal nanoparticles. Our results show that a sp2 bonded cap is formed on an iron catalyst, following the diffusion of C atoms from hydrocarbon precursors on the nanoparticle surface. The weak adhesion between the cap and iron enables the graphene sheet to "float" on the curved surface, as additional C atoms covalently bonded to the catalyst "hold" the tube walls. Hence the SWCNT grows capped. At the nanoscale, we did not observe any tendency of C atoms to penetrate inside the catalyst, consistent with total energy calculations showing that alloying of Fe and C is very unlikely for 1 nm particles. Root growth was observed on Fe but not on Au, consistent with experiment.     

Size-dependent magnetic properties of iron oxide nanoparticles

Uniform iron oxide nanoparticles in the size range from 10 to 24 nm and polydisperse 14 nm iron oxide particles were prepared by thermal decomposition of Fe(III) carboxylates in the presence of oleic acid and co-precipitation of Fe(II) and Fe(III) chlorides by ammonium hydroxide followed by oxidation, respectively. While the first method produced hydrophobic oleic acid coated particles, the second one formed hydrophilic, but uncoated, nanoparticles. To make the iron oxide particles water dispersible and colloidally stable, their surface was modified with poly(ethylene glycol) and sucrose, respectively. Size and size distribution of the nanoparticles was determined by transmission electron microscopy, dynamic light scattering and X-ray diffraction. Surface of the PEG-functionalized and sucrose-modified iron oxide particles was characterized by Fourier transform infrared (FT-IR) and Raman spectroscopy and thermogravimetric analysis (TGA). Magnetic properties were measured by means of vibration sample magnetometry and specific absorption rate in alternating magnetic fields was determined calorimetrically. It was found, that larger ferrimagnetic particles showed higher heating performance than smaller superparamagnetic ones. In the transition range between superparamagnetism and ferrimagnetism, samples with a broader size distribution provided higher heating power than narrow size distributed particles of comparable mean size. Here presented particles showed promising properties for a possible application in magnetic hyperthermia.     

Uptake and Sequestration of Naphthalene and 1,2-Dichlorobenzene by C60

The interactions of common environmental contaminants with C₆₀ have been studied to evaluate the environmental impact of carbon nanomaterials. The adsorption and desorption interaction of the hydrophobic contaminants naphthalene and 1,2-dichlorobenzene with C₆₀ was characterized. Processes that cause the wetting and disaggregating of C₆₀ particles also affect the extent of organic contaminant sorption to C₆₀ aggregates by orders of magnitude. C₆₀ dissolved in organic solvents such as toluene can form stable nanoscale aggregates upon vigorous mixing in water. These nanoscale C₆₀ particles form stable suspensions in water and are referred to as ‘nano-C₆₀’. Desorption of contaminants from stable suspensions of nano-C₆₀ exhibits hysteresis. The experimentally observed adsorption/desorption hysteresis is described by a two-compartment desorption model: first, adsorption to the external surfaces that are in contact with water, and second, adsorption to the internal surfaces within the aggregates.     

A study on hydrogen adsorption behaviors of open-tip carbon nanocones

We report a new chemical approach toward air-stable nanoscale zero-valent iron (nZVI). The uniformly sized (approx. 80?nm) particles, formed by the reduction of Fe(II) salt by borohydride in the presence of glutamic acid, are coated by a thin inner shell of amorphous ferric oxide/hydroxide and a secondary shell consisting of glutamic acid. The as-prepared nanoparticles stabilized by the inorganic?Corganic double shell create 2D chain morphologies. They are storable for several months under ambient atmosphere without the loss of Fe(0) relative content. They show one order of magnitude higher rate constant for trichlorethene decomposition compared with the pristine particles possessing only the inorganic shell as a protective layer. This is the first example of the inorganic?Corganic (consisting of low-molecular weight species) double-shell stabilized nanoscale zero-valent iron material being safely transportable in solid-state, storable on long-term basis under ambient conditions, environmentally acceptable for in situ applications, and extraordinarily reactive if contacted with reducible pollutants, all in one.     

Catalytic dechlorination of 2,4-dichlorophenol by Ni/Fe nanoparticles prepared in the presence of ultrasonic irradiation

In this study, nickle/iron (Ni/Fe) nanoparticles were synthesized by liquid phase reductive method in the presence of 20 kHz ultrasonic irradiation to improve nanoparticles’ disparity and avoid agglomeration. The characterized results showed that this method has obviously modified most of the particles in term of sizes and specific surface areas. Meanwhile, the improved nanoscale Ni/Fe particles were employed for the reductive dechlorination of 2,4-dichlorophenol (2,4-DCP) as a function of some influential factors (Ni content, Ni/Fe nanoparticles dosage, reaction temperature and initial pH values) and degradation path. Experimental results showed that 2,4-DCP was first adsorbed by Ni/Fe nanoparticles, then quickly reduced to o-chlorophenol (o-CP), p-chlorophenol (p-CP), and finally to phenol (P). The application of ultrasonic irradiation for Ni/Fe nanoparticles synthesis was found to significantly enhance the removal efficiency of 2,4-DCP. Consequently, the phenol production rates increased from 68% (in the absence of ultrasonic irradiation) to 87% (in the presence of ultrasonic irradiation) within 180 min. Nearly 96% of 2,4-DCP was removed after 300 min reaction with these optimized conditions: Ni content over Fe⁰ 3 wt%, initial 2,4-DCP concentration 20 mg L⁻¹, Ni/Fe dosage 3 g L⁻¹, initial pH value 3.0, and reaction temperature 25 °C. The degradation of 2,4-DCP followed pseudo-first-order kinetics reaction and the apparent pseudo-first-order kinetics constant was 0.0737 min⁻¹. This study suggested that the presence of ultrasonic irradiation in the synthesis of nanoscale Ni/Fe particles could be a promising technique to enhance nanoparticle’s disparity and avoid agglomeration.     

The key role of biochar in the rapid removal of decabromodiphenyl ether from aqueous solution by biochar-supported Ni/Fe bimetallic nanoparticles

Some problems exist in the current remediation of polybrominated diphenyl ethers (PBDEs) from aqueous solution by using iron-based nanoparticles. Our efforts have contributed to the synthesis of biochar-supported Ni/Fe bimetallic nanoparticle composites (BC@Ni/Fe). Under the optimum operating parameters of BC@Ni/Fe, the morphologic analysis revealed that biochar effectively solved the agglomeration of Ni/Fe nanoparticles and the removal efficiency of BDE209 obtained by BC@Ni/Fe (91.29%) was seven times higher than the sum of biochar (2.55%) and Ni/Fe (11.22%) in 10 min. The degradation products of BDE209 in the solution and absorbed on the BC@Ni/Fe were analyzed with gas chromatography-mass spectroscopy, which indicated that the degradation of BDE209 was mainly a process of stepwise debromination. Meanwhile, compared with Ni/Fe nanoparticles, the adsorption ability of the by-products of BDE209 by BC@Ni/Fe was greater, to a certain extent, which reduced the additional environmental burden. In addition, the concentration of nickle ion leaching from the Ni/Fe nanoparticles was 3.09 mg/L; conversely, the concentration of nickle leaching from BC@Ni/Fe was not detected. This excellent performance in our study indicates a possible means to enhance the reactivity and reduce the secondary risks of Ni/Fe nanoparticles.     

Synthesis of Nanoscale Bimetallic Particles in Polyelectrolyte Membrane Matrix for Reductive Transformation of Halogenated Organic Compounds

Nanosized Fe/Ni and Fe/Pd particles were synthesized in the polyacrylic acid (PAA)/polyether sulfone (PES) composite membrane matrix for reductive transformation of halogenated organic compounds (HOCs). The advantages of using membrane to immobilize nanoparticles are the reduction of particles loss, prevention of particles agglomeration, and potential application of convective flow. Cross-linked PAA/PES composite membranes containing metal ions as particles precursor were prepared by heat treatment with ethylene glycol (EG) as a cross-linking agent. Nanoscale metal particles were formed and immobilized inside the membrane matrix after reduction with sodium borohydride. Membrane morphology and structure were observed by scanning electron microscopy (SEM). Particle size and distribution were characterized by SEM and transmission electron microscopy (TEM). Energy dispersive X-ray spectroscopy (EDS) was used to obtain the qualitative and quantitative element information of particles. A specimen-drift-free EDS line profile and EDS mapping system was performed in a scanning transmission electron microscopy (STEM) to determine the two-dimensional element distribution of iron and nickel in the nano domain. In the dechlorination study with trichloroethylene (TCE) as a representative HOCs, rapid and complete destruction of TCE was achieved by using nanosized bimetallic Fe/Ni or Fe/Pd in PAA/PES composite membranes. Typically more than 95% of 10 mg/l TCE was reduced within 1 h. Ethane was found in the headspace as the main product.