Актуальне конституційно-правове дослідження з проблематики муніципальної влади в Україні

Рецензія на кн.: Батанов О.В. Муніципальна влада в Україні: проблеми теорії та практики: Монографія /Відп. ред. М.О. Баймуратов.- К.: ТОВ «Видавництво «Юридична думка», 2010. - 656 с

Reductive dealkylation of anisole and phenetole: towards practical lignin conversion

We present and develop alternative catalysts for biomass conversion and specifically lignin conversion into aromatics. Unlike the conventional CoMo and NiMo formulations, our catalysts can convert low-sulfur feedstocks. A set of five magnesia–alumina mixed oxides were screened in the hydrodealkylation of alkyl phenyl ethers as lignin model compounds. The typical selectivity to phenol is 30–75 %. Interestingly, we saw that the more basic the catalyst, the higher the selectivity for phenol. The results concur with the formation of phenoxide (PhO(–)) and RH(3)(+) fragments on the catalyst surface. These can then react with H(+) and H(–) species formed by the hydrogen dissociation on the MgO surface, giving phenol and hydrocarbons. We conclude that magnesia–alumina mixed oxides are attractive candidates for catalyzing lignin breakdown. These catalysts are highly stable, inexpensive, and readily available

Seasonal cultivated and fallow cropland mapping using MODIS-based automated cropland classification algorithm

Increasing drought occurrences and growing populations demand accurate, routine, and consistent cultivated and fallow cropland products to enable water and food security analysis. The overarching goal of this research was to develop and test automated cropland classification algorithm (ACCA) that provide accurate, consistent, and repeatable information on seasonal cultivated as well as seasonal fallow cropland extents and areas based on the Moderate Resolution Imaging Spectroradiometer remote sensing data. Seasonal ACCA development process involves writing series of iterative decision tree codes to separate cultivated and fallow croplands from noncroplands, aiming to accurately mirror reliable reference data sources. A pixel-by-pixel accuracy assessment when compared with the U.S. Department of Agriculture (USDA) cropland data showed, on average, a producer's accuracy of 93% and a user's accuracy of 85% across all months. Further, ACCA-derived cropland maps agreed well with the USDA Farm Service Agency crop acreage-reported data for both cultivated and fallow croplands with R-square values over 0.7 and field surveys with an accuracy of >= 95% for cultivated croplands and >= 76% for fallow croplands. Our results demonstrated the ability of ACCA to generate cropland products, such as cultivated and fallow cropland extents and areas, accurately, automatically, and repeatedly throughout the growing season

Influence of reaction conditions on the composition of liquid products from two-stage catalytic hydrothermal processing of lignin.

The influence of reaction conditions on the composition of liquid products during two-stage hydrothermal conversion of alkali lignin has been investigated in a batch reactor. Reactions were carried out in the presence of formic acid (FA) and Pt/Al2O3 catalyst. The two different sets of reaction conditions involved alternative reaction times of 1 h and 5 h at 265 °C and 350 °C, respectively. These provided different contributions to reaction severity, which affected the compositions of liquid products. Yields of liquid products reached up to 40 wt% (on lignin feed basis) in the presence of FA under the less severe reaction condition. With 5 h reaction time at 350 °C, alkylphenols, alkylguaiacols and hydrocarbons were the dominant liquid products. However, with 5 h reaction time at 265 °C, phenol and methanol became dominant. The two-stage hydrothermal process led to improved lignin conversion, with the potential to manipulate the liquid product range

Investigating the roles of T224 and T232 in the oxidation of cinnamaldehyde catalyzed by myxobacterial CYP260B1

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/136018/1/feb212519-sup-0001-Supinfo.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/136018/2/feb212519.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/136018/3/feb212519_am.pd

Regioselective Baeyer-Villiger oxidation of lignin model compounds with tin beta zeolite catalyst and hydrogen peroxide

Lignin depolymerization represents a promising approach to the sustainable production of aromatic molecules. One potential approach to the stepwise depolymerization of lignin involves oxidation of the benzylic alcohol group in β-O-4 and β-1 linkages, followed by Baeyer-Villiger oxidation (BVO) of the resulting ketones and subsequent ester hydrolysis. Towards this goal, BVO reactions were performed on 2-adamantanone, a series of acetophenone derivatives, and lignin model compounds using a tin beta zeolite/hydrogen peroxide biphasic system. XRD, 119Sn MAS NMR spectroscopy, DRUVS and XPS were used to determine tin speciation in the catalyst, the presence of both framework Sn and extra framework SnO2 being inferred. Conversion of ketones to BVO products was affected by electron donation as well as steric hindrance, 4′-methoxyacetophenone affording the highest yield of ester (81%). As the size and complexity of the ketone increased, excess hydrogen peroxide was typically needed for successful BVO. Yields of ester products derived from β-O-4 and β-1 lignin models were modest due to the formation of polymeric material stemming from direct ring hydroxylation

Influence of Carbon Supports on Palladium Nanoparticle Activity toward Hydrodeoxygenation and Aerobic Oxidation in Biomass Transformations

[EN] Three palladium catalysts at similar loadings supported on few-layers graphene (FLG), carbon nanotubes (CNT) and carbon nanofibers (CNF) have been prepared by wet impregnation of palladium nitrate with the purpose of determine the influence of the support on Pd catalytic activity. The supports and catalysts have been characterized by chemical analysis, Raman spectroscopy, XRD, electron microscopy and XPS. The average Pd particle size depends on the carbon support, ranging from 1.6 nm for CNF to 2.6 nm for FLG. The catalytic activity of these catalysts was evaluated for two different reactions of interest for biomass transformations, namely hydrodeoxygenation of vanillin to 2-methoxy-4-methyl-phenol (creosol) that requires a bifunctional catalyst with hydrogenating and Lewis acid sites, and aerobic oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid. Both compounds have application either as food flavouring additive and polyester co-monomer. For the two reactions the activity order of the fresh catalyst was Pd/FLG > Pd/CNF > Pd/CNT, indicating that FLG contributes favorably to the activity in spite of the larger Pd size of the nanoparticles on this support, a fact that has been attributed to the interaction with the prismatic planes on where Pd nanoparticles are located.Financial support by the Spanish Ministry of Economy and Competitiveness (Severo Ochoa GTQ2015-65163-C02-R1 and CTQ2014-53292-R) is gratefully acknowledged. Generalidad Valenciana is also thanked for funding (Prometeo 2017/063). S. N. thanks financial support by the Fundacion Ramon Areces (XVIII Concurso Nacional para la Adjudicacion de Ayudas a la Investigacion en Ciencias de la Vida y de la Materia, 2016). C. R. C. thanks CONICYT for the financial support (Becas de doctorado en el extranjero "Becas Chile" - no 72170200). The authors thank Dr. Tobias Placke (Universitat Munster, Germany) for nitrogen adsorption measurements and adsorptive potential distributions calculations.Espinosa-López, JC.; Castro Contreras, R.; Navalón Oltra, S.; Rivera-Cárcamo, C.; Alvaro Rodríguez, MM.; Machado, BF.; Serp, P.... (2019). Influence of Carbon Supports on Palladium Nanoparticle Activity toward Hydrodeoxygenation and Aerobic Oxidation in Biomass Transformations. European Journal of Inorganic Chemistry. (14):1979-1987. https://doi.org/10.1002/ejic.201900190S1979198714Corma, A., Iborra, S., & Velty, A. (2007). Chemical Routes for the Transformation of Biomass into Chemicals. Chemical Reviews, 107(6), 2411-2502. doi:10.1021/cr050989dHuber, G. W., Iborra, S., & Corma, A. (2006). Synthesis of Transportation Fuels from Biomass:  Chemistry, Catalysts, and Engineering. Chemical Reviews, 106(9), 4044-4098. doi:10.1021/cr068360dNavarro, R. M., Peña, M. A., & Fierro, J. L. G. (2007). Hydrogen Production Reactions from Carbon Feedstocks:  Fossil Fuels and Biomass. Chemical Reviews, 107(10), 3952-3991. doi:10.1021/cr0501994Chheda, J. N., Huber, G. W., & Dumesic, J. A. (2007). Liquid-Phase Catalytic Processing of Biomass-Derived Oxygenated Hydrocarbons to Fuels and Chemicals. Angewandte Chemie International Edition, 46(38), 7164-7183. doi:10.1002/anie.200604274Zhou, C.-H., Xia, X., Lin, C.-X., Tong, D.-S., & Beltramini, J. (2011). Catalytic conversion of lignocellulosic biomass to fine chemicals and fuels. Chemical Society Reviews, 40(11), 5588. doi:10.1039/c1cs15124jWildgoose, G. G., Banks, C. E., & Compton, R. G. (2006). Metal Nanoparticles and Related Materials Supported on Carbon Nanotubes: Methods and Applications. Small, 2(2), 182-193. doi:10.1002/smll.200500324Zhu, J., Holmen, A., & Chen, D. (2013). Carbon Nanomaterials in Catalysis: Proton Affinity, Chemical and Electronic Properties, and their Catalytic Consequences. ChemCatChem, 5(2), 378-401. doi:10.1002/cctc.201200471Calvo-Flores, F. G., & Dobado, J. A. (2010). Lignin as Renewable Raw Material. ChemSusChem, 3(11), 1227-1235. doi:10.1002/cssc.201000157Upton, B. M., & Kasko, A. M. (2015). Strategies for the Conversion of Lignin to High-Value Polymeric Materials: Review and Perspective. Chemical Reviews, 116(4), 2275-2306. doi:10.1021/acs.chemrev.5b00345Zhang, F., Jin, Y., Fu, Y., Zhong, Y., Zhu, W., Ibrahim, A. A., & El-Shall, M. S. (2015). Palladium nanoparticles incorporated within sulfonic acid-functionalized MIL-101(Cr) for efficient catalytic conversion of vanillin. Journal of Materials Chemistry A, 3(33), 17008-17015. doi:10.1039/c5ta03524dSantos, J. L., Alda-Onggar, M., Fedorov, V., Peurla, M., Eränen, K., Mäki-Arvela, P., … Murzin, D. Y. (2018). Hydrodeoxygenation of vanillin over carbon supported metal catalysts. Applied Catalysis A: General, 561, 137-149. doi:10.1016/j.apcata.2018.05.010Hao, P., Schwartz, D. K., & Medlin, J. W. (2018). Phosphonic acid promotion of supported Pd catalysts for low temperature vanillin hydrodeoxygenation in ethanol. Applied Catalysis A: General, 561, 1-6. doi:10.1016/j.apcata.2018.05.008Zhang, F., Zheng, S., Xiao, Q., Zhong, Y., Zhu, W., Lin, A., & Samy El-Shall, M. (2016). Synergetic catalysis of palladium nanoparticles encaged within amine-functionalized UiO-66 in the hydrodeoxygenation of vanillin in water. Green Chemistry, 18(9), 2900-2908. doi:10.1039/c5gc02615fDavis, S. E., Ide, M. S., & Davis, R. J. (2013). Selective oxidation of alcohols and aldehydes over supported metal nanoparticles. Green Chem., 15(1), 17-45. doi:10.1039/c2gc36441gZhang, Z., & Deng, K. (2015). Recent Advances in the Catalytic Synthesis of 2,5-Furandicarboxylic Acid and Its Derivatives. ACS Catalysis, 5(11), 6529-6544. doi:10.1021/acscatal.5b01491Teong, S. P., Yi, G., & Zhang, Y. (2014). Hydroxymethylfurfural production from bioresources: past, present and future. Green Chemistry, 16(4), 2015. doi:10.1039/c3gc42018cSiyo, B., Schneider, M., Radnik, J., Pohl, M.-M., Langer, P., & Steinfeldt, N. (2014). Influence of support on the aerobic oxidation of HMF into FDCA over preformed Pd nanoparticle based materials. Applied Catalysis A: General, 478, 107-116. doi:10.1016/j.apcata.2014.03.020Rathod, P. V., & Jadhav, V. H. (2018). Efficient Method for Synthesis of 2,5-Furandicarboxylic Acid from 5-Hydroxymethylfurfural and Fructose Using Pd/CC Catalyst under Aqueous Conditions. ACS Sustainable Chemistry & Engineering, 6(5), 5766-5771. doi:10.1021/acssuschemeng.7b03124Machado, B. F., Oubenali, M., Rosa Axet, M., Trang NGuyen, T., Tunckol, M., Girleanu, M., … Serp, P. (2014). Understanding the surface chemistry of carbon nanotubes: Toward a rational design of Ru nanocatalysts. Journal of Catalysis, 309, 185-198. doi:10.1016/j.jcat.2013.09.016Placke, T., Siozios, V., Schmitz, R., Lux, S. F., Bieker, P., Colle, C., … Winter, M. (2012). Influence of graphite surface modifications on the ratio of basal plane to «non-basal plane» surface area and on the anode performance in lithium ion batteries. Journal of Power Sources, 200, 83-91. doi:10.1016/j.jpowsour.2011.10.085Themed Issue: Lithium Ions in Solids - Between Basics and Better Batteries / Paul Heitjans. Zeitschrift für Physikalische ChemieReshetenko, T. V., Avdeeva, L. B., Ismagilov, Z. R., Pushkarev, V. V., Cherepanova, S. V., Chuvilin, A. L., & Likholobov, V. A. (2003). Catalytic filamentous carbon. Carbon, 41(8), 1605-1615. doi:10.1016/s0008-6223(03)00115-5Estrade-Szwarckopf, H. (2004). XPS photoemission in carbonaceous materials: A «defect» peak beside the graphitic asymmetric peak. Carbon, 42(8-9), 1713-1721. doi:10.1016/j.carbon.2004.03.005Ganesan, K., Ghosh, S., Gopala Krishna, N., Ilango, S., Kamruddin, M., & Tyagi, A. K. (2016). A comparative study on defect estimation using XPS and Raman spectroscopy in few layer nanographitic structures. Physical Chemistry Chemical Physics, 18(32), 22160-22167. doi:10.1039/c6cp02033jOkpalugo, T. I. T., Papakonstantinou, P., Murphy, H., McLaughlin, J., & Brown, N. M. D. (2005). High resolution XPS characterization of chemical functionalised MWCNTs and SWCNTs. Carbon, 43(1), 153-161. doi:10.1016/j.carbon.2004.08.033Müller, J.-O., Su, D. S., Wild, U., & Schlögl, R. (2007). Bulk and surface structural investigations of diesel engine soot and carbon black. Phys. Chem. Chem. Phys., 9(30), 4018-4025. doi:10.1039/b704850eCançado, L. G., Jorio, A., Ferreira, E. H. M., Stavale, F., Achete, C. A., Capaz, R. B., … Ferrari, A. C. (2011). Quantifying Defects in Graphene via Raman Spectroscopy at Different Excitation Energies. Nano Letters, 11(8), 3190-3196. doi:10.1021/nl201432gCançado, L. G., Takai, K., Enoki, T., Endo, M., Kim, Y. A., Mizusaki, H., … Pimenta, M. A. (2006). General equation for the determination of the crystallite size La of nanographite by Raman spectroscopy. Applied Physics Letters, 88(16), 163106. doi:10.1063/1.2196057Domínguez-Domínguez, S., Berenguer-Murcia, Á., Pradhan, B. K., Linares-Solano, Á., & Cazorla-Amorós, D. (2008). Semihydrogenation of Phenylacetylene Catalyzed by Palladium Nanoparticles Supported on Carbon Materials. The Journal of Physical Chemistry C, 112(10), 3827-3834. doi:10.1021/jp710693uToebes, M. L., van Dillen, J. A., & de Jong, K. P. (2001). Synthesis of supported palladium catalysts. Journal of Molecular Catalysis A: Chemical, 173(1-2), 75-98. doi:10.1016/s1381-1169(01)00146-7Dong Jin Suh, Tae-Jin, P., & Son-Ki, I. (1993). Effect of surface oxygen groups of carbon supports on the characteristics of Pd/C catalysts. Carbon, 31(3), 427-435. doi:10.1016/0008-6223(93)90130-3Kang, M., Song, M. W., & Kim, K. L. (2002). Reaction Kinetics and Catalysis Letters, 76(2), 207-212. doi:10.1023/a:101656332309