- New Insights into CO2 Absorption Mechanisms with Amino-Acid Ionic Liquids
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The last decade saw an explosion of interest in using amine-functionalized materials for CO2 capture and conversion, and it is of great importance to elucidate the relationship between the molecular structure of amine-functionalized materials and their CO2 capacity. In this work, based on a new quantitative analysis method for the CO2 absorption mechanism of amino-acid ionic liquids (ILs) and quantum chemical calculations, we show that the small difference in the local structure of amine groups in ILs could lead to much different CO2 absorption mechanisms, which provides an opportunity for achieving higher CO2 capacity by structure design. This work revealed that the actual CO2 absorption mechanism by amino-acid ILs goes beyond the apparent CO2/amine stoichiometry; a rigid ring structure around the amine group in ILs creates a unique electrostatic environment that inhibits the deprotonation of carbamic acid and enables actually equimolar CO2/amine absorption.
- Yang, Qiwei,Wang, Zhiping,Bao, Zongbi,Zhang, Zhiguo,Yang, Yiwen,Ren, Qilong,Xing, Huabin,Dai, Sheng
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- Low-Temperature Tailoring of Copper-Deficient Cu3- xP - Electric Properties, Phase Transitions, and Performance in Lithium-Ion Batteries
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A convenient approach for a controlled and high-yield synthesis of copper-deficient Cu3-xP (0.1 3-xP shows a high degree of tolerance for cation vacancies without major structural reorganization, as evidenced by X-ray diffraction and solid-state nuclear magnetic resonance spectroscopy. Measurements of the electric properties reveal that Cu3-xP is a bad metallic p-type conductor. The resistivity is composition-dependent and displays a distinct anomaly from a phase transition, leading to the discovery and structural characterization of two hitherto unknown low temperature polymorphs. Electrochemical evaluation of copper-deficient Cu3-xP as anode material for lithium ion batteries reveals a drastic change in the cycling mechanism leading to an increase of the initial capacities by about 70%. This work gives a comprehensive insight into the chemical and structural features of copper-deficient Cu3-xP and should lead to an improved understanding of its properties, not just for battery applications.
- Wolff, Alexander,Doert, Thomas,Hunger, Jens,Kaiser, Martin,Pallmann, Julia,Reinhold, Romy,Yogendra, Sivatmeehan,Giebeler, Lars,Sichelschmidt, J?rg,Schnelle, Walter,Whiteside, Rachel,Gunaratne, H. Q. Nimal,Nockemann, Peter,Weigand, Jan J.,Brunner, Eike,Ruck, Michael
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p. 7111 - 7123
(2018/10/15)
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- Amphiphilic and phase-separable ionic liquids for biomass processing
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One main limiting factor for the technoeconomics of future bioprocesses that use ionic liquids (ILs) is the recovery of the expensive and potentially toxic IL. We have demonstrated a new series of phase-separable ionic liquids, based on the hydrophobic tetraalkylphosphonium cation ([PRRRR] +), that can dissolve lignin in the neat state but also hemicellulose and high-purity cellulose in the form of their electrolyte solutions with dipolar aprotic solvents. For example, the IL trioctylmethylphosphonium acetate ([P8881][OAc]) was demonstrated to dissolve up to 19 wt % of microcrystalline cellulose (MCC) at 60 °C with the addition of 40 wt % of DMSO. It was found that the MCC saturation point is dependent on the molar ratio of DMSO and IL in solution. At the optimum saturation, a ~1:1 molar ratio of [P8881][OAc] to anhydroglucose units is observed, which demonstrates highly efficient solvation. This is attributed to the positive contribution that these more amphiphilic cation-anion pairs provide, in the context of the Lindman hypothesis. This effective dissolution is further illustrated by solution-state HSQC NMR spectroscopy on MCC. Finally, it is also demonstrated that these electrolytes are phase separable by the addition of aqueous solutions. The addition of 10 % NaOAc solution allows a near quantitative recovery of high-purity [P8881][OAc]. However, increased volumes of aqueous solution reduced the recovery. The regenerated material was found to partially convert into the cellulose II crystalline polymorph. Solving the dissolving: Hydrophobic wood-biopolymer-solvating ionic liquids are developed that are phase separable from aqueous solutions as a means of recycling. These ionic liquids are excellent solvents for cellulose in the form of their DMSO electrolyte solutions but only dissolve lignin as the pure ionic liquids.
- Holding, Ashley J.,Heikkilae, Mikko,Kilpelaeinen, Ilkka,King, Alistair W. T.
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p. 1422 - 1434
(2014/06/09)
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- Tuning anion-functionalized ionic liquids for improved SO2 capture
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You can have your cake and eat it too: A "dual-tuning" strategy for improving the capture of SO2 was developed by introducing electron-withdrawing sites on the anions to produce several kinds of functionalized ionic liquids. Those functionalize
- Cui, Guokai,Zheng, Junjie,Luo, Xiaoyan,Lin, Wenjun,Ding, Fang,Li, Haoran,Wang, Congmin
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p. 10620 - 10624
(2013/10/21)
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