Leaching Stability and Redox Activity of Copper-MFI Zeolites Prepared by Solid-State Transformations: Comparison with Ion-Exchanged and Impregnated Samples.

The catalyst preparation route is well known to affect the copper loading and its electronic state, which influence the properties of the resulting catalyst. Electronic states of copper ions in copper-containing silicalites with the MFI-framework topology obtained by a solid-state transformation S (SST) were studied with using EPR, UV-Vis DR, XRD, H2-TPR and chemical differentiating dissolution. They were compared with Cu-ZSM-5 and Cu-MFI (silicalite) prepared via the ion-exchange and incipient wetness impregnation. SST route was shown to provide the formation of MFI structure and favor clustering of Cu-ions near surface and subsurface of zeolite crystals. The square-planar oxide clusters of Cu2+-ions and the finely dispersed CuO nanoparticles with the size down to 20 nm were revealed in Cu-MFI-SST samples with low (0.5-1.0 wt.%) and high (16 wt.%) Cu-content. The CuO nanoparticles were characterized by energy band gap 1-1.16 eV. The CuO-like clusters were characterized by ligand-to-metal charge transfer band (CTB L → M) at 32,000 cm-1 and contain EPR-visible surface Cu2+-ions. The low Cu-loaded SST-samples had poor redox properties and activity towards different solvents due to decoration of copper-species by silica; whereas CuO nanoparticles were easily removed from the catalyst by HCl. In the ion-exchanged samples over MFI-silicalite and ZSM-5, Cu2+-ions were mainly CuO-like clusters and isolated Cu2+ ions inside MFI channels. Their redox properties and tendency to dissolve in acidic solutions differed from the behavior of SST-series samples.

One-pot synthesis of sorbitol via hydrolysis-hydrogenation of cellulose in the presence of Ru-containing composites.

The aim of this work was to study the one-pot synthesis of sorbitol via hydrolysis-hydrogenation of cellulose in the presence of Ru-containing composites based on H3PW12O40 supported on ZrO2 and Nb2O5 (Ru-PW/ZrO2 and Ru-PW/Nb2O5). The main parameters impacted the reaction rate and yield of sorbitol, i.e. reaction conditions and type of catalyst were investigated. Ru-PW/ZrO2 systems were more active than Ru-PW/Nb2O5. The yield of sorbitol was found to depend on the activation temperature of PW/ZrO2 and PW/Nb2O5 which affected textural properties, the amount of acid sites and size of Ru nanoparticles. The highest 66% sorbitol yield was observed in the presence of 3%Ru-PW/ZrO2 activated at 550 °C and 1/1 of weight ratio of cellulose/catalyst, 180 °C, 7 MPa hydrogen pressure. This catalyst was stable for three cycles of the reaction without lost of it's activity.

Young «oil site¼ of the Uzon Caldera as a habitat for unique microbial life.

BACKGROUND: The Uzon Caldera is one of the places on our planet with unique geological, ecological, and microbiological characteristics. Uzon oil is the youngest on Earth. Uzon oil has unique composition, with low proportion of heavy fractions and relatively high content of saturated hydrocarbons. Microbial communities of the «oil site¼ have a diverse composition and live at high temperatures (up to 97 °C), significant oscillations of Eh and pH, and high content of sulfur, sulfides, arsenic, antimony, and mercury in water and rocks. RESULTS: The study analyzed the composition, structure and unique genetics characteristics of the microbial communities of the oil site, analyzed the metabolic pathways in the communities. Metabolic pathways of hydrocarbon degradation by microorganisms have been found. The study found statistically significant relationships between geochemical parameters, taxonomic composition and the completeness of metabolic pathways. It was demonstrated that geochemical parameters determine the structure and metabolic potential of microbial communities. CONCLUSIONS: There were statistically significant relationships between geochemical parameters, taxonomic composition, and the completeness of metabolic pathways. It was demonstrated that geochemical parameters define the structure and metabolic potential of microbial communities. Metabolic pathways of hydrocarbon oxidation was found to prevail in the studied communities, which corroborates the hypothesis on abiogenic synthesis of Uzon hydrothermal petroleum.

Production of biodiesel and succinic acid from the biomass of the microalga Micractinium sp. IC-44.

In this study, a combined approach to produce fatty acid methyl esters (FAMEs) and succinic acid from the biomass of the microalga Micractinium sp. IC-44 using ionic liquids (ILs) was presented. After 22 days of cultivation, the biomass productivity was 0.034 ± 0.001 g L-1day-1, and the lipid content was 11.5 ± 0.5%. Direct biomass transesterification using H2SO4 in the presence of IL [BMIM][HSO4] resulted in a FAME yield of 42.0 ± 4.3%, which exceeded the yields obtained after transesterification of extracted lipids (20.5 ± 3.5% using ILs and 27.1 ± 2.4% using methanol/chloroform) and direct biomass transesterification without using ILs (31.6 ± 1.7%). The residual biomass obtained after direct transesterification using ILs was subjected to acid hydrolysis (sugar yield was 81.1 ± 2.4%). The purified hydrolysate was fermented using Actinobacillus succinogenes 130Z to obtain a succinic acid yield of 0.67 g g-1 of fermentable sugars. Therefore, this study demonstrated the successful conversion of the Micractinium sp. IC-44 biomass into biodiesel and succinic acid.

One-pot synthesis of formic acid via hydrolysis-oxidation of potato starch in the presence of cesium salts of heteropoly acid catalysts.

Solid bifunctional catalysts based on cesium salts of V-containing heteropoly acids (CsHPA: Cs3.5H0.5PW11VO40, Cs4.5H0.5SiW11VO40, Cs3.5H0.5PMo11VO40) and Cs2.5H0.5PMo12O40 were used for studying one-pot hydrolysis-oxidation of potato starch to formic acid at 413-443 K and 2 MPa air mixture. It was shown that the optimum process temperature that prevents formic acid from destruction is 423 K. The studies were focused on the influence of the composition of heteropoly anions on the yield and selectivity of formic acid. Using W-V-P(Si) CsHPA results in the product overoxidation compared to Mo-V-containing CsHPA. The activity of Cs-PMo was significantly lower compared to Cs-PMoV. This may indicate that vanadium plays an important role in the oxidation process. The most promising catalyst was Cs3.5H0.5PMo11VO40 which provided the maximum yield of formic acid equal to 51%. Cs3.5H0.5PMo11VO40 was tested during nine cycles of starch hydrolysis-oxidation to demonstrate its high stability and efficiency.

Spontaneous Resolution and Super-coiling in Xerogels of the Products of Photo-Induced Formose Reaction.

This work addresses the supramolecular self-organization in the xerogels of formose reaction products. The UV-induced formose reaction was held in over-saturated formaldehyde solutions at 70∘C without a catalyst. The solutions of the obtained carbohydrates were dried on a glass slide, and the obtained xerogels demonstrated a prominent optical activity, while the initial solutions were optically inactive. The xerogels contained highly elongated crystalline elements of a helical structure as well as the isometric ones. Thus xerogel formation was accompanied by a spontaneous resolution of enantiomers and separation of different-shaped supramolecular structures. The thick helices were twisted of thinner ones, while the latter were twisted of elementary structures having a diameter much smaller than 400 nm. Similar structural hierarchy is typical of biological macromolecules (DNA, proteins, and cellulose). Summarizing the obtained results, we proposed a hypothetical mechanism explaining the amplification of the initial enantiomeric excess, as well as chiral and chemical purification of the substances which were essential for the evolution of Life to start.

Colloidal FeIII , MnIII , CoIII , and CuII Hydroxides Stabilized by Starch as Catalysts of Water Oxidation Reaction with One Electron Oxidant Ru(bpy)33.

Colloidal catalysts for oxidation of water to dioxygen, which are stable on storage and under the reaction conditions, are synthesized based on CoIII , MnIII , FeIII and CuII hydroxides. Stabilization of the colloids with dextrated starch allows the process of hydroxide ageing to be stopped at the stage of the formation of primary nuclei (ca. 2-3 nm from transmission electron microscopy data). Molecular mechanics and dynamic light scattering studies indicate a core-shell type structure of the catalysts, where the hydroxide core is stabilized by the molecular starch network (ca. 5-7 nm). The colloidal catalysts are highly efficient in oxidizing water with one electron oxidant Ru(bpy)33+ at pH 7 to 10. The influence of pH, catalyst concentration, and buffer nature on the oxygen yield is studied. The maximal yields are 72, 53, and 78 % over Fe-, Mn- and Co-containing catalysts, respectively, and turnover numbers are 7.8; 54 and 360, respectively. The Cu-containing catalyst is poorly effective to the water oxidation (the maximal yield is 28 % O2 ). The synthesized catalysts are of interest for stopped-flow kinetic studies of the mechanism of the water oxidation and as precursors for anchoring nanosized hydroxides onto various supports in order to develop biomimetic systems for artificial photosynthesis.

Highly Stable Single-Atom Catalyst with Ionic Pd Active Sites Supported on N-Doped Carbon Nanotubes for Formic Acid Decomposition.

Single-atom catalysts with ionic Pd active sites supported on nitrogen-doped carbon nanotubes have been synthesized with a palladium content of 0.2-0.5 wt %. The Pd sites exhibited unexpectedly high stability up to 500 °C in a hydrogen atmosphere which was explained by coordination of the Pd ions by nitrogen-containing fragments of graphene layers. The active sites showed a high rate of gas-phase formic acid decomposition yielding hydrogen. An increase in Pd content was accompanied by the formation of metallic nanoparticles with a size of 1.2-1.4 nm and by a decrease in the catalytic activity. The high stability of the single-atom Pd sites opens possibilities for using such catalysts in high-temperature reactions.

Cloning, expression and characterization of the esterase estUT1 from Ureibacillus thermosphaericus which belongs to a new lipase family XVIII.

A new esterase gene from thermophilic bacteria Ureibacillus thermosphaericus was cloned into the pET32b vector and expressed in Escherichia coli BL21(DE3). Alignment of the estUT1 amino acid sequence revealed the presence of a novel canonical pentapeptide (GVSLG) and 41-47% identity to the closest family of the bacterial lipases XIII. Thus the esterase estUT1 from U. thermosphaericus was assigned as a member of the novel family XVIII. It also showed a strong activity toward short-chain esters (C2-C8), with the highest activity for C2. When p-nitrophenyl butyrate is used as a substrate, the temperature and pH optimum of the enzyme were 70-80 °C and 8.0, respectively. EstUT1 showed high thermostability and 68.9 ± 2.5% residual activity after incubation at 70 °C for 6 h. Homology modeling of the enzyme structure showed the presence of a putative catalytic triad Ser93, Asp192, and His222. The activity of estUT1 was inhibited by PMSF, suggesting that the serine residue is involved in the catalytic activity of the enzyme. The purified enzyme exhibited high stability in organic solvents. EstUT1 retained 85.8 ± 2.4% residual activity in 30% methanol at 50 °C for 6 h. Stability at high temperature and tolerance to organic solvents make estUT1 a promising enzyme for biotechnology application.

Cellulose Biorefinery Based on a Combined Catalytic and Biotechnological Approach for Production of 5-HMF and Ethanol.

In this study, a combination of catalytic and biotechnological processes was proposed for the first time for application in a cellulose biorefinery for the production of 5-hydroxymethylfurfural (5-HMF) and bioethanol. Hydrolytic dehydration of the mechanically activated microcrystalline cellulose over a carbon-based mesoporous Sibunt-4 catalyst resulted in moderate yields of glucose and 5-HMF (21.1-25.1 and 6.6-9.4 %). 5-HMF was extracted from the resulting mixture with isobutanol and subjected to ethanol fermentation. A number of yeast strains were isolated that also revealed high thermotolerance (up to 50 °C) and resistance to inhibitors found in the hydrolysates. The strains Kluyveromyces marxianus C1 and Ogataea polymorpha CBS4732 were capable of producing ethanol from processed catalytic hydrolysates of cellulose at 42 °C, with yields of 72.0±5.7 and 75.2±4.3 % from the maximum theoretical yield of ethanol, respectively.

Terminology spectrum analysis of natural-language chemical documents: term-like phrases retrieval routine.

BACKGROUND: This study seeks to develop, test and assess a methodology for automatic extraction of a complete set of 'term-like phrases' and to create a terminology spectrum from a collection of natural language PDF documents in the field of chemistry. The definition of 'term-like phrases' is one or more consecutive words and/or alphanumeric string combinations with unchanged spelling which convey specific scientific meanings. A terminology spectrum for a natural language document is an indexed list of tagged entities including: recognized general scientific concepts, terms linked to existing thesauri, names of chemical substances/reactions and term-like phrases. The retrieval routine is based on n-gram textual analysis with a sequential execution of various 'accept and reject' rules with taking into account the morphological and structural information. RESULTS: The assessment of the retrieval process, expressed quantitatively with a precision (P), recall (R) and F1-measure, which are calculated manually from a limited set of documents (the full set of text abstracts belonging to 5 EuropaCat events were processed) by professional chemical scientists, has proved the effectiveness of the developed approach. The term-like phrase parsing efficiency is quantified with precision (P = 0.53), recall (R = 0.71) and F1-measure (F1 = 0.61) values. CONCLUSION: The paper suggests using such terminology spectra to perform various types of textual analysis across document collections. This sort of the terminology spectrum may be successfully employed for text information retrieval, for reference database development, to analyze research trends in subject fields of research and to look for the similarity between documents.Graphical abstractTerminology spectrum building process with term-like phrases retrieval.

Catalytic formation of monosaccharides: from the formose reaction towards selective synthesis.

The formose reaction (FR) has been long the focus of intensive investigations as a simple method for synthesis of complex biologically important monosaccharides and other sugar-like molecules from the simplest organic substrate-formaldehyde. The fundamental importance of the FR is predominantly connected with the ascertainment of plausible scenarios of chemical evolution which could have occurred on the prebiotic Earth to produce the very first molecules of carbohydrates, amino- and nucleic acids, as well as other vitally important substances. The practical importance of studies on the FR is the elaboration of catalytic methods for the synthesis of rare and non-natural monosaccharides and polyols. This Minireview considers the FR from the point of view of chemists working in the field of catalysis with emphasis on the mechanisms of numerous parallel and consequent catalytic transformations that take place during the FR. Based on its kinetics, the FR may be considered as a non-radical chain process with degenerate branching. The Minireview also considers different approaches to the control of selectivity of carbohydrate synthesis from formaldehyde and lower monosaccharides.

Quantitative temperature mapping within an operating catalyst by spatially resolved 27Al NMR.

Spatially resolved NMR is employed to quantitatively map the temperature of a solid catalyst under operating conditions during H(2) oxidation with O(2) over Pt/γ-Al(2)O(3). As this new non-invasive in situ technique utilizes the (27)Al NMR signal of the solid phase, it is suitable for catalyst temperature mapping in both liquid- and gas-phase heterogeneous catalytic processes.

Pyrolysis of heavy hydrocarbons under microwave heating of catalysts and adsorbents.

The main features of high temperature chemical reactions under microwave (MW) heating have been considered. The efficiency of the MW power to heat conversion in a MW cavity is estimated, theoretically and experimentally, for different substances and conditions. The new approaches for MW processing of high-molecular hydrocarbons are proposed: (i) thermal decomposition in contact with microwave absorbing catalyst particles placed into liquid substrate; (ii) cracking of hydrocarbons pre-absorbed inside porous granules under rapid MW heating of adsorbent. It has been experimentally found that these approaches provide non-traditional conditions of reaction and can lead to the formation of valuable chemical products.

The state of absorbed hydrogen in the structure of reduced copper chromite from the vibration spectra.

The reduction of copper chromite, CuCr(2)O(4), is followed by means of thermogravimetric analysis. The reduced state is studied by means of FT IR spectroscopy, Raman spectroscopy and inelastic neutron scattering. The reduction of copper occurs in two stages: absorption of hydrogen at 250-400 degrees C and dehydration of the reduced state at above 450 degrees C. The measured vibrational spectra prove that a considerable amount of hydrogen is absorbed by the oxide structure with absorbed protons stabilized in OH and HOH-groups (geminal protons). Three groups of vibration bands are observed in the INS spectra, which can be assigned to stretching, bending and libration vibrations. An increase in the reduction temperature of copper chromite results in softening of the stretching and hardening of the bending vibrations, what can be related to the strengthening of hydrogen bonding.

Significant influence of Zn on activation of the C-H bonds of small alkanes by Brønsted acid sites of zeolite.

Herein, we analyze earlier obtained and new data about peculiarities of the H/D hydrogen exchange of small C(1)-n-C(4) alkanes on Zn-modified high-silica zeolites ZSM-5 and BEA in comparison with the exchange for corresponding purely acidic forms of these zeolites. This allows us to identify an evident promoting effect of Zn on the activation of C-H bonds of alkanes by zeolite Brønsted sites. The effect of Zn is demonstrated by observing the regioselectivity of the H/D exchange for propane and n-butane as well as by the increase in the rate and a decrease in the apparent activation energy of the exchange for all C(1)-n-C(4) alkanes upon modification of zeolites with Zn. The influence of Zn on alkane activation has been rationalized by dissociative adsorption of alkanes on Zn oxide species inside zeolite pores, which precedes the interaction of alkane with Brønsted acid sites.

On the influence of the metal loading on the structure of carbon-supported PtRu catalysts and their electrocatalytic activities in CO and methanol electrooxidation.

PtRu (1:1) catalysts supported on low surface area carbon of the Sibunit family (S(BET) = 72 m(2) g(-1)) with a metal percentage ranging from 5 to 60% are prepared and tested in a CO monolayer and for methanol oxidation in H(2)SO(4) electrolyte. At low metal percentage small (<2 nm) alloy nanoparticles, uniformly distributed on the carbon surface, are formed. As the amount of metal per unit surface area of carbon increases, particles start coalescing and form first quasi two-dimensional, and then three-dimensional metal nanostructures. This results in a strong enhancement of specific catalytic activity in methanol oxidation and a decrease of the overpotential for CO monolayer oxidation. It is suggested that intergrain boundaries connecting crystalline domains in nanostructured PtRu catalysts produced at high metal-on-carbon loadings provide active sites for electrocatalytic processes.

Mechanism studies of the conversion of 13C-labeled n-butane on zeolite H-ZSM-5 by using 13C magic angle spinning NMR spectroscopy and GC-MS analysis.

By using 13C MAS NMR spectroscopy (MAS = magic angle spinning), the conversion of selectively 13C-labeled n-butane on zeolite H-ZSM-5 at 430-470 K has been demonstrated to proceed through two pathways: 1) scrambling of the selective 13C-label in the n-butane molecule, and 2) oligomerization-cracking and conjunct polymerization. The latter processes (2) produce isobutane and propane simultaneously with alkyl-substituted cyclopentenyl cations and condensed aromatic compounds. In situ 13C MAS NMR and complementary ex situ GC-MS data provided evidence for a monomolecular mechanism of the 13C-label scrambling, whereas both isobutane and propane are formed through intermolecular pathways. According to 13C MAS NMR kinetic measurements, both pathways proceed with nearly the same activation energies (E(a) = 75 kJ mol(-1) for the scrambling and 71 kJ mol(-1) for isobutane and propane formation). This can be rationalized by considering the intermolecular hydride transfer between a primarily initiated carbenium ion and n-butane as being the rate-determining stage of the n-butane conversion on zeolite H-ZSM-5.

Noninvasive in situ visualization of supported catalyst preparations using multinuclear magnetic resonance imaging.

Multinuclear magnetic resonance imaging (MRI) is employed as a new noninvasive tool for monitoring supported catalyst preparation by visualizing precursor transport within the porous support. In particular, liquid phase 31P MRI experiments were used to visualize the dynamics of H3PO4 penetration into an alumina pellet and have revealed a strong interaction of H3PO4 with the support. Solid state 31P MRI was applied to map the distribution of the adsorbed phosphate inside the support after its drying. Comparison of the liquid phase and solid phase MRI results confirms the correlation of the phosphate distribution in the liquid phase during impregnation and the phosphate adsorbed on the support. The possibility to monitor the transport of metal atoms within the support by a direct detection of their NMR signal is demonstrated for 195Pt nucleus during impregnation of an alumina pellet with an aqueous solution of H2PtCl6. Other possible strategies for the utilization of MRI to characterize in situ the preparation of supported catalysts and other supported materials are briefly discussed.