Solubility of Bioactive, Inorganic and Polymeric Solids in Ionic Liquids — Experimental and Prediction Perspectives

This work was supported by Fundação para a Ciência e a Tecnologia through projects (PEstC/LA0006/2013, PTDC/CTM/103664/2008, EXPL/QEQ ERQ/2243/2013) one contract under Investigador FCT (L.C. Branco); two Postdoctoral fellowships (G.V.S.M. Carrera - SFRH/BPD/72095/2010 and A. V. M. Nunes - SFRH/BPD/74994/2010) and one doctoral fellowship (M. E.Zakrzewska SFRH/BD/74929/2010).publishersversionpublishe

Influence of ionic liquid on polar organic compounds solubility in dense CO2 phase

Accurate measurement and prediction of the phase behaviour of mixtures involved in a chemical process are crucial for its optimisation. Given the importance of CO2 conversion technologies and considering possible benefits of CO2-ionic liquid biphasic systems, i.e., facilitating a product separation, we investigated the high-pressure behaviour of components of interest in a recently developed process of cyclic carbonate synthesis directly from CO2 and potentially bio-based alcohols. The solubility of 1,2-butanediol and 1,2-butylene carbonate in a dense carbon dioxide phase was determined experimentally at the temperature of 313.2 K and pressures between 6 and 18 MPa. The influence of 1-hexyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate ionic liquid, [hmim][FAP], as a solvent, on the solubility of these compounds in CO2-rich phase, in ternary (CO2 + 1,2-butanediol + [hmim][FAP]), CO2 + butylene carbonate + [hmim][FAP]) and quaternary (CO2 + 1,2-butanediol + butylene carbonate + [hmim][FAP]) mixtures was investigated. The experimental results of the two binary systems were correlated using the density-based Chrastil equation. The knowledge of phase equilibria behaviours reported in this work will be useful for designing chemical conversions of carbon dioxide using [hmim][FAP] ionic liquid as reaction solvents

Synthesis, Characterization and an Electrochemical Study

This study was funded in part by the Coordenação de Aperfeiçoamento de Pessoal de Nível Superior—Brasil (CAPES)—Finance Code 001 and FCT-CAPES project (2019–2020). The authors also thank the funding agencies FAPERJ, CNPq and Fundação para a Ciência e Tecnologia (PTDC/QUI-QOR/32406/2017, PEst-C/LA0006/2013, RECI/BBBBQB/0230/2012 as well as “SunStorage—Harvesting and storage of solar energy”, with reference POCI-01-0145-FEDER-016387. The NMR spectrometers are part of the National NMR Network (PTNMR) and are partially supported by Infrastructure Project N° 022161 (co-financed by FEDER through COMPETE 2020, POCI and PORL and FCT through PIDDAC). Ž.P. and H.C. acknowledge Fundação para a Ciência e a Tecnologia, MCTES, for the Norma Transitória DL57/2016 Program contract. A.F.M.S. also thanks FCT-MCTES for the PhD Grant (SFRH/BD/132551/2017).Ferrocene-based porous organic polymers (FPOPs) were prepared fromphenol-formaldehyde polymer (Bakelite) and phenol as starting materials; and two possible mechanisms for polymerization were discussed. Solid-state 13C CP-MAS NMR, FTIR, powder XRD, elemental analysis and ICP (Fe, Na, B) were performed to characterize the prepared materials. The two synthetic approaches produced polymers with different pore sizes: the FPOP synthesized through Bakelite presented a higher surface area (52 m2 g1) when compared to the one obtained by the bottom-up polymerization from phenol (only 5 m2 g1). Thermogravimetric analysis confirmed the thermal stability of the material, which decomposed at 350 C. Furthermore, cyclic voltammetry (CV) of the new FPOP on modified electrodes, in ACN and 0.1 M TBAP as an electrolyte, showed fully reversible electron transfer, which is similar to that observed for the ferrocene probe dissolved in the same electrolyte. As a proof-of-concept for an electrochromic device, this novel material was also tested, with a color change detected between yellow/brownish coloration (reduced form) and green/blue coloration (oxidized form). The new hybrid FPOP seems very promising for material science, energy storage and electrochromic applications, as well as for plastic degradation.publishersversionpublishe