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There is a need to develop highly CU2+ selective materials which can potentially remediate copper contaminated soils and water. Here we show that several highly charged synthetic swelling mica-type clays are highly selective for copper exchange. The synthetic micas have cation exchange capacities (CECs), which are close to their theoretical values. Both Na-saturated and Mg-saturated micas were investigated for Cu ion exchange selectivity. Ion exchange isotherms and Kielland plots were constructed using the equilibrated solution analyses. From these studies it was found that Na-4-mica and Na-3-mica could selectively exchange copper at lower concentrations from solution, whereas Na-2-mica sample performed better by showing Cu ion exchange selectively to almost its capacity. The EPR spectra of Cu-exchanged micas coincide with the mica's charge characteristics that predict increased binding strength of exchangeable Cu in Na-4-mica and Na-3-mica than in Na-2-mica.

This research studied a relative comparison of the hydrocarbon emissions during pyrolysis of four carbonaceous additives that can be used in green sand foundries. These included a highly volatile bituminous coal, anthracite, lignite, and cellulose. Analytic pyrolysis was conducted to simulate the heating conditions that the carbonaceous additives would experience during metal pouring. Specifically, the samples were flash pyrolyzed in a Curie-point pyrolyzer at 920 degrees C with a heating rate of about 3000 degrees C/sec. This simulated some key features of the fast heating conditions that the carbonaceous additives would experience at the metal-mold interface when molten metal is poured into green sand molds. The samples were also pyrolyzed in a thermogravimetric analyzer (TGA) from ambient temperature to 1000 degrees C with a heating rate of 20 degrees C/min; and this simulated key features of the slow heating conditions that the carbonaceous additives would experience within the bulk of green sand molds that is further away from the metal-mold interface. Hydrocarbon emissions from flash pyrolysis were analyzed with GC-FID, while those from TGA pyrolysis were monitored with mass spectroscopy and GC-FID. The anthracite exhibited very low volatile hydrocarbons during both flash pyrolysis and TGA pyrolysis. The cellulose released less hydrocarbons than bituminous coal or lignite in TGA pyrolysis, but more hydrocarbons than those two during flash pyrolysis. This means that cellulose can release sufficient volatile hydrocarbons at the intensely heated molten metal-mold interface where they are most desired for ensuring casting quality, but much less within the bulk of the mold where they are undesirable. This characteristic of cellulose offers an important opportunity for green sand foundries to diminish their hazardous air pollutant (HAP) emissions.

The microwave-hydrothermal method has been investigated for the fast synthesis of rare earth cerium oxide (CeO2) nanoparticles and nanorods. This approach combines the advantages of both hydrothermal and microwave heating techniques. It is facile, rapid, energy-saving, and environmentally-benign and leads to high-yields. The average sizes of the obtained CeO2 nanoparticles could be adjusted from approximatrly 1.6 nm to approximately 20 nm. Moreover, by changing cerium source and adjusting the amount of the added ammonia water, CeO2 nanorods could be synthesized under microwave-assisted conditions for the first time. No calcination process or surfactant is required in our experiments for both CeO2 nanoparticles and nanorods. The ultraviolet and visible (UV-vis) spectra show the obvious size-dependence of the position of the absorbance peak. The Brunaur Emmett Teller (BET) nitrogen adsorption indicates that these nanoparticles and nanorods have high specific surface areas, which are needed for potential applications in many fields. Compared with conventional hydrothermal method, microwave-assisted hydrothermal method shows its advantages of rapidity, convenience and perhaps cost-effectiveness and could be extended to the synthesis of other nanoparticles and nanorods.

Solid-state NMR spectroscopy and ab initio computational chemistry are used to determine the structure of the complex formed upon adsorption of the mononucleotide 2'-deoxyadenosine 5'-monophosphate (dAMP) to the surface of a mesoporous alumina. In this multi-technique approach, rotational-echo double-resonance NMR results reveal that the phosphate group of dAMP interacts predominantly with octahedrally coordinated aluminum species at the surface, and therefore, adsorption is modeled with both mono- and bidentate sorption of the nucleotide phosphate group with octahedral aluminum. 31P chemical shielding tensors are calculated from the structure of the lowest energy conformations, and these results are compared to tensor values extracted from analysis of spinning-sideband patterns in the experimental 31P cross-polarization magic-angle-spinning NMR spectrum. The chemical shift anisotropy and asymmetry parameter indicate that the binding is via a monodentate, inner-sphere complex.

A new concept of multi-level assemblies of nanorod-based structures has been proposed, which could give new insight into the construction of nanorod-based complex structures from the bottom up. Multi-level architectures of complex lead sulphide (PbS) nanorod-based structures have been realized by a simple and general amino acid-mediated approach. First-level structure (multi-arm horn-like structure), second-level structure (bi-pyramid structure formed by several horn-like structures), and third-level structure (multi-pyramid structure formed by several pyramid-like structures) can be synthesized with the assistance of different amino acids: aspartic acid, serine, and histidine, respectively. The amino acids have several functional groups, such as -NH(2) and -COOH, which have strong abilities for coordination with the metal ions, and might provide reaction sites by coordinating with metal ions to initiate and then confine the assemblies of the PbS nanorods. This amino acid-mediated method provides a possibility of studying the formation and assembly mechanisms from the bottom up and might open a door to constructing complex nanorod-based structures at different levels.

The effects of advanced oxidation (AO) processing on the properties of green sand were studied via pouring cast iron into green sand molds. Upon cooling, the green sand molds were autopsied at various distances from the metal-sand interface. Autopsy green sand samples collected from a mold that incorporated AO water were characterized and compared to controlled samples collected from a similar autopsied mold made with conventional tap water (TAP). It was found that the AO processing removed a coating of coal pyrolysis products from the clay surface that typically accumulated on the clay surface. As a result, the AO-conditioned green sand retained 10-15% more active clay as measured bythe standard ultrasonic methylene blue titration than did the TAP-conditioned green sand. The AO processing also nearly doubled the generation of activated carbon from the normalized amount of coal composition of the green sand during the casting process. The AO-enhanced activated carbon generation and the AO-incurred clay surface cleaning provided the AO-conditioned green sand with higher normalized pore volume, and thus higher normalized m-xylene adsorption capacity, i.e., relative to before-metal-pouring conditions. Furthermore, mathematical analysis indicated that the AO-conditioned green sand better retained its important properties after pouring than did the TAP-conditioned green sand. Effectively, this meant after metal pouring, the AO-conditioned sample offered about the same net properties as the TAP-conditioned sample, even though the AO-conditioned sample contained less clay and coal before metal pouring. These results conformed to the full-scale foundry empirical finding that when AO is used, foundries need less makeup clay and coal addition through each casting cycle, and they release less air emissions.

The nature of strontium binding by soil minerals directly affects the transport and sequestration/remediation of radioactive strontium species released from leaking high-level nuclear waste storage tanks. However, the molecular-level structure of strontium binding sites has seldom been explored in phyllosilicate minerals by direct spectroscopic means and is not well-understood. In this work, we use solid-state NMR to analyze strontium directly and indirectly in a fully strontium-exchanged synthetic mica of nominal composition Na(4)Mg(6)Al(4)Si(4)O(20)F(4). Thermogravimetric analysis, X-ray diffraction analysis, and NMR evidence supports that heat treatment at 500 degrees C for 4 h fully dehydrates the mica, creating a hydrogen-free interlayer. Analysis of the strontium NMR spectrum of the heat-treated mica shows a single strontium environment with a quadrupolar coupling constant of 9.02 MHz and a quadrupolar asymmetry parameter of 1.0. These quadrupolar parameters are consistent with a highly distorted and asymmetric coordination environment that would be produced by strontium cations without water in the coordination sphere bound deep within the ditrigonal holes. Evidence for at least one additional strontium environment, where proton-strontium couplings may occur, was found via a (1)H-(87)Sr transfer of populations by double resonance NMR experiment. We conclude that the strontium cations in the proton-free interlayer are observable by (87)Sr NMR and bound through electrostatic interactions as nine coordinate inner-sphere complexes sitting in the ditrigonal holes. Partially hydrated strontium cations invisible to direct (87)Sr NMR are also present and located on the external mica surfaces, which are known to hydrate upon exposure to atmospheric moisture. These results demonstrate that modern pulsed NMR techniques and high fields can be used effectively to provide structural details of strontium binding by phyllosilicate minerals.

Prior full-scale foundry data have shown that when an advanced oxidation (AO) process is employed in a green sand system, the foundry needs 20-35% less makeup bentonite clay than when AO is not employed. We herein sought to explore the mechanism of this enhancement and found that AO water displaced the carbon coating of pyrolyzed carbonaceous condensates that otherwise accumulated on the bentonite surface. This was discerned by surface elemental analysis. This AO treatment restored the clay's capacity to adsorb methylene blue (as a measure of its surface charge) and water vapor (as a reflection of its hydrophilic character). In full-scale foundries, these parameters have been tied to improved green compressive strength and mold performance. When baghouse dust from a full-scale foundry received ultrasonic treatment in the lab, 25-30% of the dust classified into the clay-size fraction, whereas only 7% classified this way without ultrasonics. Also, the ultrasonication caused a size reduction of the bentonite due to the delamination of bentonite particles. The average bentonite particle diameter decreased from 4.6 to 3 microm, while the light-scattering surface area increased over 50% after 20 min ultrasonication. This would greatly improve the bonding efficiency of the bentonite according to the classical clay bonding mechanism. As a combined result of these mechanisms, the reduced bentonite consumption in full-scale foundries could be accounted for.

Zeolites can accommodate a considerable amount of occluded salt such as NH4NO3, which can serve as a good source of slow-release plant nutrient. This study evaluates the kinetics of ion release from NH4NO3-occluded Na-P1 (N-NaP) using a simulated soil solution and deionized water as leaching solutions. The patterns of ion releases were examined as a function of leaching time under both static and continuous-flow conditions for more than one month. Releases of both NH4+ and NO3- from N-NaP were found to be slow and steady under both the above conditions. The soil solution affected the release of NH4+ and NO3- differently, while deionized water released nearly the same equivalents of these ions. This clearly indicates that ion release from salt-occluded zeolite involves two different reactions, cation exchange and dissolution. The kinetics of ion release from occluded NH4NO3 under static condition was best described by the standard Elovich model while the power function model best expressed these under continuous-flow condition. The initial ion release patterns under both conditions exhibited considerable deviation from the simulated models, probably as a result of the presence of hydrated occluded NH4NO3. Flow condition and the presence of electrolytes in leaching solution affected the release kinetics significantly. Release of occluded NH4NO3 was delayed by the presence of the NH4NO3 coated on zeolite crystals. These results indicate that the ion release property of occluded salt could be predicted and controlled. This study clearly shows that NH4NO3-occluded zeolites could be developed as slow release fertilizers.

Lysozyme, a protein, has been found to be a new morphology-directing agent and a simple and mild bio-molecule assisted method has been proposed for the synthesis of single-crystal bismuth sulfide and oxide nanowires.

The growth of ordered nanorods of mesoporous SBA-15 inside a porous alumina membrane has been achieved for the first time by a simple sol-gel method. The obtained SBA-15 nanorods themselves have ordered hexagonal mesochannels with a size of about 6 nm and have been arranged to form hexagonal arrays by the limitation of pores of the alumina membrane. The synthesized alumina membrane with mesoporous SBA-15 inside combines the advantages of porous alumina membranes and mesoporous SBA-15 and provides fine and vertical mesochannels, which may serve as a new and efficient mold and lead to extensive applications in nanodevice fabrication, biomacromolecule separations, etc.

Two SiO2 and three Al2O3 adsorbents with varying degrees of mesoporosity (pore diameter 2-50 nm) were reacted with 2,4-dichlorophenoxyacetic acid (2,4-D) at pH 6 to investigate the effects of intraparticle mesopores on adsorption/desorption. Anionic 2,4-D did not adsorb onto either SiO2 solid, presumably because of electrostatic repulsion, but it did adsorb onto positively charged Al2O3 adsorbents, resulting in concave isotherms. The Al2O3 adsorbent of highest mesoporosity consistently adsorbed more 2,4-D per unit surface area than did the nonporous and less mesoporous Al2O3 adsorbents over a range of initial 2,4-D solution concentrations (0.025-2.5 mM) and reaction times (30 min-55 d). Differences in adsorption efficiency were observed despite equivalent surface site densities on the three Al2O3 adsorbents. Hysteresis between the adsorption/desorption isotherms was not observed, indicating that adsorption is reversible. Attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy studies confirm that 2,4-D adsorption does not occur via ligand exchange, but rather via electrostatic interaction. The results indicate that adsorbent intraparticle mesopores can result in consistently greater 2,4-D adsorption, but the amount adsorbed is dependent upon surface charge and the presence of adsorbent mesoporosity. The data also suggest that when mineral pores are significantly larger than the adsorbate, they do not contribute to diffusion-limited adsorption/desorption hysteresis. Adsorbent transformations through time are discussed.

A biomolecule-assisted simple technique has been developed for the spontaneous ordering of the Bi2S3 nanorods into snowflakelike superstructures in high yield under microwave-hydrothermal conditions. In this method, glutathione (GSH) is used as both an assembling agent and a sulfur source. By controlling the molar ratio between bismuth nitrate and glutathione as well as the synthetic temperature, several kinds of Bi2S3 one-dimensional nanomaterials such as snowflakelike structures, nanowires constructed of particles, short nanorods, and fine and long nanowires have been controllably synthesized.

Synthesis of micropore-free hydrothermally stable mesoporous silica SBA-15 has been accomplished by templating a silica precursor (sodium silicate/tetraethylorthosilicate) with pluroni123 copolymer (EO20PO70EO20; M.W. 5,800) in the presence of cosolvent (ethanol) using a minimum salt (sodium chloride) content, under microwave-hydrothermal conditions at 373 K in 120 mins.

The structural changes of synthetic and natural beidellites during dehydroxylation have been studied using infrared emission spectroscopy of the OH-stretching and bending regions. The OH-stretching region is characterized by two OH-stretching modes around 3600-3615 cm-1 and around 3650 cm-1. These bands strongly decrease in intensity upon dehydroxylation up to 600 degrees C for the natural beidellite and 700-750 degrees C for the synthetic ones. The differences in bandwidth, intensity, and dehydroxylation behavior are interpreted as due to differences in crystallinity with crystallinity increasing in the order natural beidellite < synthetic beidellite BSK3 < synthetic beidellite E498. Above 400 degrees C a new band attributed to silanol groups becomes visible in all samples due to transfer of the hydroxyls from the octahedral layer to the siloxane layer before they are lost. The broad band around 3300-3400 cm-1 is assigned to both H-bonding in H2O and H-bonding to Si-O-Al linkages. The presence of two different OH groups is also reflected in the OH-bending modes around 875-895 cm-1 and 915-925 cm-1 and in the OH-libration modes around 780 and 800-820 cm-1. These bands show a decrease in intensity upon heating and dehydroxylation of the clay structure. Here again the same order can be observed for the disappearance of the bands as for the OH-stretching region. Copyright 1999 Academic Press.

The microscopic structure of oxygen confined in silica xerogels has been studied as a function of temperature. In large pores, a crystalline solid forms with a structure consistent with that of the bulk. The size of the crystallites is much larger than the pore size, indicating that cooperative effects among pores are important in freezing. As the pore size is decreased, a crossover occurs where solidification results in an amorphous phase in the pores. The resulting amorphous phase is solid but is less ordered than the liquid phase.

Tobermorites have cation-exchange and selectivity properties intermediate between those of clay minerals and zeolites. Aluminum-substituted tobermorites in particular show high selectivity for cesium. This new group of cation exchangers may find applications in catalysis and in nuclear and hazardous waste disposal.

Ahydrated, sodium phlogopite mica with a c-axis spacing [d(001)] of 12.23 A made by careful low-temperature leaching, showed extremely high selectivity for cesium. This newly discovered cesium ion sieve is useful in the decontamination as well as immobilization of cesium at room temperature through chemical bonding and may find applications in nuclear waste disposal and in decontamination of the environment after accidental releases of nuclear materials.