Özgür Birer

A high-performance metal-free hydrogen-evolution reaction electrocatalyst from bacterium derived carbon

We report a sustainable approach to obtain carbon materials with nitrogen and phosphorus dual functionalities from a common bacterium strain (S. aureus) as a highly efficient hydrogen-evolution reaction (HER) catalyst. With mesoporous structure introduced by ZnCl2 salt and cathodic activation, it demonstrates an onset overpotential as low as 76 mV, a Tafel slope of 58.4 mV dec−1 and a large normalized exchange current density of 1.72 × 10−2 mA cm−2, which are comparable to those of hitherto best metal-free and well-fabricated metallic HER catalysts.

Catalytic activity of copper (II) oxide prepared via ultrasound assisted Fenton-like reaction.

Copper (II) oxide nanoparticles were synthesized in an ultrasound assisted Fenton-like aqueous reaction between copper (II) cations and hydrogen peroxide. The reactions were initiated with the degradation of hydrogen peroxide by ultrasound induced cavitations at 0 °C or 5 °C and subsequent generation of the OH radical. The radical was converted into hydroxide anion in Fenton-like reactions and copper hydroxides were readily converted to oxides without the need of post annealing or aging of the samples. The products were characterized with X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and Brunauer-Emmett-Teller (BET) surface area analysis. Catalytic activity of the nanoparticles for the hydrogen peroxide assisted degradation of polycyclic aromatic hydrocarbons in the dark was tested by UV-visible spectroscopy with methylene blue as the model compound. The rate of the reaction was first order, however the rate constants changed after the initial hour. Initial rate constants as high as 0.030 min(-1) were associated with the high values of surface area, i.e. 70 m(2)/g. Annealing of the products at 150 °C under vacuum resulted in the decrease of the catalytic activity, underlying the significance of the cavitation induced surface defects in the catalytic process.

Bacterial physiology is a key modulator of the antibacterial activity of graphene oxide

Carbon-based nanomaterials have a great potential as novel antibacterial agents; however, their interactions with bacteria are not fully understood. This study demonstrates that the antibacterial activity of graphene oxide (GO) depends on the physiological state of cells for both Gram-negative and -positive bacteria. GO susceptibility of bacteria is the highest in the exponential growth phase, which are in growing physiology, and stationary-phase (non-growing) cells are quite resistant against GO. Importantly, the order of GO susceptibility of E. coli with respect to the growth phases (exponential ≫ decline > stationary) correlates well with the changes in the envelope ultrastructures of the cells. Our findings are not only fundamentally important but also particularly critical for practical antimicrobial applications of carbon-based nanomaterials.

Sonochemical synthesis and electrochemical characterization of α-nickel hydroxide: precursor effects

Sonochemical degradation of urea was employed to synthesize alpha-nickel hydroxide from different nickel salts. Utilization of ultrasound yielded products with properties significantly different than the products obtained by thermal degradation of urea. The effect of intercalating chloride, nitrate, acetate, and sulfate anions on morphology and electrochemical performance was studied. The sulfate-intercalated sample had the smallest interlayer spacing when obtained by the sonochemical method, contradicting all the previous thermal synthesis results. The specific capacitance trend also differed from the literature values, and the value for the sulfate-intercalated sample was larger than that of acetate- and nitrate-intercalated samples. Ultrasonic synthesis increased the specific capacitance of the sulfate-intercalated sample significantly. This sample was also the most reversible and had the highest charge efficiency.

Sonochemical shape control of copper hydroxysulfates

Shape control of inorganic nanoparticles generally requires the use of surfactants or ligands to passivate certain crystallographic planes. Additive free shape control methods utilize the differences in the growth rates of crystallographic planes. We combined this approach with the sonochemical method to synthesize copper hydroxysulfate (Brochantite) with morphologies ranging from flowers, to bricks, belts and needles. Sodium peroxydisulfate, which was used as the sulfate and hydroxide source, was decomposed thermally and/or sonically under various pH and temperature conditions. The relative release rates of the sulfate and hydroxide anions determined the final form of the crystals. This technique yielded products even at acidic pH, marking a distinction from the literature reactions, which start with stoichiometric amounts of sulfate and hydroxide anions and yield only a single crystal morphology.

Discovery of Superior Cu-GaOx-HoOy Catalysts for the Reduction of Carbon Dioxide to Methanol at Atmospheric Pressure

Catalytic conversion of carbon dioxide to liquid fuels and basic chemicals by using solar‐derived hydrogen at, or near, ambient pressure is a highly desirable goal in heterogeneous catalysis. If realized, this technology could lead to a more sustainable society together with decentralized power generation. A novel class of holmium‐containing multi‐metal oxide Cu catalysts, discovered through the application of high‐throughput methods, is reported. In particular, ternary systems of Cu‐GaOx‐HoOy>Cu‐CeOx‐HoOy∼Cu‐LaOx‐HoOy supported on γ‐Al2O3 exhibited superior methanol production (10×) with less CO formation than previously reported catalysts at 1 atm pressure. Holmium was shown to be highly dispersed as few‐atom clusters, suggesting that the formation of trimetallic sites could be the key for the promotion of methanol synthesis by Ho.

Simultaneous DLS–SLS study of titanium and titanium/silicon oxide sol growth

AbstractA commercial DLS setup was used for simultaneous DLS/SLS analysis of sol growth of titanium and titanium/silicon oxides. The scattering data were analyzed in dynamic and static modes which allowed evaluating particle size and concentration simultaneously. A binary solvent (acetone/ethanol mixture) was introduced which effectively controls monodisperse growth behavior by simply adjusting its ratio. Fixing the solvent composition to the ratio which delayed gelation the most, the effect of the amount of catalyst (acetic acid), hydrolyzing agent (water) and titanium oxide precursor (titanium tetraisopropoxide) on growth kinetics were studied. Taking the advantage of extra functionalities of the catalyst used, acetic acid, i.e., decreasing the reactivity of titanium tetraisopropoxide and increasing the reactivity of tetraethyl orthosilicate, hybrid titanium/silicon oxide growth was also studied. Here, we step-by-step showed that particle size, particle concentration and sol-to-gel transition time of titanium and titanium/silicon oxide systems can be well controlled by adjusting the composition of formulations in ambient conditions. We also showed how practical the laser light scattering is to evaluate even the early onsets of growth profiles long before visual identification of clouding. The findings reported here are particularly important for practical applications of sol–gel technology where the control of particle size/concentration and gelation time is advantageous. Graphical Abstract

Sonochemical zinc oxide and layered hydroxy zinc acetate synthesis in fenton-like reactions

Zinc acetate solution is sonicated at high power in water and in ethanol in the absence and presence of various peroxides. In the absence of peroxides, the products are zinc oxide and layered hydroxy zinc acetate in water and in ethanol, respectively. Layered basic zinc acetate are prepared for the first time using sonochemical methods. The addition of peroxides alters the reaction mechanisms. In water, insoluble peroxides produce zinc oxides while the water soluble peroxide, i.e. hydrogen peroxide, completely destroyed the structure and casted a doubt on the accepted peroxide initiated mechanism of reactions. In ethanol, peroxide addition caused the reaction mechanism to change and some oxide formation is observed. The reaction mechanism is sensitive to water/ethanol amounts as well as the peroxide to zinc ion mole ratio. Thin zinc oxide wafers (ca. 30nm) with band gaps of 3.24eV were obtained.

Formation and distribution of ZnO nanoparticles and its effect on E. coli in the presence of sepiolite and silica within the chitosan matrix via sonochemistry

In this study, a new bio-nanocomposite was prepared and characterized with a focus on the formation of hexagonal ZnO and orthorhombic zinc silicate (Zn2SiO3(OH)2) phases under ultrasonic irradiation. Chitosan/sepiolite/ZnO and chitosan/silica/ZnO bio-nanocomposites were synthesized using a simple solution method in which extreme physical and chemical conditions created by cavitation within the chitosan solution allowed for the transformation of aqueous Zn(OH)2 to crystallized ZnO and Zn2SiO3(OH)2 in room temperature. Both the loading of sepiolite and silica with the zinc precursor significantly influenced the morphology and crystalline structure of the product, however, different zinc compounds were observed. Sepiolite was exfoliated, resulting in a fine, even colloidal solution through ultrasonic dispersion. Exfoliation of sepiolite nanofibers led to the homogeneous dispersion of Zinc in the form of Zn(OH)2 in chitosan matrix. When the same procedure was conducted using the silica component, a formation of ZnO and Zn2SiO3(OH)2 was observed, components that were not observed when the procedure was conducted using sepiolite. The average crystalline size of ZnO was calculated as 36nm for ZnO. In addition, the quantities of crystalline and the ZnO phase volume was determined as 15%. Through zone of inhibition, the silica nanocomposite was discovered to have antibacterial activity. In contrast, the sepiolite compound did not exhibit these properties. We thus hypothesize that HO radicals, formed during ultrasonic irradiation trigger the formation of a silicate ion (SiO32-) and formation of ZnO and Zn2SiO3(OH)2 species in chitosan/silica/ZnO bio-nanocomposite, which causes to exhibit these antibacterial properties against Gram-negative E. coli. Chemical characterization and dispersion of the structure of the ZnO and Zn2SiO3(OH)2 phases were done using X-ray diffraction (XRD) and scanning electron microscopy techniques (SEM) with EDAX and X-ray photoelectron spectroscopy (XPS).