Understanding photochemical pathways of laser-induced metal ion reduction through byproduct analysis.

Laser-induced reduction of metal ions is attracting increasing attention as a sustainable route to ligand-free metal nanoparticles. In this work, we investigate the photochemical reactions involved in reduction of Ag+ and [AuCl4]- upon interaction with lasers with nanosecond and femtosecond pulse duration, using strong-field ionization mass spectrometry and spectroscopic assays to identify stable molecular byproducts. Whereas Ag+ in aqueous isopropyl alcohol (IPA) is reduced through plasma-mediated mechanisms upon femtosecond laser excitation, low-fluence nanosecond laser excitation induces electron transfer from IPA to Ag+. Both nanosecond and femtosecond laser excitation of aqueous [AuCl4]- produce reactive chlorine species by Au-Cl bond homolysis. Formation of numerous volatile products by IPA decomposition during both femtosecond and nanosecond laser excitation of [AuCl4]- is attributed to enhanced optical breakdown by the Au nanoparticle products of [AuCl4]- reduction. These mechanistic insights can inform the design of laser synthesis procedures to improve control over metal nanoparticle properties and enhance byproduct yields.

Facile Microwave Synthesis of Hierarchical Porous Copper Oxide and Its Catalytic Activity and Kinetics for Carbon Monoxide Oxidation.

The synthesis of copper oxide (CuO)-based nanomaterials has received a tremendous deal of interest in recent years. Particularly, the design and development of novel CuO structures with improved physical and chemical properties have attracted immense attention, especially for catalysis applications. We report on a rational, rapid, and surfactant-free microwave synthesis (MWS) of hierarchical porous copper oxide (HP-CuO) with a three-dimensional (3D) sponge-like topology using an MWS reactor. The activity of the microwave (MW)-synthesized HP-CuO catalysts for carbon monoxide (CO) oxidation was studied and compared to CuO prepared by the conventional heating method (CHM). Results showed that HP-CuO catalysts prepared by MWS for 10 and 30 min surpassed the CuO catalyst prepared by CHM, exhibiting T 80 of 98 and 115 °C, respectively, as compared to 185 °C of CuO prepared by CHM (T80 is the temperature corresponding to 80% CO conversion). In addition, the MW-synthesized HP-CuO catalysts outperformed the CHM-synthesized CuO, achieving a 100% CO conversion at 150 °C compared to 240 °C in the case of CuO prepared by CHM. Interestingly, the HP-CuO catalyst expressed workable CO conversion kinetics with a reaction rate of c.a.35 µmol s-1 g-1 at 150 °C and apparent activation energy (E a) of 82 kJ mol-1. The HP-CuO catalyst showed excellent cycling and long-term stabilities for CO oxidation up to 4 cycles and 72 h on the stream, respectively. The enhanced catalytic activity and stability of the HP-CuO catalyst appear to result from the unique topological and structural features of HP-CuO, which were revealed by SEM, XRD, Raman, BET, TGA, XPS, and TPR techniques.

Gas-Phase External Solvation of Protonated Benzonitrile by Eight Methanol Molecules.

The gas-phase sequential association of methanol onto protonated benzonitrile (C6H5CNH+) and the proton-bound dimer (C6H5CN)2H+ have been examined experimentally by equilibrium thermochemical measurements and computationally by density functional theory (DFT). The bonding enthalpy (ΔH°) for the association of methanol with protonated benzonitrile (25.2 kcal mol-1) reflects the strong electrostatic interaction provided by the formation of an ionic hydrogen bond in the C6H5CNH+OHCH3 cluster in excellent agreement with a DFT-calculated binding energy of 24.9 kcal mol-1. The sequential bonding enthalpy within the (C6H5CN)H+(OHCH3)n clusters decreases from 25.2 to 10.6 kcal mol-1 for the eighth solvation step (n = 8), which remains more than 25% above the enthalpy of vaporization of liquid methanol (8.4 kcal mol-1). The nonbulk convergence of ΔH°n-1,n with eight solvent molecules is attributed to the external solvation of a benzonitrile molecule by an extended hydrogen bonding network of protonated methanol clusters H+(CH3OH)n. In the external solvation of protonated benzonitrile by methanol, the proton resides on the methanol subcluster and the neutral benzonitrile molecule remains outside and bonded to the surface of the protonated methanol cluster. The bonding enthalpy of methanol to the proton-bound benzonitrile dimer (C6H5CN)H+(NCC6H5) is measured to be 18.0 kcal mol-1, in good agreement with a DFT-calculated value of 17.1 kcal mol-1, which reflects the association of the proton with the lower proton affinity methanol molecule, thus forming a highly stable structure of protonated methanol terminated by two ionic hydrogen bonds to the two benzonitrile molecules. The external solvation of benzonitrile by methanol ices in space allows benzonitrile to remain on the ice grain surface rather than being isolated inside the ice. This could provide accessibility for reactions with incoming ions and molecules or for photochemical processes by UV irradiation, leading to the formation of complex organics on the surface of ice grains.

Water-Assisted Proton Transfer in the Sequential Hydration of Benzonitrile Radical Cation C6H5CN•+(H2O)n: Transition to Hydrated Distonic Cation •C6H4CNH+(H2O)n with n ≥ 4.

The stepwise hydration of the benzonitrile•+ radical cation with one-seven H2O molecules was investigated experimentally and computationally with density functional theory in C6H5CN•+(H2O)n clusters. The stepwise binding energies (ΔHn-1,n°) were determined by equilibrium measurements for C6H5CN•+(H2O) and for •C6H4CNH+(H2O)n with n = 5, 6, and 7 to be 8.8 and 11.3, 11.0, and 10.0 kcal/mol, respectively. The populations of n = 2 and 3 of the C6H5CN•+(H2O)n clusters were observed only in trace abundance due to fast depletion processes leading to the formation of the hydrated distonic cations •C6H4CNH+(H2O)n with n = 4-7. The observed transition occurs between conventional radical cations hydrated on the ring in C6H5CN•+(H2O)n clusters with n = 1-3 and the protonated radical •C6H4CNH+ (distonic ion) formed by a proton transfer to the CN nitrogen and ionic hydrogen bonding to water molecules in •C6H4CNH+(H2O)n clusters with n = 4-7. The measured binding energy of the hydrated ion C6H5CN•+(H2O) (8.8 kcal/mol) is similar to that of the hydrated benzene radical cation (8.5 kcal/mol) that involves a relatively weak CHδ+···O hydrogen bonding interaction. Also, the measured binding energies of the •C6H4CNH+(H2O)n clusters with n = 5-7 are similar to those of the protonated benzonitrile (methanol)n clusters [C6H5CNH+(CH3OH)n, n = 5-7] that involve CNH+···O ionic hydrogen bonds. The proton shift from the para-•C ring carbon to the nitrogen of the benzonitrile radical cation is endothermic without solvent but thermoneutral for n = 1 and exothermic for n = 2-4 in C6H5CN•+(H2O)n clusters to form the distonic •C6H4CN···H+(OH2)n clusters. The distonic clusters •C6H4CN···H+(OH2)n constitute a new class of structures in radical ion/solvent clusters.

Zinc ferrite nanoparticles from industrial waste for Se (IV) elimination from wastewater.

The presence of high concentrations of selenium ions in wastewater is considered an environmental problem. However, the mechanism of selenium ions (Se (IV)) removal by the adsorption process has not been investigated in-depth so far. Also, the recovery and conversion of the industrial waste materials into valuable materials is a vital issue. Therefore, in this study, zinc ferrite nanopowders are economically synthesized from steel-making wastes by co-precipitation method for investigating as adsorbents of selenium species. The produced nanopowders were annealed at 150, 300, 500, and 850 °C for 5 h to scrutinize the impact of annealing temperature on their crystallite size. The compositional, optical, and magnetic features of the nanopowders were defined by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM), UV-Vis. spectrophotometer along with vibrating sample magnetometer (VSM). Optical absorbance spectra were found characteristic due to the electronic structure of Fe3+ (3d5) considering the C3v local symmetry of Fe3+ ions. The prepared nanopowders demonstrated good adsorption capacity toward selenium ions (43.67 mg/g at pH 2.5) from an aqueous medium. Adsorption data were found fitting to Freundlich isotherm model. Thus, ZnFe2O4 can be recommended to effectively eliminate selenium ions from aqueous solutions.

Co-Cu Bimetallic Metal Organic Framework Catalyst Outperforms the Pt/C Benchmark for Oxygen Reduction.

Platinum (Pt)-based-nanomaterials are currently the most successful catalysts for the oxygen reduction reaction (ORR) in electrochemical energy conversion devices such as fuel cells and metal-air batteries. Nonetheless, Pt catalysts have serious drawbacks, including low abundance in nature, sluggish kinetics, and very high costs, which limit their practical applications. Herein, we report the first rationally designed nonprecious Co-Cu bimetallic metal-organic framework (MOF) using a low-temperature hydrothermal method that outperforms the electrocatalytic activity of Pt/C for ORR in alkaline environments. The MOF catalyst surpassed the ORR performance of Pt/C, exhibiting an onset potential of 1.06 V vs RHE, a half-wave potential of 0.95 V vs RHE, and a higher electrochemical stability (ΔE1/2 = 30 mV) after 1000 ORR cycles in 0.1 M NaOH. Additionally, it outperformed Pt/C in terms of power density and cyclability in zinc-air batteries. This outstanding behavior was attributed to the unique electronic synergy of the Co-Cu bimetallic centers in the MOF network, which was revealed by XPS and PDOS.

Efficient removal of heavy metals from polluted water with high selectivity for Hg(ii) and Pb(ii) by a 2-imino-4-thiobiuret chemically modified MIL-125 metal-organic framework.

A highly porous adsorbent based on a metal-organic framework was successfully designed and applied as an innovative adsorbent in the solid phase for the heavy metal removal. MIL-125 was densely decorated by 2-imino-4-thiobiuret functional groups, which generated a green, rapid, and efficacious adsorbent for the uptake of Hg(ii) and Pb(ii) from aqueous solutions. ITB-MIL-125 showed a high adsorption affinity toward mercury(ii) ions of 946.0 mg g-1 due to covalent bond formation with accessible sulfur-based functionality. Different factors were studied, such as the initial concentration, pH, contact time, and competitive ions, under same circumstances at the room temperature. Moreover, the experimental adsorption data were in excellent agreement with the Langmuir adsorption isotherm and pseudo-second order kinetics. At a high concentration of 100 ppm mixture of six metals, ITB-MIL-125 exhibited a high adsorption capacity, reaching more than 82% of Hg(ii) compared to 62%, 30%, 2%, 1.9%, and 1.6% for Pb(ii), Cu(ii), Cd(ii), Ni(ii), and Zn(ii), respectively.

Metal-free functionalized carbonized cotton for efficient solar steam generation and wastewater treatment.

Water desalination via solar steam generation is one of the most important technologies to address the increasingly pressing global water scarcity. Materials for solar photothermal energy conversion are highly sought after for their cost savings, environmental friendliness and broad utility in many applications including domestic water heating and solar-driven desalination. Herein, we report the successful development of metal-free, low weight and cost effective functionalized carbonized cotton (CC) fibers for efficient solar water desalination and wastewater treatment. The CC fibers with nearly full solar spectrum absorption, efficient photo-thermal conversion and low-cost could provide excellent alternatives to the high-cost plasmonic-based materials for solar water desalination. We also report on a novel and simple device to mitigate the issues associated with conductive heat loss by utilizing the economically viable carbonized cotton materials as an irradiation surface placed on a low-density polyethylene foam that floats on the surface of seawater. The CC solar steam generation device exhibits average water evaporation rates of 0.9, 6.4 and 10.9 kg m-2 h-1 with impressive solar-to-vapor efficiencies of 59.2, 88.7 and 94.9% under 1, 5 and 8 sun illumination, respectively. Moreover, the device displays excellent durability showing stable evaporation rates over 10 steam generation cycles under 5 sun of solar intensity. Furthermore, the applicability of the CC device for the removal of organic dyes from contaminated water through solar steam generation is also demonstrated. The low-cost, simple design, high solar thermal evaporation efficiency, excellent stability and long-term durability make this CC device a perfect candidate for applications in seawater desalination and wastewater treatment by solar steam generation.

Highly fluorescent hematoporphyrin modified graphene oxide for selective detection of copper ions in aqueous solutions.

Here, a highly sensitive and selective copper ion (Cu2+) fluorescence sensor is reported. The Hematoporphyrin functionalized Graphene Oxide (HP-GO) fluorescence sensor were synthesized via esterification reaction between Graphene Oxide and Hematoporphyrin (HP). The HP-GO sensor was fully characterized by Fourier Transform Infrared Spectroscopy (FTIR), X-ray diffraction (XRD), Scanning Electrom Microscopy (SEM), UV-Vis spectroscopy, Transmission Electron Microscopy (TEM), Fluor meter spectroscopy, X-Ray photoelectron spectroscopy(XPS), and Raman spectroscopy measurements. The HP-GO sensor advertised two linear regions over the range of 0-1.18 × 103 nM and 3.93 × 103 to 47.27 nM of copper (II) with detection limit of 54 nM in the aqueous solution. The selectivity of HP-GO for Cu2+ is much higher than that of other metal ions due to the presence of aza macrocyclic ring on the surface of HP-GO which has a high binding affinity with Cu2+. Additionally, the HP-GO shows wide pH viable range (pH 6-10). The effect of other metal ions on the fluorescence intensity of the HP-GO was also studied and other metal ions show a low interference response in the detection of Cu2+. HP-GO sensor manifests advantages of high reproducibility (The quenched fluorescence of HP/GO-Cu can be recovered by EDTA), attractive long term fluorescence stability (>21 days) in water, also remarkable selectivity regarding number of metal ions (Na+, K+, Ca2+, Fe3+, Fe2+, Al3+, Pb2+, Mn2+, Mg2+, Co2+, Ni2+, Cr6+, Cd2+, Hg2+, and Zn2+), low toxicity and can detect Cu2+ in real water samples which acquire well for its promising in environmental applications.

Heterogeneous catalysis by ultra-small bimetallic nanoparticles surpassing homogeneous catalysis for carbon-carbon bond forming reactions.

Palladium catalyzed cross-coupling reactions represent a significant advancement in contemporary organic synthesis as these reactions are of strategic importance in the area of pharmaceutical drug discovery and development. Supported palladium-based catalysts are highly sought-after in carbon-carbon bond forming catalytic processes to ensure catalyst recovery and reuse while preventing product contamination. This paper reports the development of heterogeneous Pd-based bimetallic catalysts supported on fumed silica that have high activity and selectivity matching those of homogeneous catalysts, eliminating the catalyst's leaching and sintering and allowing efficient recycling of the catalysts. Palladium and base metal (Cu, Ni or Co) contents of less than 1.0 wt% loading are deposited on a mesoporous fumed silica support (surface area SABET = 350 m2 g-1) using strong electrostatic adsorption (SEA) yielding homogeneously alloyed nanoparticles with an average size of 1.3 nm. All bimetallic catalysts were found to be highly active toward Suzuki cross-coupling (SCC) reactions with superior activity and stability for the CuPd/SiO2 catalyst. A low CuPd/SiO2 loading (Pd: 0.3 mol%) completes the conversion of bromobenzene and phenylboronic acid to biphenyl in 30 minutes under ambient conditions in water/ethanol solvent. In contrast, monometallic Pd/SiO2 (Pd: 0.3 mol%) completes the same reaction in three hours under the same conditions. The combination of Pd with the base metals helps in retaining the Pd0 status by charge donation from the base metals to Pd, thus lowering the activation energy of the aryl halide oxidative addition step. Along with its exceptional activity, CuPd/SiO2 exhibits excellent recycling performance with a turnover frequency (TOF) of 280 000 h-1 under microwave reaction conditions at 60 °C. Our study demonstrates that SEA is an excellent synthetic strategy for depositing ultra-small Pd-based bimetallic nanoparticles on porous silica for SCC. This avenue not only provides highly active and sintering-resistant catalysts but also significantly lowers Pd contents in the catalysts without compromising catalytic activity, making the catalysts very practical for large-scale applications.

Laser-assisted synthesis of gold-graphene oxide nanocomposites: effect of pulse duration.

Laser photoreduction of metal ions onto graphene oxide (GO) is a facile, environmentally friendly method to produce functional metal-GO nanocomposites for a variety of applications. This work compares Au-GO nanocomposites prepared by photoreduction of [AuCl4]- in aqueous GO solution using laser pulses of nanosecond (ns) and femtosecond (fs) duration. The presence of GO significantly accelerates the [AuCl4]- photoreduction rate, with a more pronounced effect using ns laser pulses. This difference is rationalized in terms of the stronger interaction of the 532 nm laser wavelength and long pulse duration with the GO. Both the ns and fs lasers produce significant yields of sub-4 nm Au nanoparticles attached to GO, albeit with different size distributions: a broad 5.8 ± 1.9 nm distribution for the ns laser and two distinct distributions of 3.5 ± 0.8 and 10.1 ± 1.4 nm for the fs laser. Despite these differences, both Au-GO nanocomposites had the same high catalytic activity towards p-nitrophenol reduction as compared to unsupported 4-5 nm Au nanoparticles. These results point to the key role of GO photoexcitation in catalyzing metal ion reduction and indicate that both ns and fs lasers are suitable for producing functional metal-GO nanocomposites.

Green Synthesis of Oxide-Supported Pd Nanocatalysts by Laser Methods for Room-Temperature Carbon-Carbon Cross-Coupling Reactions.

This work reports the design and development of a new class of highly active Pd nanocatalysts supported on substoichiometric oxides. These novel catalysts are generated by green laser synthesis methods to generate high-surface-area substoichiometric oxide nanoparticles followed by photoreduction in aqueous solutions to deposit highly active Pd nanocatalysts within the surface defects of the oxides. The laser methods eliminate the use of toxic chemicals, including hazardous solvents and chemical reducing agents, and allow efficient reduction of the Pd ions in aqueous solutions aided by the photogenerated electrons from the semiconductor support. The Pd catalysts incorporated within these oxides exhibit high activity for carbon-carbon bond-forming reactions. The Pd/TiO2 catalyst with 0.3 mol % Pd achieves 100% conversion in the reaction between bromobenzene and benzeneboronic acid to the biphenyl product within 240 minutes at room temperature without any external heating. With a catalyst loading of 0.3 mol % Pd in the microwave-assisted reaction between bromobenzene and benzeneboronic acid at 60 °C, 92 and 83% conversions to the biphenyl product are achieved within 5 min of reaction time using the Pd/TiO2 and Pd/ZnO catalysts, respectively. The results demonstrate a remarkable catalytic activity of the substoichiometric oxide-supported Pd catalysts with turnover frequencies (TOF, h-1) of 24 000, 10 000, and 3200 achieved under mirowave-assisted reactions at 60 °C for the 0.03 mol% Pd of the Pd/TiO2, Pd/ZnO, and Pd/ZrO2 catalysts, respectively. The high activity and good reusability of these nanocatalysts are attributed to the optimum catalyst-support interaction between the small Pd nanoparticles and the surface defects of the substoichiometric oxide support prepared by the laser vaporization-controlled condensation method.

Melamine-based functionalized graphene oxide and zirconium phosphate for high performance removal of mercury and lead ions from water.

Heavy metal ions are highly toxic and widely spread as environmental pollutants. This work reports the development of two novel chelating adsorbents, based on the chemical modifications of graphene oxide and zirconium phosphate by functionalization with melamine-based chelating ligands for the effective and selective extraction of Hg(ii) and Pb(ii) from contaminated water sources. The first adsorbent melamine, thiourea-partially reduced graphene oxide (MT-PRGO) combines the heavier donor atom sulfur with the amine and triazine nitrogen's functional groups attached to the partially reduced GO nanosheets to effectively capture Hg(ii) ions from water. The MT-PRGO adsorbent shows high efficiency for the extraction of Hg(ii) with a capacity of 651 mg g-1 and very fast kinetics resulting in a 100% removal of Hg(ii) from 500 ppb and 50 ppm concentrations in 15 second and 30 min, respectively. The second adsorbent, melamine zirconium phosphate (M-ZrP), is designed to combine the amine and triazine nitrogen's functional groups of melamine with the hydroxyl active sites of zirconium phosphate to effectively capture Pb(ii) ions from water. The M-ZrP adsorbent shows exceptionally high adsorption affinity for Pb(ii) with a capacity of 681 mg g-1 and 1000 mg g-1 using an adsorbent dose of 1 g L-1 and 2 g L-1, respectively. The high adsorption capacity is also coupled with fast kinetics where the equilibrium time required for the 100% removal of Pb(ii) from 1 ppm, 100 ppm and 1000 ppm concentrations is 40 seconds, 5 min and 30 min, respectively using an adsorbent dose of 1 g L-1. In a mixture of six heavy metal ions at a concentration of 10 ppm, the removal efficiency is 100% for Pb(ii), 99% for Hg(ii), Cd(ii) and Zn(ii), 94% for Cu(ii), and 90% for Ni(ii) while at a higher concentration of 250 ppm the removal efficiency for Pb(ii) is 95% compared to 23% for Hg(ii) and less than 10% for the other ions. Because of the fast adsorption kinetics, high removal capacity, excellent regeneration, stability and reusability, the MT-PRGO and M-ZrP are proposed as top performing remediation adsorbents for the solid phase extraction of Hg(ii) and Pb(ii), respectively from contaminated water.

Multifunctional Binding Sites on Nitrogen-Doped Carboxylated Porous Carbon for Highly Efficient Adsorption of Pb(II), Hg(II), and Cr(VI) Ions.

Heavy metal ions represent one of the most toxic and environmentally harmful pollutants of water sources. This work reports the development of a novel chelating nitrogen-doped carboxylated porous carbon (ND-CPC) adsorbent for the effective removal of the heavy metal ions Pb(II), Hg(II), and Cr(VI) from contaminated and polluted water sources. The ND-CPC adsorbent is designed to combine four different types of nitrogen functional groups (graphitic, pyrrolic, pyridinic, and pyridine oxide) with the carboxylic acid functional groups within a high surface area of 1135 ± 20 m2/g of the porous carbon structure. The ND-CPC adsorbent shows exceptionally high adsorption affinity for Pb(II) with a capacity of 721 ± 14 mg/g in addition to high uptake values of 257 ± 5 and 104 ± 2 mg/g for Hg(II) and Cr(VI), respectively. The high adsorption capacity is also coupled with fast kinetics where the equilibrium time required for the 100% removal of Pb(II) from 50 ppb and 10 ppm concentrations is 30 s and 60 min, respectively. Even with the very high concentration of 700 ppm, 74% uptake of Pb(II) is achieved within 90 min. Removal efficiencies of 100% of Pb(II), 96% of Hg(II), 91% of Cu(II), 82% of Zn(II), 25% of Cd(II), and 13% of Ni(II) are achieved from a solution containing 10 ppm concentrations of these ions, thus demonstrating excellent selectivity for Pb(II), Hg(II), and Cu(II) ions. Regeneration of the ND-CPC adsorbent shows excellent desorption efficiencies of 99 and 95% for Pb(II) and Cr(VI) ions, respectively. Because of the fast adsorption kinetics, high removal capacity and excellent regeneration, stability, and reusability, the ND-CPC is proposed as a highly efficient remediation adsorbent for the solid-phase removal of Pb(II), Hg(II), and Cr(VI) from contaminated water.

Growth Mechanism of Sea Urchin ZnO Nanostructures in Aqueous Solutions and Their Photocatalytic Activity for the Degradation of Organic Dyes.

This work reports the development of a fast and simple route for the synthesis of ZnO sea urchin (SU) nanostructures by the formation and assembly of ZnO nanorods under favorable growth conditions in an aqueous solution. The thermal treatment of a basic zinc acetate solution in ethanol results in the formation of aggregated seed clusters consisting of small ZnO nanorods, which were then grown in a precursor solution containing Zn(NO3)2·6H2O and hexamethylenetetramine to assemble the SU structures from the anisotropic ZnO nanorods on the surface of the seed clusters. Each ZnO nanoparticle in the aggregated seed clusters grew sequentially into a ZnO nanorod, and the nanorods were concentric to the core of the clusters yielding the unique SU-like shape. In the presence of a capping agent such as cetyl trimethyl ammonium bromide (CTAB), the aggregated seed clusters were not formed, and the growth of the CTAB-capped ZnO nanorods resulted in separated rods with average aspect ratios of ∼10. The SU ZnO nanostructures exhibit a hexagonal wurtzite crystal structure and higher specific surface area (26.9 m2/g) than the CTAB-capped nanorods (17.7 m2/g). The SU ZnO nanostructures show superior photocatalytic efficiency for the degradation of three common organic dyes compared to the ZnO nanorods. The removal efficiencies of indigo carmine, methylene blue, and rhodamine B by the SU nanostructures were 99, 86, and 96%, respectively, after 1 h of UV irradiation. Therefore, the ZnO SU structures have the potential to be a versatile photocatalyst for the photodegradation of organic dyes in industrial wastewater.

Structures of benzonitrile dimer radical cation and the protonated dimer: Observation of hydronium ion core solvated by benzonitrile molecules.

The recent discovery of benzonitrile (C6H5CN), one of the simplest nitrogen-bearing polar aromatic molecules, in the interstellar medium motivates structural characterization of the benzonitrile-containing molecular ions as potential precursors for nitrogen-containing complex organics in space. Herein, we present mass-selected ion mobility measurements combined with density functional theory (DFT) calculations to reveal, for the first time, the structures of the benzonitrile dimer radical cation, the protonated dimer, and the protonated hydrated small clusters in the gas phase. The measured collision cross sections of the investigated ions in helium are in excellent agreement with the calculated values of the lowest energy DFT structures. Unlike the dimer radical cations of nonpolar aromatic molecules which adopt parallel sandwich configurations, the (C6H5CN)2 ·+ displays a symmetrically planar geometry with a double hydrogen bond formed between the nitrogen and hydrogen atoms. The protonated dimer has the structure of a proton-bound dimer (C6H5CNH+NCC6H5) where the bridging proton connects the nitrogen atoms in the two benzonitrile molecules resulting in a calculated collision cross section of 101.1 Å2 in excellent agreement with the measured value of 103.3 Å2. The structure of the hydrated protonated trimer consists of a hydronium ion core solvated by three benzonitrile molecules. By locating the proton on the lower proton affinity water molecule, the resulting hydronium ion can be fully solvated by forming three ionic hydrogen bonds with the benzonitrile molecules. These unique structural motifs could be useful for the molecular design and recognition involving charged aromatic systems and also for the search of nitrogen-containing complex organics in space.

Ionic Hydrogen and Halogen Bonding in the Gas Phase Association of Acetonitrile and Acetone with Halogenated Benzene Cations.

We report on the gas phase association of the small polar and aprotic solvent molecules acetonitrile (CH3CN) and acetone (CH3COCH3) with the halogenated benzene radical cations (C6H5X•+, X = F, Cl, Br, and I) using the mass-selected ion mobility technique and density functional theory calculations. The association energies (-Δ H°) of CH3CN (CH3COCH3) with C6H5F•+ and C6H5I•+ are similar [13.0 (13.3) and 13.2 (14.1) kcal/mol, respectively] but higher than those of CH3CN (CH3COCH3) with C6H5Cl•+ and C6H5Br•+ [10.5 (11.5) and 10.9 (10.6) kcal/mol, respectively]. However, the electrostatic potentials of the lowest energy structures of C6H5Br•+(CH3CN) and C6H5Br•+(CH3COCH3) or C6H5I•+(CH3CN) and C6H5I•+(CH3COCH3) complexes clearly show the formation of the ionic halogen bonds (IXBs) C-Brδ+- -NCCH3 and C-Brδ+- -OC(CH3)2 or C-Iδ+- -NCCH3 and C-Iδ+- -OC(CH3)2 driven by positively charged σ-holes on the external sides of the C-Br and C-I bond axes of the bromobenzene and iodobenzene radical cations, respectively. For the C6H5F•+(CH3CN) complex, the dominant interaction involves a T-shaped structure between the N atom of CH3CN and the C atom of the C-F bond of C6H5F•+. The structure of the C6H5Cl•+(CH3CN) complex shows the formation of unconventional ionic hydrogen bonds (uIHBs) between the N atom of CH3CN and the C-H bonds of the C6H5Cl•+ cation. Similar results are obtained for the association of acetone with the halogenated benzene radical cations. The formation of IXBs of the iodobenzene cation with acetonitrile or acetone involves a significant entropy loss (-Δ S° = 25-27 cal /(mol K)) resulting from the formation of more ordered and highly directional structures between the nitrogen or oxygen lone pair of electrons of acetonitrile or acetone, respectively, and the electropositive region around the iodine atom of the iodobenzene cation. In comparison, for the association of acetonitrile or acetone with the fluorobenzene, chlorobenzene, and bromobenzene cations, -Δ S° = 16-23 cal/(mol K), consistent with the formation of less ordered structures and loose interactions. The lowest energy structures of the C6H5Br•+(CH3COCH3)2 and C6H5I•+(CH3COCH3)2 clusters show a novel combination of ionic halogen bonding and hydrogen bonding where the oxygen atom of one acetone molecule forms the halogen bond while the oxygen atom of the second acetone molecule becomes the hydrogen acceptor from the methyl group of the first acetone molecule.

Nucleation and growth of gold nanoparticles initiated by nanosecond and femtosecond laser irradiation of aqueous [AuCl4].

Irradiation of aqueous [AuCl4]- with 532 nm nanosecond (ns) laser pulses produces monodisperse (PDI = 0.04) 5 nm Au nanoparticles (AuNPs) without any additives or capping agents via a plasmon-enhanced photothermal autocatalytic mechanism. Compared with 800 nm femtosecond (fs) laser pulses, the AuNP growth kinetics under ns laser irradiation follow the same autocatalytic rate law, but with a significantly lower sensitivity to laser pulse energy. The results are explained using a simple model for simulating heat transfer in liquid water and at the interface with AuNPs. While the extent of water superheating with the ns laser is smaller compared to the fs laser, its significantly longer duration can provide sufficient energy to dissociate a small fraction of the [AuCl4]- present, resulting in the formation of AuNPs by coalescence of the resulting Au atoms. Irradiation of initially formed AuNPs at 532 nm results in plasmon-enhanced superheating of water, which greatly accelerates the rate of thermal dissociation of [AuCl4]- and accounts for the observed autocatalytic kinetics. The plasmon-enhanced heating under ns laser irradiation fragments the AuNPs and results in nearly uniform 5 nm particles, while the lack of particles' heating under fs laser irradiation results in the growth of the particles as large as 40 nm.

Plasmonic chemically modified cotton nanocomposite fibers for efficient solar water desalination and wastewater treatment.

Water desalination and wastewater treatment via solar photothermal energy conversion are among the most important technologies to address the increasing pressing global water scarcity. Solar energy is the cleanest, most abundant, renewable natural resource available. Herein, we report the development of highly efficient, flexible, low weight, and cost effective Plasmonic Functionalized Cotton (PFC) nanocomposite materials for solar steam generation through the efficient evaporation of surface water pools. The PFC nanocomposites contain metallic nanoparticles that exhibit strong solar absorption followed by non-radiative relaxation causing the absorbed energy to be converted into heat for efficient water evaporation. The chemically modified cotton leads to a partial hydrophobic surface that allows the material to float on the water's surface and provide excellent thermal insulation properties in addition to facile and scalable synthesis. The PFC nanocomposites containing Au and Ag nanoparticles are demonstrated to be among the most efficient solar thermal converters reported to date for solar water desalination. The Au/Ag-PFC fibers exhibit average water evaporation rates of 1.4 and 11.3 kg m-2 h-1 with superb solar thermal efficiencies of up to 86.3% and 94.3% under 1 and 8 sun illumination, respectively. Furthermore, the Au/Ag-PFC fibers display stable evaporation rates over more than 10 repeated evaporation cycles without any performance decline under acidic solution at pH 2 or basic solution at pH 10. The successful application of the Au/Ag-PFC fibers for the removal of organic dyes from contaminated water through the solar steam generation is also demonstrated. The high solar thermal evaporation efficiency, excellent stability and long-time durability make the PFC nanocomposites excellent candidates for applications in seawater desalination and wastewater treatment by solar-steam generation.

Tailoring the reducibility and catalytic activity of CuO nanoparticles for low temperature CO oxidation.

Copper oxide (CuO) nanoparticles have received considerable interest as active and inexpensive catalysts for various gas-solid reactions. The CuO reducibility and surface reactivity are of crucial importance for the high catalytic activity. Herein, we demonstrate that the reducibility and stability of CuO nanoparticles can be controlled and tailored for the high catalytic activity of CO oxidation. The synthesized CuO nanoparticles possessed enhanced reducibility in CO atmosphere at lower reduction temperature of 126 °C compared to 284 °C for that of reference CuO particles. Moreover, the CuO catalysts with tailored reducibility demonstrated a reaction rate of 35 µmol s-1 g-1 and an apparent activation energy of 75 kJ mol-1. Furthermore, the tailored catalysts exhibited excellent long-term stability for CO oxidation for up to 48 h on stream. These readily-reducible CuO nanoparticles could serve as efficient, inexpensive and durable catalysts for CO oxidation at low temperatures.