Cafer T. Yavuz

The effect of nanocrystalline magnetite size on arsenic removal

Abstract Higher environmental standards have made the removal of arsenic from water an important problem for environmental engineering. Iron oxide is a particularly interesting sorbent to consider for this application. Its magnetic properties allow relatively routine dispersal and recovery of the adsorbent into and from groundwater or industrial processing facilities; in addition, iron oxide has strong and specific interactions with both As(III) and As(V). Finally, this material can be produced with nanoscale dimensions, which enhance both its capacity and removal. The objective of this study is to evaluate the potential arsenic adsorption by nanoscale iron oxides, specifically magnetite (Fe3O4) nanoparticles. We focus on the effect of Fe3O4 particle size on the adsorption and desorption behavior of As(III) and As(V). The results show that the nanoparticle size has a dramatic effect on the adsorption and desorption of arsenic. As particle size is decreased from 300 to 12 nm the adsorption capacities for both As(III) and As(V) increase nearly 200 times. Interestingly, such an increase is more than expected from simple considerations of surface area and suggests that nanoscale iron oxide materials sorb arsenic through different means than bulk systems. The desorption process, however, exhibits some hysteresis with the effect becoming more pronounced with small nanoparticles. This hysteresis most likely results from a higher arsenic affinity for Fe3O4 nanoparticles. This work suggests that Fe3O4 nanocrystals and magnetic separations offer a promising method for arsenic removal.

Unprecedented high-temperature CO2 selectivity in N2-phobic nanoporous covalent organic polymers

Post-combustion CO(2) capture and air separation are integral parts of the energy industry, although the available technologies remain inefficient, resulting in costly energy penalties. Here we report azo-bridged, nitrogen-rich, aromatic, water stable, nanoporous covalent organic polymers, which can be synthesized by catalyst-free direct coupling of aromatic nitro and amine moieties under basic conditions. Unlike other porous materials, azo-covalent organic polymers exhibit an unprecedented increase in CO(2)/N(2) selectivity with increasing temperature, reaching the highest value (288 at 323 K) reported to date. Here we observe that azo groups reject N(2), thus making the framework N(2)-phobic. Monte Carlo simulations suggest that the origin of the N(2) phobicity of the azo-group is the entropic loss of N(2) gas molecules upon binding, although the adsorption is enthalpically favourable. Any gas separations that require the efficient exclusion of N(2) gas would do well to employ azo units in the sorbent chemistry.

Synthesis of monodisperse iron oxide nanocrystals by thermal decomposition of iron carboxylate salts

Iron oxide (Fe(3)O(4), magnetite) nanocrystals of 6 to 30 nm with narrow size distributions (sigma = 5-10%) were prepared by the pyrolysis of iron carboxylate salts.

High capacity carbon dioxide adsorption by inexpensive covalent organic polymers

Efficient CO2 scrubbing without a significant energy penalty remains an outstanding challenge for the fossil fuel-burning industry where aqueous amine solutions are still widely used. Porous materials have long been evaluated for next generation CO2 adsorbents. Porous polymers, robust and inexpensive, show promise as feasible materials for the capture of CO2 from warm exhaust fumes. We report the syntheses of porous covalent organic polymers (COPs) with CO2 adsorption capacities of up to 5616 mg g−1 (measured at high pressures, i.e. 200 bar) and industrially relevant temperatures (as warm as 65 °C). COPs are stable in boiling water for at least one week and near infinite CO2/H2 selectivity is observed.

Noninvasive functionalization of polymers of intrinsic microporosity for enhanced CO2 capture

Modifying sorbents for the purpose of improving carbon dioxide capture often results in the loss of surface area or accessible pores, or both. We report the first noninvasive functionalization of the polymers of intrinsic microporosity (PIMs) where inclusion of the amidoxime functionality in PIM-1 increases carbon dioxide capacity up to 17% and micropore surface area by 20% without losing its film forming ability.

Pd-Sensitized Single Vanadium Oxide Nanowires: Highly Responsive Hydrogen Sensing Based on the Metal−Insulator Transition

Exceptionally sensitive hydrogen sensors were produced using Pd-nanoparticle-decorated, single vanadium dioxide nanowires. The high-sensitivity arises from the large downward shift in the insulator to metal transition temperature following the adsorption on and incorporation of atomic hydrogen, produced by dissociative chemisorption on Pd, in the VO(2), producing approximately 1000-fold current increases. During a rapid initial process, the insulator to metal transition temperature is decreased by >10 degrees C even when exposed to trace amounts of hydrogen gas. Subsequently, hydrogen continues to diffuse into the VO(2) for several hours before saturation is achieved with only a modest change in the insulator to metal transition temperature but with a significant increase in the conductivity. The two time scales over which H-related processes occur in VO(2) likely signal the involvement of two distinct mechanisms influencing the electronic structure of the material one of which involves electron-phonon coupling pursuant to the modification of the vibrational normal modes of the solid by the introduction of H as an impurity.

Size-dependent sedimentation properties of nanocrystals.

Centrifugation is an increasingly important technique for nanomaterial processing. Here, we examine this process for gold, cadmium selenide, and iron oxide nanocrystals using an analytical ultracentrifuge. Such data provide an accurate measure of the sedimentation coefficients for these materials, and we find that this parameter has a significant dependence on the size and surface coating. Conventional models for particle sedimentation cannot capture the behavior of these nanocrystals unless the density of the nanocrystals is described by a size-dependent term that accounts for both the inorganic core and the organic coating. Using this modification in the particle sedimentation framework, it is possible to estimate sedimentation coefficients from information about the nanocrystal core and surface coating dimensions. Such data are useful in choosing the speeds for a centrifugation process and are particularly important when bimodal nanocrystal distributions are present.

Amidoximes: promising candidates for CO2 capture

Monoethanolamine (MEA) dominates power plant carbon dioxide (CO2) scrubbing processes, though with major disadvantages such as a 8–35% energy penalty. Here we report that structurally comparable amidoximes are promising CO2 capture agents based on RIMP2 electronic structure calculations. This was experimentally verified by the synthesis and testing of representative amidoximes for capture efficiencies at pressures as high as 180 bar. Acetamidoxime, which has the highest percent amidoxime functionality showed the highest CO2 capacity (2.71 mmol g−1) when compared to terephthalamidoxime (two amidoximes per molecule) and tetraquinoamidoxime (four amidoximes per molecule). Polyamidoxime surpassed activated charcoal Norit RB3 for CO2 capture per unit surface area. Adsorption isotherms exhibit Type IV behavior and acetamidoxime found to increase CO2 capture with temperature, a less observed anomaly. Porous amidoximes are proposed as valuable alternatives to MEA.

Growth of Metal Oxide Nanowires from Supercooled Liquid Nanodroplets

Nanometer-sized liquid droplets formed at temperatures below the bulk melting point become supercooled as they grow through Ostwald ripening or coalescence and can be exploited to grow nanowires without any catalyst. We used this simple approach to synthesize a number of highly crystalline metal oxide nanowires in a chemical or physical vapor deposition apparatus. Examples of nanowires made in this way include VO(2), V(2)O(5), RuO(2), MoO(2), MoO(3), and Fe(3)O(4), some of which have not been previously reported. Direct evidence of this new mechanism of nanowire growth is found from in situ 2-dimensional GISAXS (grazing incidence small angle X-ray scattering) measurements of VO(2) nanowire growth, which provides quantitative information on the shapes and sizes of growing nanowires as well as direct evidence of the presence of supercooled liquid droplets. We observe dramatic changes in nanowire growth by varying the choice of substrate, reflecting the influence of wetting forces on the supercooled nanodroplet shape and mobility as well as substrate-nanowire lattice matching on the definition of nanowire orientation. Surfaces with defects can also be used to pattern the growth of the nanowires. The simplicity of this synthesis concept suggests it may be rather general in its application.

Pollution magnet: nano-magnetite for arsenic removal from drinking water.

Arsenic contamination in groundwater is a severe global problem, most notably in Southeast Asia where millions suffer from acute and chronic arsenic poisoning. Removing arsenic from groundwater in impoverished rural or urban areas without electricity and with no manufacturing infrastructure remains a significant challenge. Magnetite nanocrystals have proven to be useful in arsenic remediation and could feasibly be synthesized by a thermal decomposition method that employs refluxing of FeOOH and oleic acid in 1-octadecene in a laboratory setup. To reduce the initial cost of production,