Recent advances and remaining barriers to the development of electrospun nanofiber and nanofiber composites for point-of-use and point-of-entry water treatment systems.

In this review, we focus on electrospun nanofibers as a promising material alternative for the niche application of decentralized, point-of-use (POU) and point-of-entry (POE) water treatment systems. We focus our review on prior work with various formulations of electrospun materials, including nanofibers of carbon, pure metal oxides, functionalized polymers, and polymer-metal oxide composites, that exhibit analogous performance to media (e.g., activated carbon, ion exchange resins) commonly used in commercially available, certified POU/POE devices for contaminants including organic pollutants, metals (e.g., lead) and persistent oxyanions (e.g., nitrate). We then analyze the relevant strengths and remaining research and development opportunities of the relevant literature based on an evaluation framework that considers (i) performance comparison to commercial analogs; (ii) appropriate pollutant targets for POU/POE applications; (iii) testing in flow-through systems consistent with POU/POE applications; (iv) consideration of water quality effects; and (v) evaluation of material strength and longevity. We also identify several emerging issues in decentralized water treatment where nanofiber-based POU/POE devices could help meet existing needs including their use for treatment of uranium, disinfection, and in electrochemical treatment systems. To date, research has demonstrated promising material performance toward relevant targets for POU/POE applications, using appropriate aquatic matrices and considering material stability. To fully realize their promise as an emerging treatment technology, our analysis of the available literature reveals the need for more work that benchmarks nanofiber performance against established commercial analogs, as well as fabrication and performance validation at scales and under conditions simulating POU/POE water treatment.

Synthesis and optimization of Fe2O3 nanofibers for chromate adsorption from contaminated water sources.

In this work, α-Fe2O3 nanofibers were synthesized via electrospinning and characterized to observe optimal morphological and dimensional properties towards chromate removal. The Fe2O3 nanofiber samples were tested in aqueous solutions containing chromate (CrO4(2-)) to analyze their adsorption capabilities and compare them with commercially-available Fe2O3 nanoparticles. Synthesized Fe2O3 nanofibers were observed with a variety of different average diameters, ranging from 23 to 63 nm, while having a constant average grain size at 34 nm, point zero charge at pH 7.1, and band gap at 2.2 eV. BET analysis showed an increase in specific surface area with decreasing average diameter, from 7.2 to 59.2 m(2)/g, due to the increased surface area-to-volume ratio with decreasing nanofiber size. Based on CrO4(2-) adsorption isotherms at pH 6, adsorption capacity of the Fe2O3 nanofibers increased with decreasing diameter, with the 23 nm sized nanofibers having an adsorption capacity of 90.9 mg/g, outperforming the commercially-available Fe2O3 nanoparticles by nearly 2-fold. Additionally, adsorption kinetics was also analyzed, increasing with decreasing nanofiber diameter. The enhanced performance of the nanofiber is suggested to be caused solely due to the increased surface area, in part by its size and morphology. Electrospun Fe2O3 nanofibers provide a promising solution for effective heavy metal removal through nanotechnology-integrated treatment systems.

Synthesis and optimization of Ag-TiO2 composite nanofibers for photocatalytic treatment of impaired water sources.

In this work, Ag-TiO2 composite nanofibers were fabricated by electrospinning, where the composition and crystallinity were tuned by controlling the precursor composition and annealing conditions. Characterization revealed that bulk-embedded Ag nanoparticles inhibited anatase-to-rutile phase transformation and a decrease in band gap from 3.2 down to 2.8 eV with increase in the Ag content. The photocatalytic activity of 0.5 at.% Ag-TiO2 nanofibers toward phenol degradation was the greatest, outperforming both unmodified TiO2 nanofibers and commercially available TiO2 Aeroxide(®) P25 by a factor of ∼3. The high reactivity of the low content Ag-TiO2 nanofibers can be attributed to the addition of electron traps, which provide efficient carrier separation and, therefore, decreased recombination. However, further increase in Ag content led to lower photoreactivity, most likely due to the growth of the Ag nanoparticles, which suggests an optimal size of 2 to 3 nm for the Ag nanoparticles at 0.5 at.% provided the greatest photoreactivity. Ag-TiO2 nanofibers show great promise as innovative and highly performing nanomaterials for future nanotechnology-based treatment systems, particularly when the photoreactivity demonstrate herein is used in synergy with the established antimicrobial activity of nano-Ag.

Hydroxyl radical formation during ozonation of multiwalled carbon nanotubes: performance optimization and demonstration of a reactive CNT filter.

We explored factors influencing hydroxyl radical (•OH) formation during ozonation of multiwalled carbon nanotubes (MWCNTs) and assessed this system's viability as a next-generation advanced oxidation process (AOP). Using standard reactivity metrics for ozone-based AOPs (RCT values), MWCNTs promoted •OH formation during ozonation to levels exceeding ozone (both alone and with activated carbon) and equivalent to ozone with hydrogen peroxide. MWCNTs oxidized with nitric acid exhibited vastly greater rates of ozone consumption and •OH formation relative to as-received MWCNTs. While some of this enhancement reflects their greater suspension stability, a strong correlation between RCT values and surface oxygen concentrations from X-ray photoelectron spectroscopy suggests that surface sites generated during MWCNT oxidation promote •OH exposure. Removal of several ozone-recalcitrant species [para-chlorobenzoic acid (p-CBA), atrazine, DEET, and ibuprofen] was not significantly inhibited in the presence of radical scavengers (humic acid, carbonate), in complex aquatic matrices (Iowa River water) and after 12 h of continuous exposure of MWCNTs to concentrated ozone solutions. As a proof-of-concept, oxidized MWCNTs deposited on a ceramic membrane chemically oxidized p-CBA in a flow through system, with removal increasing with influent ozone concentration and mass of deposited MWCNTs (in mg/cm2). This hybrid membrane platform, which integrates adsorption, oxidation, and filtration via an immobilized MWCNT layer, may serve as the basis for future novel nanomaterial-enabled technologies, although long-term performance trials under representative treatment scenarios remain necessary.

Tailored synthesis of photoactive TiO 2 nanofibers and Au/TiO 2 nanofiber composites: structure and reactivity optimization for water treatment applications.

Titanium dioxide (TiO2) nanofibers with tailored structure and composition were synthesized by electrospinning to optimize photocatalytic treatment efficiency. Nanofibers of controlled diameter (30-210 nm), crystal structure (anatase, rutile, mixed phases), and grain size (20-50 nm) were developed along with composite nanofibers with either surface-deposited or bulk-integrated Au nanoparticle cocatalysts. Their reactivity was then examined in batch suspensions toward model (phenol) and emerging (pharmaceuticals, personal care products) pollutants across various water qualities. Optimized TiO2 nanofibers meet or exceed the performance of traditional nanoparticulate photocatalysts (e.g., Aeroxide P25) with the greatest reactivity enhancements arising from (i) decreasing diameter (i.e., increasing surface area), (ii) mixed phase composition [74/26 (±0.5) % anatase/rutile], and (iii) small amounts (1.5 wt %) of surface-deposited, more so than bulk-integrated, Au nanoparticles. Surface Au deposition consistently enhanced photoactivity by 5- to 10-fold across our micropollutant suite independent of their solution concentration, behavior that we attribute to higher photocatalytic efficiency from improved charge separation. However, the practical value of Au/TiO2 nanofibers was limited by their greater degree of inhibition by solution-phase radical scavengers and higher rate of reactivity loss from surface fouling in nonidealized matrixes (e.g., partially treated surface water). Ultimately, unmodified TiO2 nanofibers appear most promising for use as reactive filtration materials because their performance was less influenced by water quality, although future efforts must increase the strength of TiO2 nanofiber mats to realize such applications.