Sample records for topochemistry
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Directory of Open Access Journals (Sweden)
Sheng Chen
2017-01-01
Full Text Available Ionic liquids (ILs as designer solvents have been applied in biomass pretreatment to increase cellulose accessibility and therefore improve the enzymatic hydrolysis. We investigated the characterization of the micromorphology and the topochemistry of poplar wood during 1-ethyl-3-methylimidazolium acetate pretreatment with mild conditions (90 °C for 20 and 40 min by multiple microscopic techniques (FE-SEM, CLSM, and CRM. Chemical composition analysis, XRD, cellulase adsorption isotherm, and enzymatic hydrolysis were also performed to monitor the variation of substrate properties. Our results indicated that the biomass conversion was greatly enhanced (from 20.57% to 73.64% due to the cell wall deconstruction and lignin dissolution (29.83% lignin was removed after incubation for 40 min, rather than the decrystallization or crystallinity transformation of substrates. The mild ILs pretreatment, with less energy input, can not only enhance enzymatic hydrolysis, but also provide a potential approach as the first step in improving the sequential pretreatment effectiveness in integrated methods. This study provides new insights on understanding the ILs pretreatment with low temperature and short duration, which is critical for developing individual and/or combined pretreatment technologies with reduced energy consumption.
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Indian Academy of Sciences (India)
Keywords. Organic solid state; topochemistry; crystal engineering; x-ray crystallography; molecular complexes; photochemistry; atom-atom potentials; solid state tautomerism; intercalation. 1. Introduction. How do organic molecules organise themselves in crystals? Can one predict the crystal structure of an organic solid?
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Pressure-induced chemistry in a nitrogen-hydrogen host-guest structure
Spaulding, Dylan K.; Weck, Gunnar; Loubeyre, Paul; Datchi, Fréderic; Dumas, Paul; Hanfland, Michael
2014-12-01
New topochemistry in simple molecular systems can be explored at high pressure. Here we examine the binary nitrogen/hydrogen system using Raman spectroscopy, synchrotron X-ray diffraction, synchrotron infrared microspectroscopy and visual observation. We find a eutectic-type binary phase diagram with two stable high-pressure van der Waals compounds, which we identify as (N2)6(H2)7 and N2(H2)2. The former represents a new type of van der Waals host-guest compound in which hydrogen molecules are contained within channels in a nitrogen lattice. This compound shows evidence for a gradual, pressure-induced change in bonding from van der Waals to ionic interactions near 50 GPa, forming an amorphous dinitrogen network containing ionized ammonia in a room-temperature analogue of the Haber-Bosch process. Hydrazine is recovered on decompression. The nitrogen-hydrogen system demonstrates the potential for new pressure-driven chemistry in high-pressure structures and the promise of tailoring molecular interactions for materials synthesis.
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Rocking-Chair Ammonium-Ion Battery: A Highly Reversible Aqueous Energy Storage System.
Wu, Xianyong; Qi, Yitong; Hong, Jessica J; Li, Zhifei; Hernandez, Alexandre S; Ji, Xiulei
2017-10-09
Aqueous rechargeable batteries are promising solutions for large-scale energy storage. Such batteries have the merit of low cost, innate safety, and environmental friendliness. To date, most known aqueous ion batteries employ metal cation charge carriers. Here, we report the first "rocking-chair" NH 4 -ion battery of the full-cell configuration by employing an ammonium Prussian white analogue, (NH 4 ) 1.47 Ni[Fe(CN) 6 ] 0.88 , as the cathode, an organic solid, 3,4,9,10-perylenetetracarboxylic diimide (PTCDI), as the anode, and 1.0 m aqueous (NH 4 ) 2 SO 4 as the electrolyte. This novel aqueous ammonium-ion battery demonstrates encouraging electrochemical performance: an average operation voltage of ca. 1.0 V, an attractive energy density of ca. 43 Wh kg -1 based on both electrodes' active mass, and excellent cycle life over 1000 cycles with 67 % capacity retention. Importantly, the topochemistry results of NH 4 + in these electrodes point to a new paradigm of NH 4 + -based energy storage. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Directory of Open Access Journals (Sweden)
Zhe Ling
2015-11-01
Full Text Available Although many studies have been conducted on the wood property and chemical changes caused by thermal modification, little has been reported on the microstructural and topochemical changes occurring in the cell wall during heat treatment. In this study, poplar (Populus cathayaha was treated within a temperature range from 180 to 220 °C for 4 h. Chemical analyses by Fourier transform infrared spectroscopy (FTIR and nuclear magnetic resonance (NMR indicated that heat treatment resulted in deacetylation of hemicelluloses and cleavage of lignin chains, thus generating new carbonyl and phenolic linkages. Transformation of matrix substances contributed to microstructural changes that appeared in clearly distorted and collapsed fiber and vessel walls along with the delamination of compound middle lamella (CML and secondary walls (S, which showed a reduced capability to resist deformation. It was also observed by fluorescence microscopy (FM and scanning electron microscope coupled with energy dispersive X-ray analysis (SEM-EDXA that the concentration of lignin increased, probably because of the degradation of hemicelluloses and the generation of new carbonyl groups. These results on cell wall microstructure and topochemistry can help explain the altered wood properties revealed by dynamic mechanical analysis (DMA and equilibrium moisture content (EMC testing after heat treatment.
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Structure and engineering of celluloses.
Pérez, Serge; Samain, Daniel
2010-01-01
This chapter collates the developments and conclusions of many of the extensive studies that have been conducted on cellulose, with particular emphasis on the structural and morphological features while not ignoring the most recent results derived from the elucidation of unique biosynthetic pathways. The presentation of structural and morphological data gathered together in this chapter follows the historical development of our knowledge of the different structural levels of cellulose and its various organizational levels. These levels concern features such as chain conformation, chain polarity, chain association, crystal polarity, and microfibril structure and organization. This chapter provides some historical landmarks related to the evolution of concepts in the field of biopolymer science, which parallel the developments of novel methods for characterization of complex macromolecular structures. The elucidation of the different structural levels of organization opens the way to relating structure to function and properties. The chemical and biochemical methods that have been developed to dissolve and further modify cellulose chains are briefly covered. Particular emphasis is given to the facets of topochemistry and topoenzymology where the morphological features play a key role in determining unique physicochemical properties. A final chapter addresses what might be considered tomorrow's goal in amplifying the economic importance of cellulose in the context of sustainable development. Selected examples illustrate the types of result that can be obtained when cellulose fibers are no longer viewed as inert substrates, and when the polyhydroxyl nature of their surfaces, as well as their entire structural complexity, are taken into account. Copyright © 2010 Elsevier Inc. All rights reserved.
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International Nuclear Information System (INIS)
Ranmohotti, K.G. Sanjaya; Montasserasadi, M. Dariush; Choi, Jonglak; Yao, Yuan; Mohanty, Debasish; Josepha, Elisha A.; Adireddy, Shiva; Caruntu, Gabriel; Wiley, John B.
2012-01-01
Highlights: ► Topochemical reactions involving intercalation allow construction of metal chalcogenide arrays within perovskite hosts. ► Gaseous chalcogen hydrides serve as effect reactants for intercalation of sulfur and selenium. ► New compounds prepared by a two-step intercalation strategy are presented. -- Abstract: A two-step topochemical reaction strategy utilizing oxidative intercalation with gaseous chalcogen hydrides is presented. Initially, the Dion-Jacobson-type layered perovskite, RbLaNb 2 O 7 , is intercalated reductively with rubidium metal to make the Ruddlesden-Popper-type layered perovskite, Rb 2 LaNb 2 O 7 . This compound is then reacted at room-temperature with in situ generated H 2 S gas to create Rb-S layers within the perovskite host. Rietveld refinement of X-ray powder diffraction data (tetragonal, a = 3.8998(2) Å, c = 15.256(1) Å; space group P4/mmm) shows the compound to be isostructural with (Rb 2 Cl)LaNb 2 O 7 where the sulfide resides on a cubic interlayer site surrounded by rubidium ions. The mass increase seen on sulfur intercalation and the refined S site occupation factor (∼0.8) of the product indicate a higher sulfur content than expected for S 2− alone. This combined with the Raman studies, which show evidence for an H-S stretch, indicate that a significant fraction of the intercalated sulfide exists as hydrogen sulfide ion. Intercalation reactions with H 2 Se (g) were also carried out and appear to produce an isostructural selenide compound. The utilization of such gaseous hydride reagents could significantly expand multistep topochemistry to a larger number of intercalants.
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Energy Technology Data Exchange (ETDEWEB)
Ranmohotti, K.G. Sanjaya; Montasserasadi, M. Dariush; Choi, Jonglak; Yao, Yuan; Mohanty, Debasish; Josepha, Elisha A.; Adireddy, Shiva; Caruntu, Gabriel [Department of Chemistry and the Advanced Materials Research Institute, University of New Orleans, New Orleans, LA 70148-2820 (United States); Wiley, John B., E-mail: jwiley@uno.edu [Department of Chemistry and the Advanced Materials Research Institute, University of New Orleans, New Orleans, LA 70148-2820 (United States)
2012-06-15
Highlights: ► Topochemical reactions involving intercalation allow construction of metal chalcogenide arrays within perovskite hosts. ► Gaseous chalcogen hydrides serve as effect reactants for intercalation of sulfur and selenium. ► New compounds prepared by a two-step intercalation strategy are presented. -- Abstract: A two-step topochemical reaction strategy utilizing oxidative intercalation with gaseous chalcogen hydrides is presented. Initially, the Dion-Jacobson-type layered perovskite, RbLaNb{sub 2}O{sub 7}, is intercalated reductively with rubidium metal to make the Ruddlesden-Popper-type layered perovskite, Rb{sub 2}LaNb{sub 2}O{sub 7}. This compound is then reacted at room-temperature with in situ generated H{sub 2}S gas to create Rb-S layers within the perovskite host. Rietveld refinement of X-ray powder diffraction data (tetragonal, a = 3.8998(2) Å, c = 15.256(1) Å; space group P4/mmm) shows the compound to be isostructural with (Rb{sub 2}Cl)LaNb{sub 2}O{sub 7} where the sulfide resides on a cubic interlayer site surrounded by rubidium ions. The mass increase seen on sulfur intercalation and the refined S site occupation factor (∼0.8) of the product indicate a higher sulfur content than expected for S{sup 2−} alone. This combined with the Raman studies, which show evidence for an H-S stretch, indicate that a significant fraction of the intercalated sulfide exists as hydrogen sulfide ion. Intercalation reactions with H{sub 2}Se{sub (g)} were also carried out and appear to produce an isostructural selenide compound. The utilization of such gaseous hydride reagents could significantly expand multistep topochemistry to a larger number of intercalants.