170,357 research outputs found
Structure and dynamics of 1-ethyl-3-methylimidazolium acetate via molecular dynamics and neutron diffraction
No full textLow-field 2D NMR relaxation and DRIFTS studies of glucose isomerization in zeolite Y: New insights into adsorption effects on catalytic performance
Full text linkSn and Ga doped zeolite Y catalysts were tested for the isomerization of glucose to fructose carried out in different solvents (water, methanol and ethanol). Therein, ethanol favoured a Lewis acid site catalyzed pathway that promotes glucose isomerization to fructose, whereas methanol resulted in an equal distribution of products (mannose, fructose and alkyl fructoside). In contrast, the catalysts were totally inactive in water solvent. NMR relaxation measurements, including solvent displacement experiments, suggested that the lack of catalytic activity in water is due to the strong adsorption of this solvent within the zeolite pores blocking reactants from the Lewis acid sites active for the sugar isomerization. In comparison, ethanol adsorbs relatively more strongly than methanol, hence is retained in the pores where solvated fructose is preferentially prevented from the further reaction on Bronsted acid sites situated outside of the pore space. NMR relaxation measurements using pyridine and tetrahydrofuran (THF) and pyridine-DRIFTS measurements suggest metal doping had little effect on the overall relative acid strength of the zeolites but resulted in zeolites with increased Lewis acid strength relative to the non-doped zeolites. The results reported provide direct experimental evidence on the importance of adsorption properties of solvents within zeolites used for glucose to fructose isomerization and may serve as a starting point for a new approach towards designing and optimizing such catalytic systems. & COPY; 2023 The Author(s). Published by Elsevier Inc. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/)
Structure of ionic liquid-benzene mixtures
No full textNeutron diffraction has been used to investigate the structure of liquid mixtures of 1,3-dimethylimidazolium hexafluorophosphate with benzene. Two concentrations of benzene were investigated, namely, 33 mol % and 67 mol %, and show similar structures in each case. The presence of benzene significantly alters the ionic liquid structure, in particular, in the cation-cation interactions, in agreement with the single-crystal structure described recently (Holbrey, J. D.; Reichert, W. M.; Nieuwenhuyzen, M.; Sheppard, O.; Hardacre, C.; Rogers, R. D. Chem. Commun. 2003, 476). In each case, the data was analyzed using an empirical potential structure refinement process.</p
Diffusion, ion pairing and aggregation in 1-ethyl-3-methylimidazolium-based ionic liquids studied by 1H and 19F PFG NMR: Effect of temperature, anion and glucose dissolutio
No full textIn this work, using 1H and 19F PFG NMR, we probe the effect of temperature, ion size/type and glucose dissolution on the rate of transport in 1-ethyl-3-methylimidazolium ([EMIM]+)-based ionic liquids by measuring self-diffusion coefficients. Using such data, we are able to establish the degree of ion pairing and quantify the extent of ionic aggregation during diffusion. For the neat 1-ethyl-3-methylimidazolium acetate ([EMIM][OAc]) a strong degree of ion pairing is observed. The substitution of the [OAc]− anion with the bis{(trifluoromethyl)sulfonyl}imide ([TFSI]−) anion reduces the pairing between the ions, which is attributed to a lower electric charge density on the [TFSI]− anion, hence a weaker electric interaction with the [EMIM]+ cation. The effect of glucose, important for applications of ionic liquids as extracting media, on the strongly paired [EMIM][OAc] sample was also investigated and it is observed that the carbohydrate decreases the degree of ion pairing, which is attributed to the ability of glucose to disrupt inter-ionic interactions by forming hydrogen bonding, particularly with the [OAc]− anion. Calculations of aggregation number from diffusion data show that the [OAc]− anion diffuses as a part of larger aggregates compared to the [EMIM]+ cation. The results and analysis presented here show the usefulness of PFG NMR in studies of ionic liquids, giving new insights into ion pairing and aggregation and the factors affecting these parameters
Assessing the effect of reducing agents on the selective catalytic reduction of NOx over Ag/Al2O3 catalysts
No full textThe selective catalytic reduction (SCR) of NOx in the presence of different reducing agents over Ag/Al2O3 prepared by wet impregnation was investigated by probing catalyst activity and using NMR relaxation time analysis to probe the strength of surface interaction of the various reducing agent species and water. The results reveal that the strength of surface interaction of the reducing agent relative to water, the latter present in engine exhausts as a fuel combustion product and, in addition, produced during the SCR reaction, plays an important role in determining catalyst performance. Reducing agents with weak strength of interaction with the catalyst surface, such as hydrocarbons, show poorer catalytic performance than reducing agents with a higher strength of interaction, such as alcohols. This is attributed to the greater ability of oxygenated species to compete with water in terms of surface interaction with the catalyst surface, hence reducing the inhibiting effect of water molecules blocking catalyst sites. The results support the observations of earlier work in that the light off-temperature and maximum NOx conversion and temperature at which that occurs are sensitive to the reducing agent present during reaction, and the proposal that improved catalyst performance is caused by increased adsorption strength of the reducing agent, relative to water, at the catalyst surface. Importantly, the NMR relaxation time analysis approach to characterising the strength of adsorption more readily describes the trends in catalytic behaviour than does a straightforward consideration of the polarity (i.e., relative permittivity) of the reducing agents studied here. In summary, this paper describes a simple approach to characterising the interaction energy of water and reducing agent so as to aid the selection of reducing agent and catalyst to be used in SCR conversions
Temperature Dependence of the Primary Relaxation in 1-Hexyl-3-methylimidazolium bis{(trifluoromethyl)sulfonyl}imide
No full textWe present results from complementary characterizations of the primary relaxation rate of a room temperature ionic liquid (RTIL), 1-hexyl-3-methylimidazolium bis{(trifluoromethyl)sulfonyl} imide, [C(6)mim][Tf2N], over a wide temperature range. This extensive data set is successfully merged with existing literature data for conductivity, viscosity, and NMR diffusion coefficients thus providing, for the case of RTILs, a unique description of the primary process relaxation map over more than 12 decades in relaxation rate and between 185 and 430 K. This unique data set allows a detailed characterization of the VTF parameters for the primary process, that are: B = 890 K, T-0 = 155.2 K, leading to a fragility index m = 71, corresponding to an intermediate fragility. For the first time neutron spin echo data from a fully deuteriated sample of RTIL at the two main interference peaks, Q = 0.76 and 1.4 angstrom(-1) are presented. At high temperature (T > 250 K), the collective structural relaxation rate follows the viscosity behavior; however at lower temperatures it deviates from the viscosity behavior, indicating the existence of a faster process
Investigation of reactivity and surface modifications of mechanochemically prepared Ag/Al2O3 catalyst for the selective catalytic reduction with hydrocarbon
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Going Beyond Counting First Authors in Author Co-citation Analysis
Full text linkThe present study examines one of the fundamental aspects of author co-citation analysis (ACA) - the way co-citation
counts are defined. Co-citation counting provides the data on which all subsequent statistical analyses and mappings
are based, and we compare ACA results based on two different types of co-citation counting - the traditional type that
only counts the first one among a cited work's authors on the one hand and a non-traditional type that takes into
account the first 5 authors of a cited work on the other hand. Results indicate that the picture produced through this non-traditional author co-citation counting contains more coherent author groups and is therefore considerably clearer. However, this picture represents fewer specialties in the research field being studied than that produced through the traditional first-author co-citation counting when the same number of top-ranked authors is selected and analyzed. Reasons for these effects are discussed
Development of a PtSn bimetallic catalyst for direct fuel cells using bio-butanol fuel
Full text linkPt and PtSn catalysts were studied for n-butanol electro-oxidation at various temperatures. PtSn showed a higher activity towards butanol electro-oxidation compared to Pt in acidic media. The onset potential for n-butanol oxidation on PtSn is ~520 mV lower than that found on Pt, and significantly lower activation energy was found for PtSn compared with that for Pt
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