Bhanukiran Sunkara

Multifunctional Iron−Carbon Nanocomposites through an Aerosol-Based Process for the In Situ Remediation of Chlorinated Hydrocarbons

Spherical iron-carbon nanocomposites were developed through a facile aerosol-based process with sucrose and iron chloride as starting materials. These composites exhibit multiple functionalities relevant to the in situ remediation of chlorinated hydrocarbons such as trichloroethylene (TCE). The distribution and immobilization of iron nanoparticles on the surface of carbon spheres prevents zerovalent nanoiron aggregation with maintenance of reactivity. The aerosol-based carbon microspheres allow adsorption of TCE, thus removing dissolved TCE rapidly and facilitating reaction by increasing the local concentration of TCE in the vicinity of iron nanoparticles. The strongly adsorptive property of the composites may also prevent release of any toxic chlorinated intermediate products. The composite particles are in the optimal range for transport through groundwater saturated sediments. Furthermore, those iron-carbon composites can be designed at low cost, the process is amenable to scale-up for in situ application, and the materials are intrinsically benign to the environment.

Multifunctional Colloidal Particles for in Situ Remediation of Chlorinated Hydrocarbons

Effective in situ injection technology for the remediation of dense nonaqueous phase liquids (DNAPLs) such as trichloroethylene (TCE) requires the use of decontamination agents that effectively migrate through the soil media and react efficiently with dissolved TCE and bulk TCE. We describe the use of a novel decontamination system containing highly uniform carbon microspheres in the optimal size range for transport through the soil. The microspheres are enveloped in a polyelectrolyte (carboxymethyl cellulose, CMC) to which a bimetallic nanoparticle system of zero-valent iron and Pd is attached. The carbon serves as a strong adsorbent to TCE, while the bimetallic nanoparticle system provides the reactive component. The polyelectrolyte serves to stabilize the carbon microspheres in aqueous solution. The overall system resembles a colloidal micelle with a hydrophilic shell (polyelectrolyte coating) and hard hydrophobic core (carbon). In contact with bulk TCE, there is a sharp partitioning of the system to the TCE side of the interface due to the hydrophobicity of the core. These multifunctional systems appear to satisfy criteria related to remediation and are made with potentially environmentally benign materials.

Modifying metal nanoparticle placement on carbon supports using an aerosol-based process, with application to the environmental remediation of chlorinated hydrocarbons.

A facile aerosol-based process (ABP) is developed to vary the placement of iron nanoparticles on the external surface of carbon microspheres or within the interior. This is accomplished through the competitive mechanisms of sucrose carbonization and the precipitation of soluble iron salts, in an aerosol droplet passing through a high temperature heating zone. At lower aerosolization temperatures, carbonization occurs first leading to iron salt precipitation on the external surface, while at higher temperatures interior placement occurs through concurrent iron salt precipitation and sucrose carbonization. The resulting composites are highly conducive to the reductive dechlorination of compounds such as trichloroethylene (TCE) as the carbon support is a strong adsorbent, and zerovalent iron effectively reduces TCE to innocuous gases such as ethane. Since both iron and carbon are widely used catalysts and catalyst supports, the simple process of modifying iron placement has significant potential applications in heterogeneous catalysis.

Water-in-trichloroethylene emulsions stabilized by uniform carbon microspheres.

Uniform hard carbon spheres (HCS), synthesized by the hydrothermal decomposition of sucrose followed by pyrolysis, are effective at stabilizing water-in-trichloroethylene (TCE) emulsions. The irreversible adsorption of carbon particles at the TCE-water interface resulting in the formation of a monolayer around the water droplet in the emulsion phase is identified as the key reason for emulsion stability. Cryogenic scanning electron microscopy was used to image the assembly of carbon particles clearly at the TCE-water interface and the formation of bilayers in regions of droplet-droplet contact. The results of this study have potential implications to the subsurface injection of carbon submicrometer particles containing zero-valent iron nanoparticles to treat pools of chlorinated hydrocarbons that are sequestered in fractured bedrock.

Synthesis of Submicrometer Hollow Particles with a Nanoscale Double-Layer Shell Structure

The morphology of hollow, double-shelled submicrometer particles is generated through a rapid aerosol-based process. The inner shell is an essentially hydrophobic carbon layer of nanoscale dimension (20 nm), and the outer shell is a hydrophilic silica layer of approximately 40 nm, with the shell thickness being a function of the particle size. The particles are synthesized by exploiting concepts of salt bridging to lock in a surfactant (CTAB) and carbon precursors together with iron species in the interior of a droplet. This deliberate negation of surfactant templating allows a silica shell to form extremely rapidly, sealing in the organic species in the particle interior. Subsequent pyrolysis results in a buildup of internal pressure, forcing carbonaceous species against the silica wall to form an inner shell of carbon. The incorporation of magnetic iron oxide into the shells opens up applications in external stimuli-responsive nanomaterials.

Iron-carbon composite microspheres prepared through a facile aerosol-based process for the simultaneous adsorption and reduction of chlorinated hydrocarbons

Iron-carbon (Fe-C) composite microspheres prepared through a facile aerosol-based process are effective remediation agents for the simultaneous adsorption and reduction of chlorinated hydrocarbons. Complete dechlorination was achieved for the class of chlorinated ethenes that include tetrachloroethylene (PCE), trichloroethylene (TCE), cis- and trans-1,2-dicloroethylene (c-DCE, t-DCE), 1,1-dichloroethylene (1,1-DCE) and, vinyl chloride (VC). The Fe-C particles potentially provides multi-functionality with requisite characteristics of adsorption, reaction, and transport for the effective in situ remediation of chlorinated hydrocarbons. The carbon support immobilizes the ferromagnetic iron nanoparticles onto its surface, thereby inhibiting aggregation. The adsorptive nature of the carbon support prevents the release of toxic intermediates such as the dichloroethylenes and vinyl chloride. The adsorption of chlorinated ethenes on the Fe-C composites is higher (>80%) than that of humic acid (<35%) and comparable to adsorption on commercial activated carbons (>90%). The aerosol-based process is an efficient method to prepare adsorptivereactive composite particles in the optimal size range for transport through the porous media and as effective targeted delivery agents for the in situ remediation of soil and groundwater contaminants.

Chapter 26 – Multifunctional Materials Containing Nanoscale Zerovalent Iron in Carbon Microspheres for the Environmentally Benign Remediation of Chlorinated Hydrocarbons

Iron–carbon submicron composite particles are developed through a facile aerosol-based process with sucrose and iron chloride as starting materials. These composites exhibit multiple functionalities relevant to the in situ remediation of chlorinated hydrocarbons such as trichloroethylene (TCE). The distribution and immobilization of iron nanoparticles on the surface of carbon spheres prevent zerovalent nanoiron aggregation with maintenance of reactivity. The aerosol-based carbon microspheres allow adsorption of TCE, thus removing dissolved TCE rapidly and facilitating reaction by increasing the local concentration of TCE in the vicinity of iron nanoparticles. The strongly adsorptive property of the composites may also prevent release of any toxic chlorinated intermediate products. The composite particles are in the optimal range for transport through groundwater saturated sediments. Furthermore, those iron–carbon composites can be designed at low cost, the process is amenable to scale up for in situ application, and the materials are intrinsically benign to the environment. The embedding of nanoscale iron in submicron carbon may provide an environmentally benign approach to the use of nanoscale zerovalent iron.