Experimental and Theoretical Study of the Effect of Moisture on Methane Adsorption and Desorption by Activated Carbon at 273.5 K

Adsorption and desorption of methane by activated carbon (AC) at constant temperature and at various pressures were investigated. The effect of moisture was also studied. A volumetric method was used, up to 40 bar, at a temperature of 273.5 K. Results of a dry AC sample were compared with those obtained from a moist sample and two different ACs with different physical and surface properties were used. As expected, the results showed that the existence of moisture, trapped in the AC pores, could lead to a decrease in the amount of methane adsorbed and a decrease in the amount of methane delivered during desorption. To model the experimental results, a large variety of adsorption isotherms were used. The regressed parameters for the adsorption isotherms were obtained using the experimental data generated in the present study. The accuracy of the results obtained from the different adsorption isotherms was favorably compared.     

Density functional theory study of the Fourier transform infrared and Raman spectra of Cu(II) bis-acetylacetone

Fourier transform infrared and Fourier transform Raman spectra of Cu(II) bis-acetylacetone have been obtained. The geometry, frequency and intensity of the vibrational bands of this compound and its 1,5-(13)C(2), 3-(13)C, 1,3,5-(13)C(3), 2,4-(13)C(2), (18)O(2) and 2,4-(13)C(2)-(18)O(2) derivatives were obtained by the density functional theory (DFT) with the B3LYP functional and using the 6-31G(*) and 3-21G(*) basis sets. The calculated frequencies are compared with the solid infrared and Raman spectra. All the measured infrared and Raman bands were interpreted in terms of the calculated vibrational modes. The percentage of deviation of the bond lengths and bond angles gives a good picture of the normal modes, and serves as a basis for the assignment of the wavenumbers. Most computed bands are predicted to be at higher wavenumbers than the experimental bands. The calculated geometrical parameters show slight differences compared with the experimental results. These differences can be explained by the different physical state of Cu(II) bis-acetylacetone. The DFT-B3LYP calculations assumed a free molecule in the gas phase. Analysis of the vibrational spectra indicates a strong coupling between the chelated ring modes.     

Synthesis and structure of diamido ether uranium(IV) and thorium(IV) halide "ate" complexes and their conversion to salt-free bis(alkyl) complexes

The high-yield synthesis, spectroscopic and structural determination of three new uranium(IV) and thorium(IV)ate complexes supported by three different diamido ether ligands are reported. The reaction of Li2[2,6-iPr2PhN(CH2CH2)]2O (Li2[DIPPNCOCN]) with 1 equiv. of UCl4 in THF generates [DIPPNCOCN]UCl3Li(THF)2(1), while reaction in toluene/ether gives salt-free [DIPPNCOCN]UCl2.1/2C7H8(2), which was identified by paramagnetically shifted 1H NMR. Reaction of 0.5 equiv. of {[tBuNON]UCl2}2([tBuNON]=[(CH3)3CN(Si(CH3)2)]2O2-) with 3.5 equiv. LiI in toluene and a minimal amount of THF results in [tBuNON]UI3Li(THF)2(3) and is very similar in structure to 1. {[MesNON]ThCl3Li(THF)}2(4), a dimeric complex with a Th2Li2Cl6 core, is prepared by reaction of Li2[2,4,6-Me3PhN(Si(CH3)2)]2O (Li2[MesNON]) with ThCl4 in THF. The analogous reaction in toluene did not yield the salt-free complex but rather a sterically crowded diligated compound, [MesNON]2Th (5), which was also structurally characterized. Complex 5 was prepared rationally by reacting 2 equiv. Li2[MesNON] with ThCl4 in toluene. The reaction of 1 and 3 with 2 equiv. of LiCH2Si(CH3)3 generates the stable, salt-free organoactinides [DIPPNCOCN]U(CH2Si(CH3)3)2(6) and [tBuNON]U(CH2Si(CH3)3)2(7). Complex 6 was structurally characterized. These reactions illustrate the viability of ate complexes as useful synthetic precursors.     

Al-doped B80 fullerene as a suitable candidate for H2, CH4, and CO2 adsorption for clean energy applications

Dispersion-corrected density functional theory method was performed to report on a high-performance adsorbent for removal of CO₂ from the precombustion and natural gases. At first, the effect of Al atom impurity on the structural and electronic properties of B₈₀ fullerene is studied. Then, the adsorption geometries and energies of gases (H₂, CH₄, or CO₂) on the B₈₀ and AlB₇₉ (amphoteric adsorbents) are explored. The Al atom enhances reactivity of the cage toward the gases and the adsorption processes are more exothermic with low and high energy barriers for chemisorption of H₂ and CO₂, respectively. Stable chemisorption of CO₂ on the AlB₇₉ is validated by the high adsorption energy and large charge transfer, while the CH₄ is just physically adsorbed on the AlB₇₉. Further, the physisorbed gases can enhance field emission current of the AlB₇₉ and in the continuous capturing of the gases, the magnetic moment of the cage is quenched. Furthermore, dependency of the electronic structure of the adsorbent on the gas adsorption is intensively studied. We suggest that the AlB₇₉ could be a promising material for capture, storage, and separation of the gases and as a novel material for sustainable energy and sweetening process in the petroleum industry.     

Green synthesis and characterization of monodispersed silver nanoparticles obtained using oak fruit bark extract and their antibacterial activity

Green synthesis of silver nanoparticles (Ag NPs) has been achieved using oak fruit bark extract as a reducing, capping and stabilizing agent. The biosynthesized Ag NPs were characterized using various techniques. UV–visible spectrum of prepared silver colloidal solution showed absorption maximum at 433 nm. X‐ray diffraction and transmission electron microscopy analysis revealed that Ag NPs have a face‐centred cubic structure being spherical in shape with an average particle size of 20–25 nm. The toxicity of the Ag NPs was tested on bacterial species such as Staphylococcus aureus, Bacillus subtilis, Pseudomonas aeruginosa and Escherichia coli by comparison based on diameter of inhibition zone in disc diffusion tests and minimum inhibitory concentration and minimum bactericidal concentration of NPs dispersed in liquid cultures. The antimicrobial activity of Ag NPs was greater towards Gram‐positive bacteria (S. aureus and B. subtilis) compared to Gram‐negative bacteria as determined using standard Kirby–Bauer disc diffusion assay and serial dilution. Copyright © 2016 John Wiley & Sons, Ltd.     

Palladium on magnetic Irish moss: A new nano‐biocatalyst for suzuki type cross‐coupling reactions

A novel heterogeneous magnetic palladium nano‐biocatalyst was designed by utilizing Irish moss, a family of sulfated polysaccharides extracted from algae, as a natural biopolymer. This magnetic Irish moss decorated with palladium (Pd–Fe₃O₄@IM) to form a biomagnetic catalytic system was synthesized and well characterized by FT–IR analysis, X‐ray powder diffraction, field emission scanning electron microscopy, energy‐dispersive X‐ray spectroscopy, atomic absorption spectroscopy and transmission electron microscopy. The catalyst was stable to air and moisture and displayed high catalytic activity in ligand‐free Suzuki–Miyaura cross‐coupling reactions conducted under green chemistry reaction conditions. The aromatic ketones are produced by the cross‐coupling reaction between acid chlorides and aryl boronic acid derivatives in high yields.     

Biosynthesis of gold nanoparticles using Allium noeanum Reut. ex Regel leaves aqueous extract; characterization and analysis of their cytotoxicity,antioxidant, and antibacterial properties

Gold nanoparticles have unique and excellent medical and nonmedical properties and application compared with other metallic nanoparticles. Recently, they have been used for the prevention, control, and treatment of bacterial and fungal diseases. In the recent study, fresh and clean leaves of Allium noeanum Reut. ex Regel leaves have been used for the synthesis of gold nanoparticles. Also, we evaluated the cytotoxicity, antioxidant, and antibacterial properties of HAuCl₄, A. noeanum, and the synthesized nanoparticles (Au NPs). These nanoparticles were analyzed by FT‐IR, UV, XRD, EDS, FE‐SEM, and TEM tests. FTIR results offered antioxidant compounds in the plant were the sources of reducing power, reducing gold ions to Au NPs. In TEM images revealed an average diameter of 10‐30 nm. At the beginning of biological experiments, DPPH free radical scavenging test was carried out to examine the antioxidant property. Also, in the bacterial part of this study, the concentration of HAuCl₄, A. noeanum, and AuNPs with minimum dilution and no turbidity was considered MIC. To determine MBC, 60 μL of MIC and three preceding chambers were cultured on Muller Hinton Agar. The minimum concentration with no bacterial growth was considered MBC. Au NPs revealed excellent antioxidant potential against DPPH, non‐toxicity property against human umbilical vein endothelial cells, and antibacterial activities against Streptococcus pneumonia, Bacillus subtilis, Staphylococcus aureus, Staphylococcus saprophyticus, Salmonella typhimurium, Pseudomonas aeruginosa, Shigella flexneri, and Escherichia coli O157:H7. These findings show that the inclusion of A. noeanum extract improves the solubility of Au NPs, which led to a notable enhancement in the antioxidant and antibacterial effects.     

Palladium nanoparticles‐decorated triethanolammonium chloride ionic liquid‐modified TiO2 nanoparticles (TiO2/IL‐Pd): A highly active and recoverable catalyst for Suzuki–Miyaura cross‐coupling reaction in aqueous medium

In this work, an easily obtained procedure was successfully implemented to prepare novel palladium nanoparticles decorated on triethanolammonium chloride ionic liquid‐functionalized TiO₂ nanoparticles [TiO₂/IL‐Pd]. Different methods were carried out for characterizations of the synthesized nanocatalyst (HR‐TEM, XPS, XRD, FE‐SEM, EDX, FT‐IR and ICP). TiO₂/IL‐Pd indicated good catalytic activity for the Suzuki–Miyaura cross‐coupling reaction of arylboronic acid with different aryl halides in aqueous media at ambient temperature. The recycled catalyst was investigated with ICP to amount of Pd leaching after 6 times that had diminished slightly, Thus, was confirmed that the nanocatalyst has a good sustainability for C–C Suzuki–Miyaura coupling reaction. The catalyst can be conveniently separated by filtration of the reaction mixture and reused for 6 times without significant loss of its activity. It supplies an environmentally benign alternative path to the existing protocols for the Suzuki–Miyaura reaction.