Catalyst Design: Counter Anion Effect on Ni Nanocatalysts Anchored on Hollow Carbon Spheres.

Herein, the influence of the counter anion on the structural properties of hollow carbon spheres (HCS) support was investigated by varying the nickel metal precursor salts applied. TEM and SEM micrographs revealed the dimensional dependence of the HCS shell on the Ni precursor salt, as evidenced by thick (~42 nm) and thin (~23 nm) shells for the acetate and chloride-based salts, respectively. Importantly, the effect of the precursor salt on the textural properties of the HCS nanosupports (~565 m2/gNi(acet)) and ~607 m2/gNiCl), influenced the growth of the Ni nanoparticles, viz for the acetate-(ca 6.4 nm)- and chloride (ca 12 nm)-based salts, respectively. Further, XRD and PDF analysis showed the dependence of the reduction mechanism relating to nickel and the interaction of the nickel-carbon support on the type of counter anion used. Despite the well-known significance of the counter anion on the size and crystallinity of Ni nanoparticles, little is known about the influence of such counter anions on the physicochemical properties of the carbon support. Through this study, we highlight the importance of the choice of the Ni-salt on the size of Ni in Ni-carbon-based nanocatalysts.

Spectroscopic characterization and antimicrobial activity of nanoparticle doped cyclodextrin polyurethane bionanosponge.

This study reports on the spectroscopic characterization and antimicrobial potency of polyurethane cyclodextrin co-polymerized phosphorylated multiwalled carbon nanotube-doped Ag-TiO2 nanoparticle (pMWCNT-CD/Ag-TiO2) bionanosponge nanocomposite. The synthesis of pMWCNT-CD/Ag-TiO2 bionanosponge nanocomposite was carried out through the combined processes of amidation and polymerization reactions as well as the sol-gel method. The native nanosponge cyclodextrin and phosphorylated multiwalled carbon nanotube-nanosponge CD (pMWCNT-CD) polyurethanes were also prepared, and their antimicrobial activities carried out for comparison purposes. The synthesized bionanosponge polyurethane materials were characterized using Fourier-transform infrared (FTIR) spectroscopy, Laser Raman spectroscopy, X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) to give clear information regarding their structural, and dynamic physicochemical properties. The potency tests of the synthesized compounds were carried out against three bacterial strains Escherichia coli, Bacillus subtilis, Staphylococcus aureus, and two fungal representatives Aspergillus ochraceus and Aspergillus fumigatus, using the disc diffusion method. Micro dilution and agar plating were used to determine the minimum bactericidal concentration (MBC) and minimum fungicidal concentration (MFC), respectively. The results obtained revealed that pMWCNT-CD/Ag-TiO2 exhibits superior antibacterial and antifungal activities when compared to the other bionanosponge polymers tested. Thus, the bionanosponge polyurethane pMWCNT-CD/Ag-TiO2 nanocomposite can be considered as an active antimicrobial compound (AMC).

Inorganic Perovskite-Induced Synergy on Highly Selective Pd-Catalyzed Hydrogenation of Cinnamaldehyde.

The transformation of various organic molecules into value-added chemicals has been driven by the success in development of highly active catalytic systems. Heterogeneous catalysts have found use in many industrial processes by virtue of their ease of separation and high activities in various reactions. However, many processes employing heterogeneous catalysts in the transformation of organic molecules suffer significantly when it comes to product selectivity. Herein, we report on the synthesis of highly selective palladium nanoparticle (Pd NP)-containing catalysts. The heterogeneous catalysts reported herein consist of active mixed-metal oxides, in the form of perovskites as catalysts, and as catalytic supports for Pd NPs. The activity of pure perovskites when applied as catalysts in the hydrogenation of cinnamaldehyde is 3 factors lower compared with Pd NPs immobilized on them. However, considering the fact that perovskites achieved percentage conversions between 18 and 25% in a short period of time makes them perfect candidates to replace platinum group metals in the future. In addition to being earmarked as the future of catalysis, perovskites induced a synergistic effect on the conversion of the substrate compared to when Pd NPs are immobilized on the silica support. Furthermore, these catalysts are 100% selective to hydrocinnamaldehyde and stable for up to five catalytic cycles. With regard to reusability of the catalysts, Pd/LaFeO3 was used as a benchmark catalyst and revealed the need for surface restructuring of the catalyst for optimum activity.

Effect of cationic disorder on the energy generation and energy storage applications of Ni x Co3-x S4 thiospinel.

Thiospinels show interesting catalytic and energy storage applications, however, the cationic disorder can have major influence on the energy generation and/or energy storage applications. In this study, the effect of stoichiometric variation of metals in a thiospinel i.e. Ni x Co3-x S4, is examined on energy generation and storage properties. Nickel- or cobalt-rich Ni x Co3-x S4 nanosheets were prepared by the hot injection method using single molecular precursors. The nanosheets were characterized by p-XRD, TEM, HR-TEM, EDX and XPS techniques. Nickel-rich and cobalt-rich nanosheets were tested for oxygen and hydrogen evolution reactions and for supercapacitance performance. It was observed that the nickel-rich Ni x Co3-x S4 nanosheets have superior energy storage and energy generation properties.

Mn substituted Mn x Zn1-x Co2O4 oxides synthesized by co-precipitation; effect of doping on the structural, electronic and magnetic properties.

Mn substituted Mn x Zn1-x Co2O4 (x = 0, 0.3, 0.5, 0.7, 1) oxides were synthesized by a facile co-precipitation method followed by calcination at 600 °C. The presence of manganese ions causes appreciable changes in the structural and magnetic properties of the Mn-substituted ZnCo2O4. The morphologies, structures, and electronic properties of Mn-Zn-Co oxide microspheres were characterized using scanning electron microscopy, transmission electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. The X-ray diffraction and Fourier transform infrared spectroscopy results confirmed the formation of spinel Mn x Zn1-x Co2O4. It was shown that the Mn-Zn-Co oxide microspheres increase in size and become regular in shape with increasing Mn concentration with the crystal size lying in the range from 19.1 nm to 51.3 nm. Magnetization measurements were carried out using a vibrating sample magnetometer at room temperature and 10 K. The saturation magnetization is observed to increase with increasing Mn concentration from x = 0 to x = 1.

Angle-resolved photoemission spectroscopy at ultra-low temperatures.

The physical properties of a material are defined by its electronic structure. Electrons in solids are characterized by energy (ω) and momentum (k) and the probability to find them in a particular state with given ω and k is described by the spectral function A(k, ω). This function can be directly measured in an experiment based on the well-known photoelectric effect, for the explanation of which Albert Einstein received the Nobel Prize back in 1921. In the photoelectric effect the light shone on a surface ejects electrons from the material. According to Einstein, energy conservation allows one to determine the energy of an electron inside the sample, provided the energy of the light photon and kinetic energy of the outgoing photoelectron are known. Momentum conservation makes it also possible to estimate k relating it to the momentum of the photoelectron by measuring the angle at which the photoelectron left the surface. The modern version of this technique is called Angle-Resolved Photoemission Spectroscopy (ARPES) and exploits both conservation laws in order to determine the electronic structure, i.e. energy and momentum of electrons inside the solid. In order to resolve the details crucial for understanding the topical problems of condensed matter physics, three quantities need to be minimized: uncertainty* in photon energy, uncertainty in kinetic energy of photoelectrons and temperature of the sample. In our approach we combine three recent achievements in the field of synchrotron radiation, surface science and cryogenics. We use synchrotron radiation with tunable photon energy contributing an uncertainty of the order of 1 meV, an electron energy analyzer which detects the kinetic energies with a precision of the order of 1 meV and a He(3) cryostat which allows us to keep the temperature of the sample below 1 K. We discuss the exemplary results obtained on single crystals of Sr2RuO4 and some other materials. The electronic structure of this material can be determined with an unprecedented clarity.