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The authors report a simulation study of the interaction between gold nanoparticles stabilized with both linear and branched alkane chains in supercritical ethane. In agreement with experimental and previous theoretical work, the authors find that increasing solvent density and making ligands more branched make the nanoparticle interaction more repulsive. These findings are analyzed in terms of the extent of the chain interdigitation and chain-solvent interaction energy. [ABSTRACT FROM AUTHOR]

We present a density-functional theory study of nanoparticle interactions in a concentrated polymer solution. The polymers are modeled as freely jointed tangent chains; all nonbonded interactions between polymer segments and nanoparticles are described by Lennard-Jones potentials. We test several recently proposed methods of treating attractive interactions within the density-functional theory framework by comparing theoretical results with recent simulation data. We find that the simple van der Waals approach provides the most accurate results for the polymer-mediated potential of mean force between two dilute nanoparticles. We employ this approach to study nanoparticle interactions as a function of nanoparticle-segment interaction strength and polymer solution density and temperature. [ABSTRACT FROM AUTHOR]

This work reports, for the first time, Co-Mo-B as a bifunctional electrocatalyst, prepared by a facile reduction method. The optimized catalyst, Co-3Mo-B shows excellent HER performance and achieves 10 mA/cm 2 at mere 96 and 66 mV (vs RHE) in pH 7 and pH 14, respectively with good stability (40 hours) and reusability (5000 cycles). Co-3Mo-B catalyst is found to be made up of nano-sized crystalline domains, separated by grain boundaries containing active under-co-ordinated sites. From morphological, physico-chemical and electrochemical analyses, it was found that Co-3Mo-B nanoparticles (NPs) exhibit small size (∼18 nm) with high specific and electrochemical surface area. Under alkaline conditions, Co-3Mo-B can also produce oxygen at meagre overpotentials (10 mA/cm 2 at 320 mV) with favourable stability. Bifunctional property is demonstrated by employing Co-3Mo-B in a 2-electrode alkaline cell to execute overall water electrolysis, producing 10 mA/cm 2 at just 1.69 V, which is maintained for at least 25 hours of operation. The nature of the catalyst to form Co oxide/hydroxide species on the surface is responsible for good OER performance. The significant activity of Co-3Mo-B makes it the best metal boride bifunctional electrocatalyst reported so far. [ABSTRACT FROM AUTHOR]

Ruthenium nanoparticles (NPs) supported over carbon thin films (Ru/C thin films) catalysts were synthesized by pulsed laser deposition and used as catalysts for hydrolysis of ammonia borane (AB). Highly irregular and porous carbon films with high surface area were deposited by varying Ar gas pressures during the deposition. By taking the advantage of phase explosion phenomena, occurring at high laser fluence, the surface of the carbon films were decorated with crystalline Ru NPs with size below ∼10 nm. Ru/C thin film catalyst produced H 2 with 6 times higher H 2 generation rate as compared to unsupported Ru NPs assembled film, and with a high turnover frequency value of 70.5 mol H 2 mol −1 Ru min −1 . A combination of morphological features and high content of sp 2 bonded C atoms provides good dispersion of Ru NPs over a large surface area. Both these features contribute in generating large number of active sites leading to the increase in catalytic efficiency. A possibility of using the present form of catalyst as an ON/OFF switch for H 2 production was also tested. Although the catalytic activity decreased with the number of hydrolysis cycles, Ru/C thin film catalyst was able to generate the expected amount of H 2 gas in each cycle when it was reused several times. The observed low activation energy (∼28 kJ mol −1 ) and high H 2 generation rate (15.5 L H 2 min −1 g −1 of Ru) by hydrolysis of AB suggest that Ru/C thin film catalyst is highly efficient. [ABSTRACT FROM AUTHOR]

Abstract: Nanoparticles (NPs) catalysts are under intense investigation in the catalysis community due to their exceptional activity and selective nature in catalytic processes as compared to the corresponding bulk counterpart, especially because of their large surface-to-volume atomic ratio, size- and shape-dependent properties, and high concentration of low-coordinated active surface sites. However, there is no general strategy to synthesize NPs of various materials with narrow size distribution, tailored properties, and desired morphologies. The development of a technique able to prepare NPs is thus a goal of great importance to avoid present trial and error approaches. Here we report on selected examples where pulsed laser deposition (PLD) technique greatly contributes toward NPs synthesis. Co NPs embedded in B matrix films have been synthesized by PLD technique by taking advantage of the phase explosion process of superheated liquid where a mixture of vapor and liquid droplets leave the irradiated target surface and get deposited on the substrate. The deposited NPs exhibit catalytic properties comparable to that of precious metals in hydrogen production by hydrolysis of NaBH4 and NH3BH3. These NPs, when supported on rough carbon film prepared by PLD, show about 30% increase in catalytic activity for H2 production as compared to unsupported NPs. Co3O4 NPs assembled coating has been produced by reactive PLD in oxygen atmosphere at various substrate temperatures from room temperature to 250°C. It was proved that the Co3O4 NPs can be obtained in a single step at low temperatures with mixed disordered-nanocrystalline phase that is a relevant feature for catalysis. The Co3O4 NPs assembled thin coating, employed in degradation of methylene blue solution, in water, via photo Fenton reaction in presence of H2O2, exhibits significantly higher activity as compared to the corresponding homogeneous catalyst. [Copyright &y& Elsevier]

Highlights: [•] Co-B catalyst particles were supported over three type of mesoporous silica of different pore sizes. [•] Co-B supported over SBA-15 showed highest H2 generation rate for hydrolysis of AB. [•] Confinement of Co-B within the pores creates smaller NPs (6nm) with uniform size distribution. [•] Thicker pore walls of SBA-15 avoid agglomeration of Co-B NPs at elevated temperature (873K). [Copyright &y& Elsevier]

Abstract: Zinc oxide (ZnO) nanoparticles with average size of ∼7.5nm were synthesized to investigate their interaction with bovine serum albumin (BSA) at different temperatures. Fluorescence quenching, synchronous and polarization spectroscopy along with UV–vis absorption, circular dichroism and resonance light scattering spectroscopy techniques were used to establish the interaction mechanism between ZnO and BSA. The obtained results confirmed that the ZnO nanoparticles (NPs) quench the fluorophore of BSA by forming ground state complex in the solution. The fluorescence quenching data was also used to determine binding sites and binding constants at different temperatures. The calculated thermodynamic parameters (ΔG°, ΔH°, and ΔS°) suggest that the binding process occurs spontaneously by involving hydrogen bond and van der Waals interactions. The synchronous fluorescence spectra reveal that the microenvironment close to both the tyrosine and tryptophan residues of BSA is perturbed and that the hydrophobicity of both the residues is increased in the presence of ZnO NPs. Resonance light scattering, circular dichroism, and fluorescence polarization spectra suggest the formation of BSA–ZnO complex and conformational changes in BSA. The calculated distance between the BSA and ZnO NPs suggests that the energy transfer from excited state of BSA to ZnO NPs occurs with high efficiency. [Copyright &y& Elsevier]

Abstract: Catalyst in the form of Co-B nanoparticles supported on mesoporous silica particles (MSP) was synthesized by chemical impregnation–reduction method. This catalyst powder was used for hydrogen production by hydrolysis of Ammonia Borane (AB) and was compared with Co-B catalyst supported on non-porous silica particles (NSP) and unsupported Co-B powder. It was found that the MSPs synthesized in the present studies have average pore size of about 3.1nm which were efficient to anchor the Co-B particles with average size of ~8nm on the surface to provide high active surface area and improved degree of dispersion. MSP-supported Co-B catalyst was able to produce expected amount of H2 gas from hydrolysis of AB with significantly superior generation rate, about 3 times higher than that produced by unsupported and NSP-supported Co-B catalyst. Availability of a large number of under-coordinated Co active atoms owing to the size of nanoparticles, better dispersion, high surface area and good stability against agglomeration during the reaction are the main features acquired by the Co-B nanoparticles supported on MSP that exhibit high catalytic efficiency. [Copyright &y& Elsevier]

Abstract: Cobalt oxide (Co3O4) nanoparticles (NPs) assembled coating have been prepared by reactive pulsed laser deposition of Co, in O2 atmosphere, on Si or glass substrate ranging from room temperature to 250°C. The NPs, having narrow size distribution with average values of around 25–50nm, were characterized by Raman, X-ray diffraction, X-ray photoelectron spectroscopy, and scanning electron microscopy. The Co3O4 NPs synthesized at 150°C comprise a mixed amorphous–nanocrystalline phase (that is unique property for catalysis) while complete crystallization of Co3O4 occurs at 250°C with formation of spinel structure. Photocatalytic properties of Co3O4 NPs assembled coating for degradation of methylene blue solution under visible light irradiation are reported. The effect of H2O2 concentration and effect of pH variation on dye degradation rate has been reported. The reusability of the Co3O4 NPs assembled thin coating catalyst was further evaluated in several recycling runs. The activity of heterogeneous Co3O4 NPs assembled thin coating catalyst was compared with homogenous catalyst producing Co+2 ions in methylene blue solution. [Copyright &y& Elsevier]

Abstract: Thin films of Carbon-supported Co–B nanoparticles were synthesized by using Pulsed Laser Deposition (PLD) and used as catalysts in the hydrolysis of Ammonia Borane (AB) to produce molecular hydrogen. Amorphous Co–B-based catalyst powders, produced by chemical reduction of cobalt salts, were used as target material for nanoparticles-assembled Co–B film catalysts preparation through PLD. Various Ar pressures (10–50 Pa) were used during deposition of carbon films to obtain extremely irregular and porous carbon support with high surface area prior to Co–B film deposition. Surface morphology of the catalyst films was studied using Scanning Electron Microscopy, while structural characterization was carried out using X-Ray diffraction. The hydrogen generation rate attained by carbon-supported Co–B catalyst film is significantly higher as compared to unsupported Co–B film and conventional Co–B powder. Almost complete conversion (95%) of AB was obtained at room temperature by using present film catalyst. Morphological analysis showed that the Co–B nanoparticles produced after the laser ablation process act as active catalytic centers for hydrolysis while the carbon support provides high initial surface area for the Co–B nanoparticles with better dispersion and tolerance against aggregation. The efficient nature of our carbon-supported Co–B film is well supported by the obtained very low activation energy (∼29 kJ (mol)−1) and exceptionally high H2 generation rate (13.5 L H2 min−1 (g of Co)−1) by the hydrolysis of AB. [Copyright &y& Elsevier]

Abstract: Co-B nanoparticles supported over carbon films were synthesized by using pulsed laser deposition (PLD) and used as catalysts in the hydrolysis of sodium borohydride (NaBH4) to produce molecular hydrogen. Amorphous Co-B-based catalyst powders, produced by chemical reduction of cobalt salts, were used as target material for nanoparticles-assembled Co-B film catalysts preparation through PLD. Various Ar pressures (10–50Pa) were used during deposition of carbon films to obtain extremely irregular and porous-carbon support with high surface area prior to Co-B film deposition. Surface morphology of the catalyst films was studied using scanning and transmission electron microscopy, while structural characterizations were carried out using X-ray diffraction. The hydrogen generation rate attained by carbon-supported Co-B catalyst film is significantly higher as compared to unsupported Co-B film and to conventional Co-B powder. Morphological analysis along with NaBH4 hydrolysis tests showed that the Co-B nanoparticles produced with PLD act as active catalytic centers for hydrolysis while the carbon support provides high initial surface area for the Co-B nanoparticles with better dispersion and tolerance against aggregation. The hydrogen generation rate obtained by the present catalyst film was also investigated as a function of Co-B loading, carbon morphology, and solution temperature. The high performance of our carbon-supported Co-B film is well supported by the obtained very low activation energy (∼31kJ (mol)−1) and exceptionally high H2 generation rate (8.1LH2 min−1 (gofcatalyst)−1) in the hydrolysis of NaBH4. [Copyright &y& Elsevier]

Abstract: Co–P–B catalyst thin films have been synthesized on Ni-foam and glass substrate by using electroless deposition (ED) and pulsed laser deposition (PLD) respectively. The efficiency of these catalyst films was tested by catalytic hydrolysis of NaBH4 for H2 generation. While the chemically produced Co–P–B film on Ni-foam shows similar activity as that of their corresponding powder, the Co–P–B film deposited by PLD exhibits much superior H2 generation rate as compared to Co–P–B powder. We attribute this increased efficiency to the special features of the Co–P–B films which are in the form of nanoparticle-assembled films, a peculiar characteristic of PLD films for appropriate choice of the pulse laser parameters. The surface nanoparticle-configuration increases the active surface area and also favors electronic exchange mechanisms to promote hydrolysis process for H2 gas generation. The films deposited by using laser energy density of 3J/cm2 show the highest activity in connection to the best configuration of the ablated nanoparticles. Different numbers of Co–P–B layers were deposited on Ni-foam by ED and it was found that at least four layers are required for complete coverage of the foam to have the best activity. [Copyright &y& Elsevier]

Abstract: Nanoparticle-assembled Co-B thin films were synthesized by Pulsed Laser Deposition (PLD) and used as catalysts for the hydrolysis of NH3BH3 (ammonia borane, AB) to produce molecular hydrogen. Amorphous Co-B-based catalyst powders, produced by chemical reduction of cobalt salts, were used as target material for Co-B thin film catalysts preparation through PLD. Surface morphology of Co-B powder and film catalyst was studied using Scanning Electron Microscopy (SEM) and Atomic Force Microscopy (AFM). Compositional and structural characterizations were carried out using X-photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) techniques, respectively. The efficiency of both powder and film catalysts was tested by comparative kinetic analysis of the AB hydrolysis for hydrogen production. It was observed that nanoparticles produced during the laser ablation process act as active catalytic centers to produce significantly higher rate (about 6 times) of H2 than the same amount of the corresponding Co-B powders. Almost complete conversion (95%) of AB was obtained, as confirmed by 11B NMR, by using Co-B films at room temperature. Active Co-B nanoparticles on the surface of the PLD-deposited films is able to decrease the activation energy, for hydrolysis of AB, to the very low value of 34kJmol−1. We also found that by adding small amount of NaBH4 to the NH3BH3 solution increases the efficiency of the Co-B catalyst films, thus generating H2 with higher rate. Maximum H2 generation rate of about ∼8.2LH2 min−1 (g of Co)−1 and ∼13LH2 min−1 (g of Co)−1 was measured by hydrolysis of AB and mixture of (AB+NaBH4) solutions, respectively. [Copyright &y& Elsevier]

Abstract: Hydrogen generation by catalytic hydrolysis of sodium borohydride (NaBH4) is studied by using Co–B-based thin film catalyst synthesized by pulsed laser deposition (PLD) technique. Co–B nanoparticles, produced in the catalyst film after the laser ablation process, act as active centers producing significantly higher H2 generation rate than Co–B bulk powder. Surface morphology was studied by using scanning electron microscopy and compositional analysis was established by using X-photoelectron and infrared spectroscopies. Films were deposited at different PLD set-up parameters in order to understand the possible role of size and density of the nanoparticles in the catalytic process. Cobalt has been found here to act as an efficient catalyst only when alloyed with boron which partially prevents cobalt oxidation. In particular we report that when used as suitable thin films, Co–B produces H2 with a maximum generation rate of about 3300ml/min per gram of catalyst. [Copyright &y& Elsevier]

Examines the preparation of silicon carbide nanofibers by use of polymer blend technique. Kinds of polycarbosilanes used as a precursor for the silicon carbide fibers; Description of the surface morphology of as spun fiber, stabilized fiber and carbonized fiber; Thermo gravimetric analysis under a nitrogen atmosphere weight loss of the fibers.

Nanocatalysts, in the form of nanoparticles assembled coatings (NPACs) of Co 3 O 4 , were synthesized by pulsed laser deposition (PLD) with optimized parameters. Phase explosion phenomena occurring at high laser fluences produce nanoparticles (NPs) with an average size of ∼5 nm having narrow size distribution (3–10 nm) and low degree of agglomeration, which are randomly arranged in the form of coating on the substrate surface. In comparison with chemically synthesized Co 3 O 4 crystalline powder, the NPACs deposited by PLD showed significantly higher catalytic activity for H 2 generation by hydrolysis of NaBH 4 . Maximum H 2 generation rate obtained by NPACs (5010 ml min −1 g cat −1 ) is about 5 times higher than that produced by Co 3 O 4 powder (1000 ml min −1 g cat −1 ), which is mainly attributed to high surface area and large number of active sites provided by the Co 3 O 4 NPs in the coating owing to their size and shape. By varying the O 2 pressure during PLD, two different cobalt oxide phases, namely Co 3 O 4 and CoO, were formed in NPACs and found that Co 3 O 4 phase is more active for hydrolysis than CoO phase with lower oxidation number. The morphology and crystallinity of Co 3 O 4 NPACs were tuned by varying the laser fluence and substrate temperature respectively, and their effect on H 2 generation rate was studied. The results showed that the NPs with mixed amorphous-nanocrystalline phase on the surface act as active sites for favorable interaction and NaBH 4 conversion. [ABSTRACT FROM AUTHOR]

[Display omitted] • gC 3 N 4 nanosheets was incorporated with O anions and Fe metallic nanoparticles by a facile method. • Hybridization between Fe, N and O leads to the formation of an intermediate band within the bandgap of gC 3 N 4. • Exfoliation strategy by mixed acid treatment increased the surface area by one order of magnitude than pristine gC 3 N 4. • Cointegration of these strategies led to ∼17 times improvement in the photocatalytic rate. • Combined experimental and theoretical approach provides concrete evidence for improvement in all intrinsic properties. With graphitic carbon nitride (gC 3 N 4) showing considerable potential for photocatalytic applications, the four significant limitations: surface area, light-harvesting capability, photogenerated charge separation, and charge transfer at the interface, need to be comprehensively addressed. The present work aims to exfoliate the gC 3 N 4 stacking layers and fragment the layers horizontally to form ultra-thin nanosheets (NS) by a facile mixed-acid treatment. The surface area of gC 3 N 4 increased by one order of magnitude (120 m2/g), due to the formation of nanosheets with planar size below ∼50 nm. Moreover, incorporating non-metal (oxygen) anion dopants and metal (iron) nanoparticles enhances the overall reactivity of gC 3 N 4 NS under light irradiation. Co-integration of these strategies led to ∼17 times improvement in the photocatalytic pollutants degradation rate compared to pristine gC 3 N 4. First-principles calculations and experimental evidence suggest the formation of an intermediate band within the bandgap of gC 3 N 4 , caused by the hybridization of N -Fe-O, which assists in harvesting a larger number of photons. Nanosheet morphology provides a shorter distance to photogenerated charges towards the surface, while the incorporation of Fe and O together offers the lowest charge transfer resistance at the interface to efficiently degrade the adsorbed pollutant molecules on the surface. With all these promoting features along with cost-effective and stable elements, Fe-O-gC 3 N 4 NS provides an ideal solution for tuning the intrinsic morphological and electronic structure of gC 3 N 4 for its effective application in various photocatalytic reactions. [ABSTRACT FROM AUTHOR]