Enhancement of Activity and Development of Low Pt Content Electrocatalysts for Oxygen Reduction Reaction in Acid Media

Platinum is a main catalyst for the electroreduction of oxygen, a reaction of primary importance to the technology of low-temperature fuel cells. Due to the high cost of platinum, there is a need to significantly lower its loadings at interfaces. However, then O₂-reduction often proceeds at a less positive potential, and produces higher amounts of undesirable H₂O₂-intermediate. Hybrid supports, which utilize metal oxides (e.g., CeO₂, WO₃, Ta₂O₅, Nb₂O₅, and ZrO₂), stabilize Pt and carbon nanostructures and diminish their corrosion while exhibiting high activity toward the four-electron (most efficient) reduction in oxygen. Porosity of carbon supports facilitates dispersion and stability of Pt nanoparticles. Alternatively, the Pt-based bi- and multi-metallic catalysts, including PtM alloys or M-core/Pt-shell nanostructures, where M stands for certain transition metals (e.g., Au, Co, Cu, Ni, and Fe), can be considered. The catalytic efficiency depends on geometric (decrease in Pt–Pt bond distances) and electronic (increase in d-electron vacancy in Pt) factors, in addition to possible metal–support interactions and interfacial structural changes affecting adsorption and activation of O₂-molecules. Despite the stabilization of carbons, doping with heteroatoms, such as sulfur, nitrogen, phosphorus, and boron results in the formation of catalytically active centers. Thus, the useful catalysts are likely to be multi-component and multi-functional.     

The symmetric amino-wagging band of hydrazine: Assignment and analysis

For the first time a weak fundamental symmetric amino-wagging band, ν₆, was assigned in the high-resolution Fourier-transform infrared spectrum of hydrazine. The analysis of the Fermi-type resonance between the ν₆ and the third excited torsional state, 3ν₇, is presented. A global fitting was carried out taking into account 3392 lines of the ν₆ band (for K′ from 0 to 10 and for all symmetry species) and 428 lines of the 3ν₇ band (for K′ from 3 to 9 and only for the symmetry species in resonance). For all 3820 rovibrational transitions the overall standard deviation of the fit of 0.019 cm⁻¹ was obtained. The band centers of the symmetric wagging state and the third torsional were determined at 795.137 and 860.138 cm⁻¹, respectively. Individual fits were also carried out for K′ from 3 to 8 for all symmetry species with much improved standard deviations. The effective group-theoretical Hamiltonian for the coupling between inversion and torsion states was used.     

Extraction of copper ions using silica gel with chemically modified surface

The applicability of silica gels for the application in solid-phase extraction was tested. Silica was modified with ketoimine groups. Surface characteristics of the modified silica were determined by elemental analysis, NMR spectra of solid phases (²⁹Si CP MAS NMR), analysis of pore size distribution of the silica support, and nitrogen adsorption-desorption. Newly proposed sorbents with ketoimine groups were applied in the preconcentration of trace amounts of the Cu (II) ions from lake water, post-industrial water, and demineralized water unburdened back to the lake. Presented at the 34th International Conference of the Slovak Society of Chemical Engineering, Tatranské Matliare, 21–25 May 2007.     

Macro- and micro- elements in some herbal drug raw materials and their water extracts consumed in Poland

The concentrations of seven macro- and microelements (K, Mg, Ca, Na, Fe, Zn, Mn) in 59 herbs (herbs, leaves, flowers, fruits, roots), which are commercially available and frequently used in Poland for medical purposes as well as in their water extracts (infusions and decoctions), were determined after microwave mineralization. The data obtained show that all herbal raw materials analysed contain macroelements in the range of mg g⁻¹ on d.w. whereas microelements in the range of mg kg⁻¹ on d.w. and that elemental concentrations varied widely. On the basis of a comparison of concentrations of elements in herbal raw materials examined and water extracts prepared from them, the extraction efficiency was expressed as a percent of the total content of each element present in the infusion or decoction. The percentages of macro- and micro- elements leaching from different morphological parts of plants into water extracts varied across a wide range of values, from 1% in the case of Na to 56% in the case of K. Real daily intake of the macro- and microelements elements through one cup of infusions or decoctions were shown that water extracts from herbal raw materials are not an important source of bioelements in human diet.      

2-Methylthio-imidazolins: a rare case of different tautomeric forms in solid state and in solution

Structural Chemistry - The synthesis and structure elucidation of two new compounds, 2-(methylthio)-1,3-diazaspiro[4.4]non-2-ene-4-one (1) and 2-(methylthio)-1,3-diazaspiro[4.4]non-2-ene-4-thione...     

Towards Extended Zinc Ethylsulfinate Networks by Stepwise Insertion of Sulfur Dioxide into Zn−C Bonds

The ability to utilize polluting gases in efficient metal-mediated transformations is one of the most pressing challenges of modern chemistry. Despite numerous studies on the insertion of SO₂ into M−C bonds, the chemical reaction of SO₂ with organozinc compounds remains little explored. To fill this gap, we report here the systematic study of the reaction of Et₂Zn towards SO₂ as well as the influence of Lewis bases on the reaction course. Whereas the equimolar reaction provided a novel example of a structurally characterized organozinc ethylsulfinate compound of general formula [(EtSO₂)ZnEt]_n, the utilization of an excess of SO₂ led to the formation of the zinc(II) bis(ethylsulfinate) compound [(EtSO₂)₂Zn]_n. Moreover, we have discovered that the presence of N-donor Lewis bases represents an efficient tool for the preparation of extended zinc ethylsulfinates, which in turn led to the formation of 1D [(EtSO₂ZnEt)₂(hmta)]_n and 2D [((EtSO₂)₂Zn)₂(DABCO)]_n ⋅ solv (in which solv=THF or toluene, hmta= hexamethylenetetramine, and DABCO=1,4-diazabicyclo[2.2.2]octane) coordination polymers, respectively. The results of DFT calculations on the reactivity of SO₂ towards selected Zn−C reactive species as well as the role of an N-donor Lewis base on the stabilization of the transition states complement the discussion.     

An In‐Depth Look at the Reactivity of Non‐Redox‐Metal Alkylperoxides

Over the past 150 years, a certain mythology has arisen around the mechanistic pathways of the oxygenation of organometallics with non‐redox‐active metal centers as well as the character of products formed. Notably, there is a widespread perception that the formation of commonly encountered metal alkoxide species results from the auto‐oxidation reaction, in which a parent metal alkyl compound is oxidized by the metal alkylperoxide via oxygen transfer reaction. Now, harnessing a well‐defined zinc ethylperoxide incorporating a β‐diketiminate ligand, the investigated alkylperoxide compounds do not react with the parent metal alkyl complex as well as Et₂Zn to form a zinc alkoxide. Upon treatment of the zinc ethylperoxide with Et₂Zn, a previously unobserved ligand exchange process is favored. Isolation of a zinc hydroxide carboxylate as a product of decomposition of the parent zinc ethylperoxide demonstrates the susceptibility of the latter to O?O bond homolysis.     

tert‐Butyl(tert‐butoxy)zinc Hydroxides: Hybrid Models for Single‐Source Precursors of ZnO Nanocrystals

Alkylzinc alkoxides, [RZnOR′]₄, have received much attention as efficient precursors of ZnO nanocrystals (NCs), and their “Zn₄O₄” heterocubane core has been regarded as a “preorganized ZnO”. A comprehensive investigation of the synthesis and characterization of a new family of tert‐butyl(tert‐butoxy)zinc hydroxides, [(tBu)₄Zn₄(μ₃‐OtBu)_x(μ₃‐OH)_4?x], as model single‐source precursors of ZnO NCs is reported. The direct reaction between well‐defined [tBuZnOH]₆ ( 1₆ ) and [tBuZnOtBu]₄ ( 2₄ ) in various molar ratios allows the isolation of new mixed cubane aggregates as crystalline solids in a high yield: [(tBu)₄Zn₄(μ₃‐OtBu)₃(μ₃‐OH)] ( 3 ), [(tBu)₄Zn₄(μ₃‐OtBu)₂(μ₃‐OH)₂] ( 4 ), [(tBu)₄Zn₄(μ₃‐OtBu)(μ₃‐OH)₃] ( 5 ). The resulting products were characterized in solution by ¹H NMR and IR spectroscopy, and in the solid state by single‐crystal X‐ray diffraction. The thermal transformations of 2 – 5 were monitored by in situ variable‐temperature powder X‐ray diffraction and thermogravimetric measurements. The investigation showed that the Zn?OH groups appeared to be a desirable feature for the solid‐state synthesis of ZnO NCs that significantly decreased the decomposition temperature of crystalline precursors 3 – 5 .