Sour Gas Adsorption on Silica Gels.

One of the essential factors for water adsorption on silica gels is the concentration of silanol groups on the silica surface. However, no systematic investigation on the adsorption of sour gas components, methane (CH4), carbon dioxide (CO2), and hydrogen sulfide (H2S) on silica gels with different textural properties and surface silanol concentrations, has been conducted. Three silica gels of 22, 30, and 60 Å pore sizes, with silanol concentrations of αtotal = 2.516, 2.340, and 2.152 OH nm-2, respectively, were studied in this work. The adsorption data for CH4, CO2, H2S, and H2O at T = 0, 25, and 50 °C on the 22 and 30 Å pore size silica gels were presented, and a comparison of the data for the 60 Å pore size silica gel on the same adsorbates was conducted. All three silica gels showed an adsorption affinity in the order of H2O > H2S > CO2 > CH4. The isosteric heats of adsorption of H2O and H2S had a greater dependence on the silanol concentration than CO2 and CH4. At p < 10 bar, there was no difference in the adsorption per m2 of CH4 between the silica gels (n ads = 1.7 mmol m-2, for all silicas at p = 10 bar), while higher pressures resulted in greater adsorption capacity in the larger pore volume silica gels (at p = 20 bar: n ads = 3.0, 3.3, and 3.4 mmol m-2 for the 22, 30, and 60 Å pore size silicas, respectively). H2S adsorption at low pressures (p < 4 bar) was larger on the samples with larger silanol concentrations (at p = 3 bar: n ads = 6.1, 4.7, and 4.5 mmol m-2 for the 22, 30, and 60 Å pore size silicas, respectively), but above p = 4 bar, the 60 Å pore size silica had a greater adsorption capacity than the 30 Å pore size (at p = 5 bar: n ads = 8.0, 6.0, and 6.2 mmol m-2 for the 22, 30, and 60 Å pore size silicas, respectively).

Metal Oxide-Related Dendritic Structures: Self-Assembly and Applications for Sensor, Catalysis, Energy Conversion and Beyond.

In the past two decades, we have learned a great deal about self-assembly of dendritic metal oxide structures, partially inspired by the nanostructures mimicking the aesthetic hierarchical structures of ferns and corals. The self-assembly process involves either anisotropic polycondensation or molecular recognition mechanisms. The major driving force for research in this field is due to the wide variety of applications in addition to the unique structures and properties of these dendritic nanostructures. Our purpose of this minireview is twofold: (1) to showcase what we have learned so far about how the self-assembly process occurs; and (2) to encourage people to use this type of material for drug delivery, renewable energy conversion and storage, biomaterials, and electronic noses.

Sol-gel synthesis of 2-dimensional TiO2: self-assembly of Ti-oxoalkoxy-acetate complexes by carboxylate ligand directed condensation.

2-Dimensional (2D) metal oxides have many potential industrial applications including heterogeneous catalysis, water splitting, renewable energy conversion, supercapacitor applications, biomaterials, gas separation and gas storage. Herein we report a simple and scalable method for the preparation of 2D TiO2 nanostructures by reaction of titanium isopropoxide with acetic acid at 333 K in isopropanol, followed by calcination at 673 K to remove the organic ligands. Both the products and reaction intermediates have been studied using electron microscopy, X-ray diffraction, N2 physisorption, nuclear magnetic resonance, thermogravimetric analysis, and X-ray photoelectron, Raman, and infrared spectroscopy. The anisotropic condensation of the planar Ti6O4(OiPr)8(OAc)8 complex is believed to be responsible for the formation of the 2D structure, where OiPr and OAc represent isopropoxide and acetate ligands, respectively. This research demonstrates that the metal complexes are promising building blocks for desired architectures, and the self-assembly of an acetate bidentate ligand is a versatile tool for manipulating the shape of final products.

Synthesizing 1D and 2D metal oxide nanostructures: using metal acetate complexes as building blocks.

1D and 2D metal oxide nanostructures are important for potential applications in alternative energy, batteries, supercapacitors, catalysts, biomaterials, and electronic nanodevices. Many current approaches for making the desired nanomaterials require multiple steps, which are often exotic and complex for production on a commercial scale. In contrast, the sol-gel reactions between metal alkoxides and organic acids have emerged as a simple protocol for producing metal oxides and inorganic/organic hybrid materials with a controllable 1D or 2D architecture. Our knowledge of this process continues to evolve through the fundamental goal of designing a desired nanostructure from the corresponding molecular building blocks. Our research was driven by the discovery of various morphologies by fine-tuning the synthesis parameters, such as the reaction temperature and molar ratio of the reactants, as well as switching solvents. These discoveries lead to several quesions: What are the building blocks of the 1D and 2D nanostructures and how does the self-assembly occur? What are the reaction kinetics and the mechanisms of nanostructure formation? What role does the solvent play in the assembly process? What are the effects of reaction temperature and pressure? How can we manipulate the nanostructure-for example, the parallel growth of 1D semiconductors-from a substrate surface? And lastly, what are the industrial applications of macroporous aerogels and xerogels? This minireview will highlight documented research accounts to answer these questions.

Viscoelastic behavior corresponding to reptative relaxation times across the λ-transition for liquid elemental sulfur.

Continued interest regarding the rheometric measurements of molten sulfur has persisted due to the need for industrial-scale transportation and handling of the material in a liquid phase. This has allowed for extended research developments to attain a fundamental understanding of the fluid. This work reports novel high temperature modulus data over the λ-transition region for liquid elemental sulfur, measured through the use of a modified Anton-Paar Modular Compact Rheometer 302. From these measurements, further insight was gained on the viscoelastic behavior and reptative relaxation times for liquid elemental sulfur. The slow relaxation time, τs, related to reptative behavior, was found to be between 0.24 s and 0.28 s at 190 °C. Utilizing the Maxwell relation, this was determined to correspond to an estimated viscosity range from 72 000 × 10-3 Pa s to 95 000 × 10-3 Pa s, which is in agreement with previous viscosity studies on liquid sulfur. A Cole-Cole plot of the experimental data also displayed characteristics of Debye-like relaxation, suggesting that the slow relaxation process was related to local S-S bond scission and recombination in sulfur chains and was not a relaxation coinciding with a polymeric chain mode. Finally, consecutive heating and cooling of the sulfur sample gave replicate values up to 210 °C on the third heating cycle, where an apparent structural change took place possibly due to cycling over the secondary transition, producing a thermal history, or sulfur reactions with trace impurities. This 210 °C temperature was found to have some recurrence within the literature.

Selective Adsorption of Thiols Using Gold Nanoparticles Supported on Metal Oxides.

Selective capture of thiols from a synthetic hydrogen sulfide containing mixture using supported nanogold materials has been explored for the potential removal of thiols from sour gas production fluids. In this research, TiO2-, Al2O3-, SiO2-, and ZnO-supported gold nanoparticles have been studied for their usage as regeneratable adsorbents to capture CH3SH, C2H5SH, and i-C3H7SH. Au/TiO2 and Au/Al2O3 showed promising properties for removing the thiols efficiently from a gas-phase mixture; however, Au/Al2O3 did catalyze some undesirable side reactions, e.g., carbonyl sulfide formation. It was found that a mild temperature of T = 200 °C was sufficient for regeneration of either Au/TiO2 or Au/Al2O3 adsorbent. The metal oxide mesopores played an important role for accommodating gold particles and chemisorption of the thiols, where smaller pore sizes were found to inhibit the agglomeration/growth of gold particles. The nature of thiol adsorption and the impact of multiple adsorption-desorption cycles on the adsorbents have been studied using electron microscopy, XPS, XRD, GC, and physi/chemiadsorption analyses.

Structural model of FeoB, the iron transporter from Pseudomonas aeruginosa, predicts a cysteine lined, GTP-gated pore.

Iron is essential for the survival and virulence of pathogenic bacteria. The FeoB transporter allows the bacterial cell to acquire ferrous iron from its environment, making it an excellent drug target in intractable pathogens. The protein consists of an N-terminal GTP-binding domain and a C-terminal membrane domain. Despite the availability of X-ray crystal structures of the N-terminal domain, many aspects of the structure and function of FeoB remain unclear, such as the structure of the membrane domain, the oligomeric state of the protein, the molecular mechanism of iron transport, and how this is coupled to GTP hydrolysis at the N-terminal domain. In the present study, we describe the first homology model of FeoB. Due to the lack of sequence homology between FeoB and other transporters, the structures of four different proteins were used as templates to generate the homology model of full-length FeoB, which predicts a trimeric structure. We confirmed this trimeric structure by both blue-native-PAGE (BN-PAGE) and AFM. According to our model, the membrane domain of the trimeric protein forms a central pore lined by highly conserved cysteine residues. This pore aligns with a central pore in the N-terminal GTPase domain (G-domain) lined by aspartate residues. Biochemical analysis of FeoB from Pseudomonas aeruginosa further reveals a putative iron sensor domain that could connect GTP binding/hydrolysis to the opening of the pore. These results indicate that FeoB might not act as a transporter, but rather as a GTP-gated channel.

Experimental and theoretical investigation of the kinetics of the reaction of atomic chlorine with 1,4-dioxane.

The rate coefficients for the reaction of 1,4-dioxane with atomic chlorine were measured from T = 292-360 K using the relative rate method. The reference reactant was isobutane and the experiments were made in argon with atomic chlorine produced by photolysis of small concentrations of Cl2. The rate coefficients were put on an absolute basis by using the published temperature dependence of the absolute rate coefficients for the reference reaction. The rate coefficients for the reaction of Cl with 1,4-dioxane were found to be independent of total pressure from p = 290 to 782 Torr. The experimentally measured rate coefficients showed a weak temperature dependence, given by k(exp)(T) = (8.4(-2.3)(+3.1)) × 10(-10) exp(-(470 ± 110)/(T/K)) cm3 molecule (-1) s(-1). The experimental results are rationalized in terms of statistical rate theory on the basis of molecular data obtained from quantum-chemical calculations. Molecular geometries and frequencies were obtained from MP2/aug-cc-pVDZ calculations, while single-point energies of the stationary points were computed at CCSD(T) level of theory. The calculations indicate that the reaction proceeds by an overall exothermic addition-elimination mechanism via two intermediates, where the rate-determining step is the initial barrier-less association reaction between the chlorine atom and the chair conformer of 1,4-dioxane. This is in contrast to the Br plus 1,4-dioxane reaction studied earlier, where the rate-determining step is a chair-to-boat conformational change of the bromine-dioxane adduct, which is necessary for this reaction to proceed. The remarkable difference in the kinetic behavior of the reactions of 1,4-dioxane with these two halogen atoms can be consistently explained by this change in the reaction mechanism.