Marcus Seferin

Solvation of Carbon Dioxide in [C4mim][BF4] and [C4mim][PF6] Ionic Liquids Revealed by High-Pressure NMR Spectroscopy†

Where is CO2 ? The intermolecular interactions of [C4 mim]BF4 and [C4 mim]PF6 ionic liquids and CO2 have been determined by high-pressure NMR spectroscopy in combination with molecular dynamic simulations. The anion and the cation are both engaged in interactions with CO2 . A detailed picture of CO2 solvation in these ILs is provided. CO2 solubility is essentially determined by the microscopic structure of the IL.

A Rational Approach to CO2 Capture by Imidazolium Ionic Liquids: Tuning CO2 Solubility by Cation Alkyl Branching

Branching at the alkyl side chain of the imidazolium cation in ionic liquids (ILs) was evaluated towards its effect on carbon dioxide (CO2 ) solubilization at 10 and 80 bar (1 bar=1×10(5)  Pa). By combining high-pressure NMR spectroscopy measurements with molecular dynamics simulations, a full description of the molecular interactions that take place in the IL-CO2 mixtures can be obtained. The introduction of a methyl group has a significant effect on CO2 solubility in comparison with linear or fluorinated analogues. The differences in CO2 solubility arise from differences in liquid organization caused by structural changes in the cation. ILs with branched cations have similar short-range cation-anion orientations as those in ILs with linear side chains, but present differences in the long-range order. The introduction of CO2 does not cause perturbations in the former and benefits from the differences in the latter. Branching at the cation results in sponge-like ILs with enhanced capabilities for CO2 capture.

Rationalizing the role of the anion in CO2 capture and conversion using imidazolium-based ionic liquid modified mesoporous silica

Covalently supported ionic liquids in mesoporous materials were prepared by grafting 1-methyl-3-(3-trimethoxysylilpropyl)imidazolium chloride in MCM-41. Subsequently, the [Cl−] anion was changed to [BF4−], [PF6−] or [Tf2N−]. These materials that present an advantageous combination of the properties of mesoporous solid materials and ionic liquids were evaluated for CO2 sorption as well as catalysts for CO2 conversion into cyclic carbonate using propylene oxide. The material with the [Cl−] anion had the best performance for both CO2 sorption and conversion. A CO2 sorption of 11 w/w% on the adsorbent was achieved and the cycloaddition reaction exhibited a conversion of 67% with 82% selectivity with the catalyst remaining active after 5 cycles, proving that the same sorbent/catalyst setup can be used for both CO2 capture and conversion. Based on the experimental data and electronic-structure numerical simulations, we have hypothesized two major reasons why chloride out performs other anions when adsorbed on MCM-41 unlike unsupported ionic liquids.

Syntheses and characterization of new poly(ionic liquid)s designed for CO2 capture

A series of new poly(ionic liquid)s-p(IL)s based on polyurethane structures were synthesized and characterized and their behavior evaluated in CO2 sorption tests under different pressures. The synthesized materials were characterized according to structure, composition, and thermal stability, by techniques such as FTIR, 1H-NMR, TGA and DSC. The CO2 sorption measurements were carried out in a Magnetic Suspension Balance-PTGA and proved that the change of the components of the polymer chain directly indicates the sorption behavior. The best performance for CO2 sorption (75.7 mol% at 20 bar) was achieved with the p(IL) PUA-02a obtained from HDI and PTMG-2000 with [bmim]+ as a counter-ion. The synthesized p(IL)s presenting nitrogenated and polyether structures into the backbone allied to imidazolium counter-cations proved to be worthy of note in the CO2 sorption besides being based on poly(urethane) a versatile and low-cost material. The results also highlighted the good performance of PUA-02 when compared with traditional solvents used in pre-combustion process, as well as the p(IL)s described in the literature.

A New Approach to CO2 Capture and Conversion Using Imidazolium Based-Ionic Liquids as Sorbent and Catalyst

Although the carbon capture and storage (CCS) technologies are receiving great attention for mitigation of greenhouse gas effect, the increasing costs and energy penalties associated to its implementation are still major drawbacks. However, the use of CO2 as a C1 building block in organic synthesis can be very attractive for the design of environmentally friendly processes. In this work, we have studied both the CO2 sorption and catalytic activities of some imidazolium based ionic liquids (ILs) for cyclic carbonate synthesis. The work demonstrates that the presence of a nucleophilic group in the catalytic system can enhance its performance by the use of an IL with a halide anion or by mixing a halide co-catalyst with ILs. The latter approach allowed to obtain an effective system for CO2 capture constituted by a fluorinated IL plus ZnBr2 that performs cyclic carbonate synthesis with 90% yield and 82% of selectivity.

Lower purity dimer acid based polyamides used as hot melt adhesives: synthesis and properties

Hot melt polyamides exhibit high adhesive strength. The polyamides synthesized from dimer fatty acids and diamines can present low crystallinity and a broad range of melting temperatures. In this work, polyamides with different compositions of dimer fatty acids, piperazine, ethylenediamine, sebacic acid and stearic acid and different content of secondary diamine (piperazine) and primary diamine (ethylenediamine) were synthesized. Polyamides with higher purity of dimer acids showed greater molecular weight, adhesion performance and a better mechanical resistance evaluated in stress/strain test. Softening point increased with increase in monomers content. By differential scanning calorimetry analysis, it was observed that polyamides with low percentage of monomer content show only one narrow melting peak in 100 °C. The increase in the acids monomer content leads to a larger temperature range of melting peak. The use of dimer fatty acid with a low content of monomers (up to 6%) in the polyamides synthesis promotes the formation of hot melt adhesives with good adhesion performances. The lowest monomer content leads to an increase in molecular weight, viscosity and mechanical properties of polyamide. Increase in the content of primary amines in polyamides increases crystallinity, viscosity and mechanical properties due to the higher number of hydrogen bonds formed by amide groups.

Potencial uso de serpentinito no armazenamento mineral do CO2

Rising anthropogenic CO2 emissions are considered a major contributor to the greenhouse effect. There are several options for reducing atmospheric CO2 levels, and among these alternatives, Carbon Capture and Storage (CCS) has been identified as an effective and promising approach. This work investigated the feasibility of using serpentinite as a vehicle for carbon storage presenting a source-sink match. The main results of the work confirmed that serpentinite is appropriate for the carbonation process due to the high concentration of Mg in its composition.

The effect of an electron-withdrawing group in the imidazolium cation: the case of nitro-functionalized imidazolium salts as acidic catalysts for the acetylation of glycerol

The acetylation of glycerol was achieved with high conversion and selectivity towards triacetin at low temperatures and short reaction times by using acidic imidazolium salts as catalysts. Moreover, the addition of a nitro group to the imidazolium cation affords a much more competent catalyst, indicating a significant effect provided by the simple electronic change in the imidazolium cation. Theoretical calculations revealed increased polarization of the acidic hydrogen bond on the nitrated salts, which may be related to their superior catalytic behavior when compared to the non-functionalized salts. Combining the preliminary experimental and theoretical results, it is possible to suppose that the catalytic activity of acidic imidazolium salts may be better comprehended by its Bronsted acidities, but other parameters such as hardness, electronegativity, electrophilicity and ion-pair binding energy were also evaluated in order to investigate their effects in the acetylation of glycerol promoted by these acidic imidazolium salts.

Development and validation of analytical methodology by GC-FID using hexadecyl propanoate as an internal standard to determine the bovine tallow methyl esters content

EN 14103:2003 and EN 14103:2011 were developed in order to determine fatty acid methyl ester (FAME) content of biodiesel. The internal standards (IS) of biodiesel include methyl heptadecanoate (MHD) and methyl nonadecanoate (MND), respectively. However, since these ISs are also present in bovine tallow methyl esters (BTME) or overlapping peaks, they have not been efficient. This work proposes an improved BTME determination method by using hexadecyl propanoate (HDP) as an IS. For this purpose, an analytical methodology by Gas Chromatography-Flame Ionization Detector (GC-FID) was developed and validated, where HDP demonstrated selectivity in retention time between peaks C16:1 and C18:0 for coconut and soybeans methyl esters and BTME, as well as resolution >1.5 for the BTME in split mode 30:1. Trueness in the determination of BTME content using the HDP as an IS was statistically equivalent to confidence interval of 95% for the null hypothesis statistic test, even when only 20% of the HDP was utilized in comparison with the IS concentrations defined by EN 14103:2003 and EN 14103:2011. This allowed the biodiesel analysis to be performed five times more with 1 g of HDP. Furthermore, the method developed enabled us to reduce the analysis time by 21.6%, without prejudice to the integration of peaks (C6:0 to C24:1). Regarding the repeatability and intermediate precision tests, results of RSD (%) ≤ 2% were reached. Additionally, the method developed has proved to be robust. HDP is a long-chain fatty alcohol ester absent from feedstocks used in biodiesel synthesis. It presents all of the characteristics for a good IS, ideal for application via internal standardization method, as recommended by EN 14103.

GC-FID methodology validation for the fatty esters content determination in biodiesel with hexadecyl acetate as the internal standard

João V. Braun,a,b Vinícius O. B. dos Santos,a,b Luiz A. M. Fontoura,a,b,* Evandro Pereira,c Amanda Napp,c Marcus Seferin,d Jeane Lima,d Rosane Ligabued e Marilene H. Vainsteinc Departamento de Engenharia de Processos, Fundação de Ciência e Tecnologia, Av. das Indústrias 2270, 94930-230 Cachoeirinha – RS, Brasil Universidade Luterana do Brasil, Av. Farroupilha 8001, 92426-900 Canoas – RS, Brasil Centro de Biotecnologia, Universidade Federal do Rio Grande do Sul, Av. Bento Gonçalves 9500, 91501-970 Porto Alegre – RS, Brasil Faculdade de Química, Pontifícia Universidade Católica do Rio Grande do Sul, Av. Ipiranga 6681, Prédio 12, 90619-900 Porto Alegre – RS, Brasil