We propose that c-valerolactone (GVL), a naturally occurring chemical in fruits and a frequently used food additive, exhibits the most important characteristics of an ideal sustainable liquid, which could be used for the production of both energy and carbon-based consumer products. GVL is renewable, easy and safe to store and move globally in large quantities, has low melting (231 uC), high boiling (207 uC) and open cup flash (96 uC) points, a definitive but acceptable smell for easy recognition of leaks and spills, and is miscible with water, assisting biodegradation. We have established that its vapor pressure is remarkably low, even at higher temperatures (3.5 kPa at 80 uC). We have also shown by using 18 O-labeled water that GVL does not hydrolyze to gammahydroxypentanoic acid under neutral conditions. In contrast, after the addition of acid (HCl) the incorporation of one or two 18 O-isotopes to GVL was observed, as expected. GVL does not form a measurable amount of peroxides in a glass flask under air in weeks, making it a safe material for large scale use. Comparative evaluation of GVL and ethanol as fuel additives, performed on a mixture of 10 v/v% GVL or EtOH and 90 v/v% 95-octane gasoline, shows very similar properties. Since GVL does not form an azeotrope with water, the latter can be readily removed by distillation, resulting in a less energy demanding process for the production of GVL than that of absolute ethanol. Finally, it is also important to recognize that the use of a single chemical entity, such as GVL, as a sustainable liquid instead of a mixture of compounds, could significantly simplify its worldwide monitoring and regulation.
The multi-step conversion of sucrose to various C 5 -oxygenates and alkanes was achieved by integrating various homogeneous and heterogeneous catalytic systems. We have confirmed that the dehydration of sucrose to levulinic and formic acids is currently limited to about 30-40% in the presence of H 2 SO 4 , HCl, or Nafion NR50 in water. Performing the dehydration in the presence of a P(m-C 6 H 4 SO 3 Na) 3 modified ruthenium catalyst under hydrogen resulted in the in situ conversion of levulinic acid to c-valerolactone (GVL). Levulinic acid can be hydrogenated to GVL quantitatively by using P(m-C 6 H 4 SO 3 Na) 3 modified ruthenium catalyst in water or Ru(acac) 3 /PBu 3 / NH 4 PF 6 catalyst in neat levulinic acid. Formic acid can be used for the transfer hydrogenation of levulinic acid in water in the presence of [(g 6 -C 6 Me 6 )Ru(bpy)(H 2 O)][SO 4 ] resulting in GVL and 1,4-pentanediol. The hydrogenation of levulinic acid or GVL can be performed to yield 1,4-pentanediol and/or 2-methyl-tetrahydrofuran (2-Me-THF). The hydrogenolysis of 2-Me-THF in the presence of Pt(acac) 2 in CF 3 SO 3 H resulted in a mixture of alkanes. We have thus demonstrated that the conversion of carbohydrates to various C 5 -oxygenates and even to alkanes can be achieved by selecting the proper catalysts and conditions, which could provide a renewable platform for the chemical industry.
Carbon dioxide methanation is well known to offer some advantages and be catalyzed by Ru, Rh, Pd, and Ni. In this study, Ni catalysts supported on various metal oxides were fabricated and their catalytic activity for CO2 methanation was evaluated. The CO2 conversion for most of catalysts drastically increased at 225-250 ºC and reached a maximal value at 300-350 ºC. The order of CH4 yield at 250 ºC was as follows; Ni/Y2O3 > Ni/Sm2O3 > Ni/ZrO2 > Ni/CeO2 > Ni/Al2O3 > Ni/La2O3. The catalytic activity could be partly explained by the basic property of the catalysts. Moreover, the chemical species formed on the catalyst surface during CO2 methanation were examined by in situ infrared spectroscopy. From the obtained results, the difference in the activity depending on the support material of Ni catalysts was discussed.
Densities and viscosities have been measured for the binary mixtures of acetonitrile with linear and brached alkanols (C1−C4) over the entire composition range at (298.15, 303.15, 308.15, and 313.15) K. The experimental density (ρ) and viscosity (η) values were used to calculate the excess molar volume (V E) and viscosity deviation (Δη). The effects of chain length and branching of alkanols on V E and Δη values have been discussed. The V E and Δη values are fitted to a Redlich−Kister equation.
Ionic liquids containing the hexafluoroacetylacetonate anion are immiscible with water and they exhibit strong metal-complexing ability.
The further development of the field of catalysis is based on the discovery, understanding, and implementation of novel activation modes that allow unprecedented transformations and open new perspectives in synthetic chemistry. In this context, the recently introduced concept of frustrated Lewis pair (FLP) from the Stephan research group represents a fundamental and novel strategy to develop catalysts based on main-group elements for small-molecule activation.[1] These sterically encumbered Lewis acid-base systems are not able to form a stable donor-acceptor adduct, nevertheless, an intermolecular association of the Lewis acidic (LA) and basic (LB) components to a unique "frustrated complex" was proposed. [2,3] Our research group has also shown that this encounter pair cleaves hydrogen in a cooperative manner and the steric congestion implies a strain, which can be directly utilized for bond activation. [2] Using steric hindrance as a critical design element, several combinations of bulky Lewis acid-base pairs were effectively probed for heterolytic cleavage of hydrogen. [4][5][6] Moreover, this remarkable capacity of FLPs was exploited in metal-free hydrogenation procedures.[7] Additionally, the bifunctional and unquenched nature of the FLPs makes them capable of reacting with alkenes, [8] dienes, [9] acetylenes, [10] and THF.[5f]Although this type of reactivity represents a breakthrough in main-group chemistry, its enhanced and non-orthogonal nature obviously limits the synthetic applicability of FLPs. Herein we report an attempt to develop frustrated Lewis pairs with orthogonal reactivity and improved functional-group tolerance for catalytic metal-free hydrogenation. The previously reported FLP-based hydrogen activation relied mostly on tris(pentafluorophenyl)borane [11] (1) as the LA component.[12] Because of the hard-type Lewis acidity of boron in 1 and its inactivation by common oxygen-and/or nitrogen-containing molecules, careful substrate design was needed for successful catalytic hydrogenation reactions. This synthetic limitation triggered us to develop FLP catalysts that have a broader range of applications and possible selectivity in reduction processes.Our design concept for increased functional-group tolerance is based on the simple hypothesis that steric hindrance in FLPs is a relative phenomenon (Figure 1): further increase of congestion around the boron center in FLP I and its parallel decrease around the LB could lead to a Lewis pair (FLP II) that may have a markedly higher tolerance for the functionalities of common organic molecules. Thus, the steric demands imposed on the boron center by additional orthoaryl substituents are such that they can prevent or markedly decrease the complexation ability with normal Lewis bases but still allow the cleavage of the small hydrogen molecule. Additionally, we assumed that the increased shielding around boron in FLP II could preclude its addition to olefins, therefore creating a unique opportunity to investigate the chemoselectivity of FLP-catalyzed hydroge...
Catalytic hydrogenation that utilizes frustrated Lewis pair (FLP) catalysts is a subject of growing interest because such catalysts offer a unique opportunity for the development of transition-metal-free hydrogenations. The aim of our recent efforts is to further increase the functional-group tolerance and chemoselectivity of FLP catalysts by means of size-exclusion catalyst design. Given that hydrogen molecule is the smallest molecule, our modified Lewis acids feature a highly shielded boron center that still allows the cleavage of the hydrogen but avoids undesirable FLP reactivity by simple physical constraint. As a result, greater latitude in substrate scope can be achieved, as exemplified by the chemoselective reduction of α,β-unsaturated imines, ketones, and quinolines. In addition to synthetic aspects, detailed NMR spectroscopic, DFT, and (2)H isotopic labeling studies were performed to gain further mechanistic insight into FLP hydrogenation.
A series of nitrile-functionalized ionic liquids were found to exhibit temperature-dependent miscibility (thermomorphism) with the lower alcohols. Their coordinating abilities toward cobalt(II) ions were investigated through the dissolution process of cobalt(II) bis(trifluoromethylsulfonyl)imide and were found to depend on the donor abilities of the nitrile group. The crystal structures of the cobalt(II) solvates [Co(C(1)C(1CN)Pyr)(2)(Tf(2)N)(4)] and [Co(C(1)C(2CN)Pyr)(6)][Tf(2)N](8), which were isolated from ionic-liquid solutions, gave an insight into the coordination chemistry of functionalized ionic liquids. Smooth layers of cobalt metal could be obtained by electrodeposition of the cobalt-containing ionic liquids.
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