Glossary of terms used in photocatalysis and radiation catalysis (IUPAC recommendations 2011)

This glossary of terms covers phenomena considered under the very wide terms photocatalysis and radiation catalysis. A clear distinction is made between phenomena related to either photochemistry and photocatalysis or radiation chemistry and radiation catalysis. The term "radiation" is used here as embracing electromagnetic radiation of all wavelengths, but in general excluding fast-moving particles. Consistent definitions are given of terms in the areas mentioned above, as well as definitions of the most important parameters used for the quantitative description of the phenomena. Terms related to the up-scaling of photocatalytic processes for industrial applications have been included. This Glossary should be used together with the Glossary of terms used in photochemistry, 3rd edition, IUPAC Recommendations 2006: (doi:10.1351/pac200779030293) as well as with the IUPAC Compendium of Chemical Terminology, 2nd ed. (the "Gold Book" 2006-; doi:10.1351/goldbook), because many terms used in photocatalysis are defined in these documents. © 2011 IUPAC

Investigation of Physicochemical and Electrochemical Properties of Single-Walled Carbon Nanotubes Modified with Nitrogen

Composites of the type “nitrogen-containing carbon coating – single-walled carbon nanotubes” were obtained by the treatment of single-walled carbon nanotubes (SWCNT) in a gaseous 40%NH3-1%C2H2-C2H4 mixture at temperatures 600–750 °C. Single-walled carbon nanotubes etched in aqua regia (SWCNTet) and doped with nitrogen (N-SWCNT) were studied by XPS, electron microscopy and IR spectroscopy. Various oxygen-containing functional groups were found to reside on the surface of initial SWCNTet. Upon treatment of SWCNTet in 40%NH3-1%С2Н2-C2H4, polymerization and condensation of hydrocarbons resulted in the formation of a thin nitrogen-containing carbon coating. Specific capacitance per a weight of initial and nitrogen-doped carbon nanotubes in an aqueous electrolyte with 1 M H2SO4 was measured. Specific capacitance of carbon electrodes was found to change symbately with the content of nitrogen-containing functional groups on the SWCNT surface

Synthesis of “Silica – Carbon Nanotubes” Composite and Investigation of its Properties

A new method for synthesis of CNT-SiO2 composite was developed. Oligomethylhydridesiloxane (OMHS) was used as the SiO2 precursor. The presence of active hydrogen in the composition of OMHS made it possible to obtain chemical interaction between the surface of carbon nanotubes and the deposited silica layer. The effect of the silica film on the CNT oxidizing ability was studied. It was found that the oxidation rate of the CNT-SiO2 composite decreases approximately by an order of magnitude in comparison with as-prepared CNT. The morphology and structure of amorphous silica obtained after oxidation of the CNT-SiO2 composite were studied. The thermal stability of the CNT-SiO2 composite was also studied. The CNT-SiO2 composite was found to be thermally stable up to temperatures of 1100-1200 ºC. An increase in the calcination temperature to 1300 ºC leads to segregation of the CNT-SiO2 composite into individual components: CNT and SiO2 particles

Development Diastolic Dysfunction Myocardium in Children with Acute Lymphoblastic Leukemia at the Stages of fhe Polychemotherapy

The development of progressive myocardial dysfunction is one of the side effects of polychemotherapy. Changes in diastolic filling of the left ventricular is the earliest marker that precedes the full-scaled clinical picture of heart failure. Purpose: Assessment of left ventricle’s diastolic function and the study of the state of lipid peroxidation processes in children with acute leukemia at the stages of polychemotherapy. Materials and Methods: We have examined 54 patients with acute lymphoblastic leukemia at the age ranging from 3 to 17 years old. Results: Complex transthoracic Doppler echocardiography shows the occurrence of diastolic dysfunction at the time when the disease is diagnosed and its progression after the end of polychemotherapy. The development of cardiac complications is accompanied by an increase in the generation of reactive oxygen species, accumulation of oxydated lipoproteins, which suggests the free-radical genesis of myocardial damage. Summary: Early detection of disorder of diastolic function of the left ventricle may allow to appoint cardiotropic therapy on the initial stage and decrease the rate of complications of polychemotherapy

New Gas-Phase Catalytic Oxidative Processes for Desulfurization of Diesel Fuel

An effective gas-phase oxidative desulfurization (ODS) process was proposed. The process was studied in a laboratory reactor with a proprietary catalyst at 300-400 ºС and ambient pressure with model fuels represented by thiophene, dibenzothiophene(DBT) and 4,6-dimethyldibenzothiophene (DMDBT) dissolved in octane, isooctane or toluene. The reactivity of different sulfur containing molecules in ODS was shown to increase in the sequence: thiophene<DBT<DMDBT. The main sulfur containing product of oxidation of these compounds was SO2. During the gas-phase ODS both processes of sulfur species oxidation and processes of their adsorption were observed and studied. Based on the conducted studies, different ODS process designs comprising its integration with adsorption and regeneration processes and with conventional hydrodesulfurization (HDS) process were proposed. One scheme is based on alternating regimes of ODS and catalyst regeneration in two reactors: sulfur is removed from organic feedstock by oxidation and adsorption in one reactor while simultaneous regeneration of the catalyst that has accumulated sulfur compounds takes place in another reactor. Two other schemes are based on joint use of ODS and HDS. The conventional HDS process is most effective for removal of low-boiling sulfur containing compounds reactive with respect to hydrogen, while removal of refractory sulfur compounds, such as DMDBT is more easily achieved by gas phase ODS. Thus the combination of these processes is expected to be most efficient for deep desulfurization of diesel fuel

Kinetic non-reversibility of the cracking reactions and its accounting during mathematical modeling of industrial process

The paper presents the approach to the catalytic cracking modeling with consideration of the reactions' reversibility/non-reversibility depending on the current concentrations and the cracking temperature. The thermodynamic analysis of the reactions using the quantum-chemical methods allows formulating a hydrocarbons conversion scheme at the thermal equilibrium temperature between the feedstock and the catalyst. The magnitude of the current chemical attraction of reactions is a criterion of thermodynamic non-reversibility of reactions, which is determined at each stage of the calculation. It has been shown that the change in the concentrations of conversion participants and cracking temperature have a significant effect on the catalytic cracking reactions. Thus, the cyclization reactions are non-reversible up to 512.9 °C (A[rij]=6.46 kJ/mol) during the processing of feedstock with saturated hydrocarbons to aromatics ratio is 2.1 and with further temperature increasing the contribution of reverse reactions rises. Also with increasing the saturated hydrocarbons to aromatics ratio from 2.1 to 3.2 in the feedstock, the equilibrium of the reaction shifts to low temperatures from 512.9 to 508.9 °C (A[rij]=6.497 kJ/mol). It is connected with the fact that intensification of the exotermic reactions (alkylation, condensation, coke formation) under certain conditions is possible. It is an important factor in terms of catalyst deactivation and has an effect on the desired product yield

Ferrosilicate-Based Heterogeneous Fenton Catalysts: Influence of Crystallinity, Porosity, and Iron Speciation

Different ferrosilicate samples have been prepared with varying degrees of crystallinity, porous texture, and speciation of the Fe sites by both hydrothermal and sol–gel procedures: Fe-silicalite-1 with microcrystals (2–10 µm) and nanocrystals (180 nm), Fe-containing composite material consisting of silicalite-1 and amorphous silica, and two samples of mesoporous Fe-containing amorphous silica Fe–SiO2. The resulting solids have been tested for their potential as organic pollutants removal under Fenton-like conditions in heterogeneous catalytic wet peroxide oxidation of phenol and clarithromycin lactobionate. Our results indicate that the three aforementioned parameters show a strong interplay towards the abatement of pollutants in liquid phase. Thus, samples with high crystallinity show an improved performance in the oxidation of organic contaminants over amorphous samples in which the Fe speciation is very well controlled.The work was financially supported by the Ministry of Education and Science of the Russian Federation (RFMEFI60417 X 0159, title of the agreement: “Development of methods for hydrotreating of vacuum residue into high-quality marine fuels on macroporous catalysts”). The authors from Spanish side thank the Spanish Ministry of Economy and Competitiveness (MINECO), Generalitat Valenciana and FEDER (CTQ2015-66080-R MINECO/FEDER and PROMETEOII/2014/010) for financial support. J.G.A. thanks the Spanish Ministry of Economy and Competitiveness (MINECO) for his fellowship (BES-2013-063678)

Self-propagating High-temperature Synthesis of Materials Based on Tungsten Carbide for One-Pot Hydrolysis-Hydrogenolysis of Cellulose Into Ethylene Glycol and 1,2-Propylene Glycol

Методом самораспространяющегося высокотемпературного синтеза из смеси оксида вольфрама, металлического магния, технического углерода и CaCO3 с использованием механохимической обработки получены каталитические системы на основе карбида вольфрама (WnC), содержащие преимущественно W2C. Показано, что фазовый состав образующихся материалов зависит от количества CaCO3. Каталитические свойства полученных материалов исследованы в реакции гидролиза-гидрогенолиза целлюлозы до низших полиолов (этиленгликоль (ЭГ) и 1,2-пропиленгликоль (ПГ)). Установлено, что в присутствии WnC основными продуктами реакции являются ЭГ и ПГ с соотношением ПГ/ЭГ – 1,5-1,8. Нанесение наночастиц никеля на поверхность WnC материалов повышает скорость реакции и выход целевых продуктов. Максимальный суммарный выход диолов составил 47,1 мол. %Catalytic systems based on tungsten carbide (WnC) containing mainly W2C were obtained by the method of self-propagating high-temperature synthesis from a mechanochemically activated mixture of tungsten oxide, metallic magnesium, carbon black and CaCO3. The phase composition of the formed materials was shown to depend on the amount of CaCO3. The catalytic properties of the materials were tested in the hydrolysis-hydrogenation of cellulose to ethylene glycol (EG) and 1,2-propylene glycol (PG). It was established that in the presence of WnC the main products of the reaction were EG and PG with a ratio of PG/EG – 1.5-1.8. The deposition of nickel nanoparticles on the WnC surface increased the reaction rate and product yields. The maximum total yield of diols was 47.1 mol. %

Effect of Gas Atmosphere on Catalytic Behaviour of Zirconia, Ceria and Ceria Zirconia Catalysts in Valeric Acid Ketonization

[EN] Ketonization of valeric acid, which can be obtained by lignocellulosic biomass conversion, was carried out in a fixed bed flow reactor over ZrO2, 5-20 % CeO2/ZrO2 and CeO2 both under hydrogen and nitrogen stream at 628 K and atmospheric pressure. Regardless gas-carrier 10 wt% CeO2/ZrO2 was found to show higher catalytic activity compared to zirconia per se as well as other ceria modified zirconia while ceria per se exhibited very low catalytic activity. All catalysts provided higher acid conversion in H-2 than in N-2 whereas selectivity to 5-nonanone was insensitive to gas atmosphere. XRD, FTIR, UV-Vis DRS, XPS, HRTEM methods were applied to characterize catalysts in reduced and unreduced states simulating corresponding reaction conditions during acid ketonization. XRD did not reveal any changes in zirconia and ceria/zirconia lattice parameters as well as crystalline phase depending on gas atmosphere while insertion of ceria in zirconia caused notable increase in lattice parameter indicating some distortion of crystalline structure. According to XPS, FTIR and UV-Vis methods, the carrier gas was found to affect catalyst surface composition leading to alteration in Lewis acid sites ratio. Appearance of Zr3+ cations was observed on the ZrO2 surface after hydrogen pretreatment whereas only Zr4+ cations were determined using nitrogen as a gas-carrier. These changes of catalyst's surface cation composition affected corresponding activity in ketonization probably being crucial for reaction mechanism involving metal cations catalytic centers for acid adsorption and COO- stabilization at the initial step.Financial support from the Russian Foundation of Basic Research (RFBR Grant No 11-03-94001-CSIC) is gratefully acknowledged. This work was supported by the Federal Program "Scientific and Educational Cadres of Russia'' (Grant No 2012-1.5-12-000-1013-002). The authors also wish to thank Dr. Evgeniy Gerasimov, Dr. Igor Prosvirin, Dr. Demid Demidov from the Department of Physicochemical Methods at the Boreskov Institute of Catalysis for TEM and XPS measurements.Zaytseva, YA.; Panchenko, VN.; Simonov, MN.; Shutilov, AA.; Zenkovets, GA.; Renz, M.; Simakova, IL.... (2013). Effect of Gas Atmosphere on Catalytic Behaviour of Zirconia, Ceria and Ceria Zirconia Catalysts in Valeric Acid Ketonization. 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