Poly(Ethylene glycol) diacrylate iongel membranes reinforced with nanoclays for co2 separation

Despite the fact that iongels are very attractive materials for gas separation membranes, they often show mechanical stability issues mainly due to the high ionic liquid (IL) content (≥60 wt%) needed to achieve high gas separation performances. This work investigates a strategy to improve the mechanical properties of iongel membranes, which consists in the incorporation of montmorillonite (MMT) nanoclay, from 0.2 to 7.5 wt%, into a cross-linked poly(ethylene glycol) diacrylate (PEGDA) network containing 60 wt% of the IL 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C2mim][TFSI]). The iongels were prepared by a simple one-pot method using ultraviolet (UV) initiated polymerization of poly(ethylene glycol) diacrylate (PEGDA) and characterized by several techniques to assess their physico-chemical properties. The thermal stability of the iongels was influenced by the addition of higher MMT contents (>5 wt%). It was possible to improve both puncture strength and elongation at break with MMT contents up to 1 wt%. Furthermore, the highest ideal gas selectivities were achieved for iongels containing 0.5 wt% MMT, while the highest CO2 permeability was observed at 7.5 wt% MMT content, due to an increase in diffusivity. Remarkably, this strategy allowed for the preparation and gas permeation of self-standing iongel containing 80 wt% IL, which had not been possible up until now.publishersversionpublishe

Deep eutectic systems for carbonic anhydrase extraction from microalgae biomass to improve carbon dioxide solubilization

This work was supported by the project “DESalgae – Capturing and re-using CO2 using deep eutectic solvents and microalgae” funded by Dutch national fund NWO Open Competition Domain Science – XS [ OCENW.XS4.162 ]; Special thanks to AlGreen B.V. (Wageningen) for providing Spirulina sp. biomass. Publisher Copyright: © 2022 The Authors.This work is the first proof-of-concept of the use of carbonic anhydrase (CA) enzyme from microalgae biomass, extracted with deep eutectic systems (DES), with the goal of engineering a solution that will lead to a breakthrough in the Carbon Capture and Utilization (CCU) strategy. Three distinct microalgae were processed-Tisochrysis lutea, Chlorella vulgaris, and Spirulina sp.-with three DES-Choline chloride-Urea (ChCl-U), Choline chloride-Poly(ethylene glycol) (ChCl-PEG), and Poly(ethylene glycol)-Urea (PEG-U). To evaluate the most promising microalgae-DES, CA activity was evaluated with a specific enzymatic activity kit and through CO2 solubility assays. Preliminary results indicate that: DES is a suitable solvent medium for CA extraction from microalgal biomass, preserving its activity (specific CA activity up to 0.70 mU.mg-1); CA extraction efficiency differs between DES and microalgal species, indicating the potential for further research; from the tested DES, the ones containing PEG were favorable to maintain CA activity (CO2 solubility up to 4 g CO2.g-1 DES). This work paves the way towards a disruptive CCU approach.publishersversionpublishe

Poly(ionic liquid)-based engineered mixed matrix membranes for CO2/H2 separation

Unformatted preprintPoly(ionic liquid)s (PIL) have emerged as a class of versatile polyelectrolites, that can be used to prepare new materials able to achieve superior performances compared to conventional polymers. The combination of PILs with ionic liquids (ILs) may serve as a suitable matrix for the preparation of membranes for gas separation. In this work, mixed matrix membranes (MMMs) combining a pyrrolidinium-based PIL, an IL and three highly CO2-selective metal organic frameworks (MOFs) were prepared. The different MOFs (MIL-53, Cu3(BTC)2 and ZIF-8) were used as fillers, aiming to maximize the membranes performance towards the purification of syngas. The influence of different MOFs and loadings (0, 10, 20 and 30 wt.%) on the thermal and mechanical stabilities of the membranes and their performance in terms of CO2 permeability and CO2/H2 ideal selectivity was assessed. The compatibility between the materials was confirmed by SEM-EDS and FTIR spectroscopy. The prepared MMMs revealed to be thermally stable within the temperature range of the syngas stream, with a loss of mechanical stability upon the MOF incorporation. The increasing MOF content in the MMMs, resulted in an improvement of both CO2 permeability and CO2/H2 ideal selectivity. Among the three MOFs studied, membranes based on ZIF-8 showed the highest permeabilities (up to 97.2 barrer), while membranes based on MIL-53 showed the highest improvement in selectivity (up to 13.3). Remarkably, all permeation results surpass the upper bound limit for the CO2/H2 separation, showing the membranes potential for the desired gas separation.This work was partially supported by R&D Units UID/Multi/04551/2013 (Green-it), UID/QUI/00100/2013 (CQE), and the Associated Laboratory Research Unit for Green Chemistry, Technologies and Clean Processes, LAQV which is financed by national funds from FCT/MCTES(UID/QUI/50006/2013) and co-financed by the ERDF under the PT2020 Partnership Agreement (POCI-01-0145-FEDER-007265). Ana R. Nabais, Luísa A. Neves and Liliana C. Tomé acknowledge FCT/MCTES for financial support through project PTDC/CTM-POL/2676/2014, FCT Investigator Contract IF/00505/2014 and Post-doctoral research grant SFRH/BDP/101793/2014, respectively. This project has received funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Sklodowska-Curie grant agreement No 745734

Influence of anion structure on thermal, mechanical and CO2 solubility properties of uv-cross-linked poly(Ethylene glycol) diacrylate iongels

PTDC/CTM-POL/2676/2014 UID/QUI/50006/2019 grant 471837 SFRH/BD/136963/2018 IF/00505/2014Iongel-based CO2 separation membranes were prepared by fast (< 1 min) UV-initiated polymerization of poly(ethylene glycol) diacrylate (PEGDA) in the presence of different ionic liquids (ILs) with the [C2mim]+ cation and anions such as [TFSI]−, [FSI]−, [C(CN)3]− and [B(CN)4]−. The four ILs were completely miscible with the non-ionic PEGDA network. Transparent and freestanding iongels containing between 60 and 90 %wt of IL were obtained and characterized by diverse techniques (FTIR, TGA, DSC, DMTA, SEM, CO2 solubility and pure gas permeability). The thermal and mechanical stability of the iongels, as well as CO2 solubility, were found to be strictly dependent on the IL content and the anion’s nature. The TGA results indicated that the iongels mostly follow the thermal profile of the respective neat ILs. The DMTA analysis revealed that the iongels based on fluorinated anions have higher storage modulus than those of cyano-functionalized anions. Conversely, the PEGDA–C(CN)3 iongels presented the highest CO2 solubility values ranging from 72 to 80 mmol/g. Single CO2 permeabilities of 583 ± 29 Barrer and ideal CO2/N2 selectivities of 66 ± 3 were obtained with the PEGDA–70 C(CN)3 iongel membrane. This work demonstrates that the combination of PEGDA with high contents of the best performing ILs is a promising and simple strategy, opening up new possibilities in the design of high-performance iongel membranes for CO2 separation.publishersversionpublishe

Characterisation of Films Based on Exopolysaccharides from Alteromonas Strains Isolated from French Polynesia Marine Environments

LA/P/0140/202019 UID/AGR/04129/2020 LA/P/0037/2020This work assessed the film-forming capacity of exopolysaccharides (EPS) produced by six Alteromonas strains recently isolated from different marine environments in French Polynesia atolls. The films were transparent and resulted in small colour alterations when applied over a coloured surface (ΔEab below 12.6 in the five different colours tested). Moreover, scanning electron microscopy showed that the EPS films were dense and compact, with a smooth surface. High water vapour permeabilities were observed (2.7–6.1 × 10−11 mol m−1 s−1 Pa−1), which are characteristic of hydrophilic polysaccharide films. The films were also characterised in terms of barrier properties to oxygen and carbon dioxide. Interestingly, different behaviours in terms of their mechanical properties under tensile tests were observed: three of the EPS films were ductile with high elongation at break (ε) (35.6–47.0%), low tensile strength at break (Ꞇ) (4.55–11.7 MPa) and low Young’s modulus (εm) (10–93 MPa), whereas the other three were stiffer and more resistant with a higher Ꞇ (16.6–23.6 MPa), lower ε (2.80–5.58%), and higher εm (597–1100 MPa). These properties demonstrate the potential of Alteromonas sp. EPS films to be applied in different areas such as biomedicine, pharmaceuticals, or food packaging.publishersversionpublishe

Mixed matrix membranes based on ionic liquids and porous organic polymers for selective CO2 separation

The Associate Laboratory Institute for Health and Bioeconomy - i4HB ( LA/P/0140/2020 ), which are financed by national funds from FCT/MCTES. The authors also thank the National Natural Science Foundation of China (No. 21772013 ) and Beijing Natural Science Foundation (No. 2202049 ) for generous support. Publisher Copyright: © 2022 Elsevier B.V.The development of more efficient materials is a crucial step in the development of gas separation membranes. In this work, we combine ionic liquids (ILs) and porous organic polymers (POPs) for the first time to fabricate a new type of mixed matrix iongel membranes, which are entirely composed of organic materials. The new azo-POPs reported in this work were specifically designed due to their “CO2-philic” feature to be incorporated in iongel materials. The membranes, comprising 80 wt% of [C2mim][TFSI] IL and 20 wt% of poly(ethylene glycol) diacrylate (PEGDA) network, were prepared using a solvent-free UV curing method. The unique properties of azo-POPs within the iongel material resulted in the fabrication of dense and defect-free membranes with improved gas separation performances, in terms of both CO2 permeability (62.3–90.6 barrer) and, CO2/CH4 (9.9–12.0), CO2/H2 (6.0–12.1) and CO2/N2 (16.8–53.1) ideal selectivities, with the latter revealing to be highly dependent on the morphological properties of the azo-POPs. Furthermore, iongel characterization in terms of morphology, chemical structure and thermal properties, confirmed the potential of the novel mixed matrix iongels for CO2 separation processes.publishersversionpublishe

Tropical tree growth driven by dry-season climate variability

Interannual variability in the global land carbon sink is strongly related to variations in tropical temperature and rainfall. This association suggests an important role for moisture-driven fluctuations in tropical vegetation productivity, but empirical evidence to quantify the responsible ecological processes is missing. Such evidence can be obtained from tree-ring data that quantify variability in a major vegetation productivity component: woody biomass growth. Here we compile a pantropical tree-ring network to show that annual woody biomass growth increases primarily with dry-season precipitation and decreases with dry-season maximum temperature. The strength of these dry-season climate responses varies among sites, as reflected in four robust and distinct climate response groups of tropical tree growth derived from clustering. Using cluster and regression analyses, we find that dry-season climate responses are amplified in regions that are drier, hotter and more climatically variable. These amplification patterns suggest that projected global warming will probably aggravate drought-induced declines in annual tropical vegetation productivity. Our study reveals a previously underappreciated role of dry-season climate variability in driving the dynamics of tropical vegetation productivity and consequently in influencing the land carbon sink.We acknowledge financial support to the co-authors provided by Agencia Nacional de Promoción Científica y Tecnológica, Argentina (PICT 2014-2797) to M.E.F.; Alberta Mennega Stichting to P.G.; BBVA Foundation to H.A.M. and J.J.C.; Belspo BRAIN project: BR/143/A3/HERBAXYLAREDD to H.B.; Confederação da Agricultura e Pecuária do Brasil - CNA to C.F.; Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES, Brazil (PDSE 15011/13-5 to M.A.P.; 88881.135931/2016-01 to C.F.; 88887.199858/2018-00 to G.A.-P.; Finance Code 001 for all Brazilian collaborators); Conselho Nacional de Desenvolvimento Científico e Tecnológico - CNPq, Brazil (ENV 42 to O.D.; 1009/4785031-2 to G.C.; 311874/2017-7 to J.S.); CONACYT-CB-2016-283134 to J.V.-D.; CONICET to F.A.R.; CUOMO FOUNDATION (IPCC scholarship) to M.M.; Deutsche Forschungsgemeinschaft - DFG (BR 1895/15-1 to A.B.; BR 1895/23-1 to A.B.; BR 1895/29-1 to A.B.; BR 1895/24-1 to M.M.); DGD-RMCA PilotMAB to B.T.; Dirección General de Asuntos del Personal Académico of the UNAM (Mexico) to R.B.; Elsa-Neumann-Scholarship of the Federal State of Berlin to F.S.; EMBRAPA Brazilian Agricultural Research Corporation to C.F.; Equatorian Dirección de Investigación UNL (21-DI-FARNR-2019) to D.P.-C.; São Paulo Research Foundation FAPESP (2009/53951-7 to M.T.-F.; 2012/50457-4 to G.C.; 2018/01847‐0 to P.G.; 2018/24514-7 to J.R.V.A.; 2019/08783-0 to G.M.L.; 2019/27110-7 to C.F.); FAPESP-NERC 18/50080-4 to G.C.; FAPITEC/SE/FUNTEC no. 01/2011 to M.A.P.; Fulbright Fellowship to B.J.E.; German Academic Exchange Service (DAAD) to M.I. and M.R.; German Ministry of Education, Science, Research, and Technology (FRG 0339638) to O.D.; ICRAF through the Forests, Trees, and Agroforestry research programme of the CGIAR to M.M.; Inter-American Institute for Global Change Research (IAI-SGP-CRA 2047) to J.V.-D.; International Foundation for Science (D/5466-1) to M.I.; Lamont Climate Center to B.M.B.; Miquelfonds to P.G.; National Geographic Global Exploration Fund (GEFNE80-13) to I.R.; USA’s National Science Foundation NSF (IBN-9801287 to A.J.L.; GER 9553623 and a postdoctoral fellowship to B.J.E.); NSF P2C2 (AGS-1501321) to A.C.B., D.G.-S. and G.A.-P.; NSF-FAPESP PIRE 2017/50085-3 to M.T.-F., G.C. and G.M.L.; NUFFIC-NICHE programme (HEART project) to B.K., E.M., J.H.S., J.N. and R. Vinya; Peru ‘s CONCYTEC and World Bank (043-2019-FONDECYT-BM-INC.INV.) to J.G.I.; Peru’s Fondo Nacional de Desarrollo Científico, Tecnológico y de Innovación Tecnológica (FONDECYT-BM-INC.INV 039-2019) to E.J.R.-R. and M.E.F.; Programa Bosques Andinos - HELVETAS Swiss Intercooperation to M.E.F.; Programa Nacional de Becas y Crédito Educativo - PRONABEC to J.G.I.; Schlumberger Foundation Faculty for the Future to J.N.; Sigma Xi to A.J.L.; Smithsonian Tropical Research Institute to R. Alfaro-Sánchez.; Spanish Ministry of Foreign Affairs AECID (11-CAP2-1730) to H.A.M. and J.J.C.; UK NERC grant NE/K01353X/1 to E.G.Peer reviewe

Impact on CO2/N2 and CO2/CH4 Separation Performance Using Cu-BTC with Supported Ionic Liquids-Based Mixed Matrix Membranes

The efficient separation of gases has industrial, economic, and environmental importance. Here, we report the improvement in gas separation performance of a polyimide-based matrix (Matrimid&reg;5218) filled with a Cu-based metal organic framework [MOF, Cu3(BTC)2] with two different ionic liquids (ILs) confined within the pores. The chosen ILs are commonly used in gas solubilization, 1-ethyl-3-methylimidazolium tetrafluoroborate ([EMIM][BF4]) and 1-Ethyl-3-methylimidazolium trifluoromethanesulfonate ([EMIM][OTf]), and the incorporation of the [EMIM][BF4]@Cu-BTC and [EMIM][OTf]@Cu-BTC composites in Matrimid&reg;5218 proved to be an efficient strategy to improve the permeability and selectivity toward CO2/N2 and CO2/CH4 mixtures