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The current study presented a porous liquid (PL) prepared from propylene glycol-based deep eutectic solvent (DES) and hyper-crosslinked polymers (HCP) that are liquids over wide temperature ranges, including ambient temperature. It was shown that the solvent molecules are too large to penetrate the pores of HCP, so the PL is maintained as a suspension with permanent free volume for several months and can absorb large amounts of gases. This study marks the pioneering use of DESs as the liquid medium, replacing ionic liquids due to their closely matched properties. The structural features of both DES and HCP are retained; the increase in CO2 absorption capacity compared to pure DES is due to the presence of a porous solid and is proportional to the amount of solid. The absorbed CO2 amount rises from 1.0105 mmol·g−1 in pure DES to 1.3232, 1.6027, and 1.2168 mmol·g−1 in PL-1, PL-2, and PL-3, respectively. Thermodynamic analysis revealed that the enthalpy of gas absorption allows straightforward regeneration of the PLs in the studied cases. The investigated PLs show great potential as gas absorbents, with the incorporation of just 0.5 wt% of porous polymer material leading to an impressive increase in solvent absorption capacity, up to 59 %.

To produce chitosan is an interesting research. Chitosan is an important polysaccharide in terms of its various applications in industries and is produced from chitin, an abundant biopolymer in crustacean shell biomass wastes. Traditional processes for chitosan manufacture are commonly based on highly concentrated alkaline or acid solutions which are, however, severely eroding and harmful to the environment. In this study, we have described a ‘greener’ method using 1-ethyl-3-methylimidazolium acetate, [Emim][OAc] ionic liquid (IL), for decrystallization of shrimp crystalline chitin flakes followed by a microwave-mediated NaOH or tetrabutylammonium hydroxide, [TBA][OH], solution-based deacetylation for chitosan production. The decrease in crystallinity in IL pre-treated chitin was confirmed by XRD and SEM analysis which subsequently benefited chitosan production with up to 85% degree of deacetylation (%DDA) in shorter time periods (1-2 hours) and lower alkaline concentrations (20-40%). The %DDA in chitin/chitosan was estimated via FT-IR and NMR analysis. Notably, we could regenerate the ionic liquids: in case of [Emim][OAc] 97 wt.% and in case of [TBA][OH] 83 wt.% could be reused. Roles of ionic liquids in the process were discussed. Molecular dynamics (MD) simulations showed the roles of [TBA]+ cations in the molecular driving forces of [TBA][OH]-induced deacetylation mechanism. The strategy promises a sustainable and milder reaction approach to the existing highly corrosive alkaline- or acid-involved processes for chitosan production.

Three short-alkyl-chain-modified [DBU][TFSI] ionic liquids (ILs) were synthesized and utilized in electrets. The electrets were prepared by mixing a UV-curable polymer with the ionic liquids followed by polymerization while applying an external electric field, thus forming spatially separated anions and cations in the proximity of opposing surfaces of the composite slabs. The immobilized surplus surface charge was measured by periodically engaging the electret with a metal counter electrode plate and detecting the displacement current using a charge amplifier. The results show that electrets based on polymerized [DBU][TFSI] ILs have a separated surface charge density of up to 64 nC × cm−2, which equals an energy harvesting density of 7.0 nJ × cm−2. Control measurements repeated after a few days to assess the stability and reproducibility of the systems showed that while charge separation reverses over time to some extent, the polymerized ionic liquid samples are resilient to exposure to atmospheric conditions and could be utilized in this type of energy harvesting scheme.

The need of new electrolytes with wide electrochemical window, good stability and conductivity has promoted novel ionic liquids (ILs) as new solutions for supercapacitors. In this work, four hydrophobic room temperature ionic liquids based on organic superbase-derived cations and Trifluoromethanesulfonimide (TFSI) anion were synthetized. The structures of the novel ILs were analyzed, characterized and their performance as a supercapacitor electrolyte was evaluated. The ILs have high decomposition temperatures of up to 490 °C and electrochemical window up to 4.8 V. It was found that there was an optimal chemical structure providing the best stability and operational potential window coupled with moderate conductivity. The IL with the shortest alkyl chain structure provided the highest conductivity but suffered from instability. The performance of the ILs with longer alkyl chains was hindered by lower conductivities and, in the case of the largest chemical structures, also by reduced cyclic stabilities in open air. However, the ionic liquid with moderate alkyl chain length was found to be stable even in open air providing decent conductivity, which can be utilized in future research to develop other hydrophobic ionic liquids suitable as supercapacitor electrolytes.

Hardwood spent mushroom substrate was employed as a carbon precursor to prepare activated biochars using phosphoric acid (H3PO4) as chemical activator. The activation process was carried out using an impregnation ratio of 1 precursor:2 H3PO4; pyrolysis temperatures of 700, 800, and 900 °C; heating rate of 10 °C min−1; and treatment time of 1 h. The specific surface area (SSA) of the biochars reached 975, 1031, and 1215 m2 g−1 for the samples pyrolyzed at 700, 800, and 900 °C, respectively. The percentage of mesopores in their structures was 75.4%, 78.5%, and 82.3% for the samples pyrolyzed at 700, 800, and 900 °C, respectively. Chemical characterization of the biochars indicated disordered carbon structures with the presence of oxygen and phosphorous functional groups on their surfaces. The biochars were successfully tested to adsorb acetaminophen and treat two simulated pharmaceutical effluents composed of organic and inorganic compounds. The kinetic data from adsorption of acetaminophen were fitted to the Avrami fractional-order model, and the equilibrium data was well represented by the Liu isotherm model, attaining a maximum adsorption capacity of 236.8 mg g−1 for the biochar produced at 900 °C. The adsorption process suggests that the pore-filling mechanism mainly dominates the acetaminophen removal, although van der Walls forces are also involved. The biochar produced at 900 °C removed up to 84.7% of the contaminants in the simulated effluents. Regeneration tests using 0.1 M NaOH + 20% EtOH as eluent showed that the biochars could be reused; however, the adsorption capacity was reduced by approximately 50% after three adsorption–desorption cycles.

The development of biomass-based carbon materials has accelerated the research interest in environmental (e.g., adsorbents for wastewater decontamination) and energy applications (e.g., batteries). In this paper, we developed a series of carbon materials (CMs) using a sulfur doping strategy to improve the physicochemical, adsorptive and energy storage properties of the aforementioned CMs. CMs were prepared and optimized using an experimental design denoted as the Box-Behnken design approach with three independent factors (i.e., the temperature of pyrolysis, zinc chloride: biomass ratio and sulfur: biomass ratio), and the responses were evaluated, namely the Specific Surface Area (SBET), mesopore area (AMeso) and micropore area (AMicro) with the help of Nitrogen Physisorption. According to the statistical analysis, under the studied conditions, the responses were mainly influenced by the pyrolysis temperature and ZnCl2 ratio, while the sulfur content did not give rise to any remarkable differences in the selected responses. The physicochemical characterization of the CMs suggested that very high Specific Surface Areas ranging from 1069 to 1925 m2 g−1 were obtained. The sulfur doping resulted in up to 7.33wt.% of sulfur in the CM structure, which yielded CMs with more defects and hydrophilic surfaces. When tested as adsorbents, CMs exhibited a very high adsorption capacity (190 – 356mgg-1), and as anodes, they demonstrated a competitive Lithium Ion Battery (LIB) storage capacity, at least during the first five cycles (306 mAhg-1 at 1C for CM9). However, further studies on long-term cyclability are required to prove the CM materials suitability in LIBs. This work extends our understanding of how pyrolysis and sulfur doping of biomass feedstock affects carbon materials' usability, final characteristics and potential to use in wastewater decontamination by adsorption and as anodes in LIBs.

Cellulose fiber rejects from industrial-scale recycling of waste papers were dried and de-ashed using a combined cyclone-drying and sieving process. The upgraded fiber reject was used as a component of substrates for the cultivation of Pleurotus ostreatus and Pleurotus eryngii mushrooms. Acetic acid (AA) and acid whey (AW) were used to adjust the pH of fiber reject-based substrates. Spent substrate (SMS) was used for the production of activated biochar using H3PO4 and KOH as activating agents and pyrolysis temperatures of 500, 600, and 700 °C. The effectiveness of the biochars in removing pollutants from water was determined using acetaminophen and amoxicillin. By using a feeding rate of 250 kg/h and a drying air temperature of 70 °C, the moisture content of the raw fiber rejects (57.8 wt %) was reduced to 5.4 wt %, and the ash content (39.2 wt %) was reduced to 21.5 wt %. Substrates with 60 and 80 wt % de-ashed cellulose fiber were colonized faster than a birch wood-based control substrate. The adjustment of the pH of these two substrates to approximately 6.5 by using AA led to longer colonization times but biological efficiencies (BEs) that were higher or comparable to that of the control substrate. The contents of ash, crude fiber, crude fat, and crude protein of fruit bodies grown on fiber reject-based substrates were comparable to that of those grown on control substrates, and the contents of toxic heavy metals, that is, As, Pb, Cd, and Hg, were well below the up-limit values for food products set in EC regulations. Activated biochar produced from fiber reject-based SMS at a temperature of 700 °C resulted in a surface area (BET) of 396 m2/g (H3PO4-activated biochar) and 199 m2/g (KOH-activated biochar). For both activated biochars, the kinetics of adsorption of acetaminophen and amoxicillin were better described using the general order model. The isotherms of adsorption were better described by the Freundlich model (H3PO4-activated biochar) and the Langmuir mod

In this study, nanostructure kazakhstanite-like iron vanadate (FexV3xOy.H2O) was synthesized and calcined at different temperatures (100-800 °C) in a nitrogen atmosphere. The material was used to modify screen-printed carbon electrodes to achieve an electrocatalytic effect on the surface. The relationship between calcination conditions and the catalytic performance of the electrode towards the oxidation of chemotherapeutic drugs, including methotrexate (MTX) and folinic acid (FA), was studied. Various spectroscopic, microscopic, and electrochemical methods were used to characterize the synthesized materials. The results show that calcination induces changes in the electronic structure, nanostructure morphology, electroactive surface area, and electrocatalytic performance of the material. Screen-printed carbon electrode modified with FexV3xOy calcinated at 450 °C (SPC/FexV3xOy-450) was used to develop a voltammetric sensor for the determination of MTX and FA in blood serum. The response of the SPC/FexV3xOy-450 towards the electrooxidation of MTX and FA was the highest in comparison to the bare SPC and SPC/FexV3xOy calcined at other temperatures. The SPC/FexV3xOy-450 exhibited a linear relationship over a wide concentration range: 0.005-200 µM for MTX and 0.05-200 µM for FA. The detection limit was 2.85 nM for MTX and 7.79 nM for FA. Compared to conventional methods, the SPC/FexV3xOy-450 sensor had a short response time (5 min) for simultaneous detection of MTX and FA without signal interferences from coexisting electroactive compounds. The accurate and precise determination of MTX in the presence of FA confirmed the potential clinical applications of SPC/FexV3xOy-450 for therapeutic drug monitoring during chemotherapy.

In this study, glutaraldehyde cross-linked chitosan support, as well as the catalysts obtained after loading Ag metal (Ag/Chitosan), were synthesised and applied for adsorption and reduction of phenol red dye in an aqueous solution. The Ag/chitosan catalysts were characterised by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR) and inductively coupled plasma-optical emission spectrometry (ICP-OES) analysis techniques. The catalytic reduction and adsorption performance of phenol red dye with Ag/chitosan and cross-linked chitosan, respectively, was performed at ambient reaction conditions. The reduction of dye was carried out using sodium borohydride (NaBH4) as the reducing agent, while the progress of adsorption and reduction study was monitored with ultraviolet-visible (UV-vis) spectrophotometry technique. The reduction of the phenol red dye varied with the amount of catalyst, the concentration of NaBH4, Ag metal loading, reaction temperature, phenol red dye concentration and initial pH of the dye solution. The dye solution with a nearly-neutral pH (6.4) allowed efficient adsorption of the dye, while acidic (pH = 4) and alkaline (pH = 8, 11, 13.8) solutions showed incomplete or no adsorption of dye. The reusability of the Ag/chitosan catalyst was applied for the complete reduction of the dye, where no significant loss of catalytic activity was observed. Hence, the applicability of cross-linked chitosan and Ag/catalyst was thus proven for both adsorption and reduction of phenol red dye in an aqueous solution and can be applied for industrial wastewater treatment.

The replacement of fossil-based plastics with biobased and biodegradable alternatives has become an important research challenge in recent years, aiming to eliminate the negative environmental impact of persistent plastics in nature. In this report, design of experiments was successfully exploited to develop an efficient and sustainable method for extracting intracellular PHA from Photobacterium ganghwense C2.2 using dihydrolevoglucosenone (Cyrene) and ethanol as biobased solvents obtainable from sustainable sources. The extraction conditions were studied and optimized against the yield and molecular weight. The temperature range for the extraction was scouted by using differential scanning calorimetry, while size exclusion chromatography coupled to refractive index and multiangle light scattering detectors was used to assess the molecular weights of the extracted polymers. The examined ranges in the model were, respectively, 1.6–8.4% (w/v) of lyophilized cells content per 10 mL of solvent, 3–17 min extraction time, and temperatures from 116 to 144 °C. Time and temperature strongly affected the extraction yields and molecular weights of the obtained polymers while the concentration of bacterial biomass only effected the molecular weight. Several quadratic and interaction coefficients were significant in the well-fit partial least-squares regression models (R2 > 0.8, Q2 > 0.6) indicating that nonlinear effects and interacting parameter contributed to the optimization targets. The optimized extraction should be performed at 130 °C for 15 min with 2% loading of bacterial biomass. The predicted yield and molecular weight of the polymer matched the values obtained from the real experiment under the optimized conditions. The method setup provided similar yield and higher molecular weight in much shorter time compared to overnight Soxhlet extraction with CHCl3. The clean 1H nuclear magnetic resonance spectra of polymers extracted from bacteria indicate that high puri

Binary and ternary composites of BiOI with NH2-MIL-101(Fe) and a functionalized biochar were synthesized through an in situ approach, aimed at spurring the activity of the semiconductor as a photocatalyst for the removal of ciprofloxacin (CIP) from water. Experimental outcomes showed a drastic enhancement of the adsorption and the equilibrium (which increased from 39.31 mg g-1 of bare BiOI to 76.39 mg g-1 of the best ternary composite in 2 h time), while the kinetics of the process was not significantly changed. The photocatalytic performance was also significantly enhanced, and the complete removal of 10 ppm of CIP in 3 h reaction time was recorded under simulated solar light irradiation for the best catalyst of the investigated batch. Catalytic reactions supported by different materials obeyed different reaction orders, indicating the existence of different mechanisms. The use of scavengers for superoxide anion radicals, holes, and hydroxyl radicals showed that although all these species are involved in CIP photodegradation, the latter play the most crucial role, as also confirmed by carrying out the reaction at increasing pH conditions. A clear correlation between the reduction of BiOI crystallite sizes in the composites, as compared to the bare material, and the material performance as both adsorbers and photocatalyst was identified.

Valorization of renewable and biodegradable biopolymers to value added chemicals and green fuels is currently considered as an important research topic aiming at reducing the dependency on fossil derived feedstocks as well as their negative consequences on the environment. In this report, we are introducing an ionic liquid (IL) mediated, sustainable, and green synthesis of crotonic acid (CA) from poly-(3-hydroxybutyrate, PHB), a biopolymer derived from microbial fermentation. In this actual case, imidazolium cation comprising ILs have been used in the synthesis, where the influence of various reaction parameters such as reaction temperature and types of ILs as well as the amount of polymer, water, and IL in the reaction mixture were examined. The conversion of PHB to CA in IL took place by a base catalyzed depolymerization with formation of crotonyl terminated polymeric entities as intermediates, a mechanism that was confirmed by NMR analysis of the reaction mixtures sampled when the reactions were carried out at various temperatures. The rate of CA formation via the IL mediated base catalyzed depolymerization increased with increasing temperature in the tested interval, and 97% yield of CA was obtained after 90 min at 140 °C. The [EMIM][AcO] IL applied as solvent and catalyst is capable of completely depolymerizing PHB to CA in 5 h at 120 °C up to a polymer loading of 40 wt%. At higher loadings the depolymerization became incomplete, which is attributed to a deactivation of the IL due to hydrogen bonding interactions with the in situ formed CA, confirmed by NMR and DSC techniques. Since the depolymerization is base catalyzed, the only tested ILs that were able to form CA were based on acetate anions, whereas the less basic or neutral [EMIM][Cl] IL was found to be inactive. Finally, more than 90% of CA as well as [EMIM][AcO] IL were recovered in high purity by solvent extraction with brine (saturated aqueous NaCl) and 2-methyl tetrahydrofuran (2-Me-THF). Most import

Polyvinylidene fluoride (PVDF) membranes were prepared by phase inversion in the most commonly used solvents for membrane manufacture, with CO2 as a non-solvent additive. The effects of changing the polymer concentration (10, 12.5 and 15% by weight), the type of solvent (NMP, DMAc and DMF) and the coagulation bath with three levels of CO2 concentration on the phase inversion process, as well as the phase diagram, morphology and transport properties of the membranes were studied. The best performing membranes were used to desalinate salt aqueous solutions and decontaminated simulated nuclear wastewater by membrane distillation using two configurations (DCMD and AGMD). All selected membranes showed high rejection with acceptable permeate fluxes reaching an infinite decontamination factor. The proposed approach of this novel idea of using CO2 dissolved in water as a coagulation medium in the field of membranes avoids the increase of the harmful effect on the environment caused by the addition of a harsh non-solvent to the coagulation bath. It constitutes a beneficial use of carbon dioxide that reduces the negative environmental impact of membrane manufacturing and represents a decisive step towards its sustainability. Furthermore, this study highlights the potential benefits of using these membranes in DM for desalination and treatment of simulated nuclear wastewater.

We investigate the performance of four Prussian blue analogues (PBAs) as catalysts for the selective degradation of ciprofloxacin in water, under both dark and illumination conditions. We show that no light is actually needed to induce a selective degradation of the molecular target, while light irradiation spurs the process, without, however, resulting in the commonly reported photolysis-supported breaking down. We present a systematic characterization of the PBAs aiming at interpreting the catalytic outcomes in the light of a classic coordination chemistry analysis, empowered by the most recent findings in literature. We show that varying the transition metal binding the N atom of the cyanide bridge is key to promote photoinduced charge generation and transfer, which effectively disrupts the molecular target. The analysis of the materials before and after the irradiation with solar simulated light results in a change of the lattice parameters, indicating the possibility of a light-induced spin cross-over.

For the first time, a tandem catalytic material namely 5 wt. % Pd/NbOPO 4 was utilized in the depolymerization of wood in supercritical-ethanol under low initial-hydrogen pressure. The experiments were conducted under various experimental conditions, wood fractionation was executed with fresh, and acetone extracted birch. A comprehensive analysis was performed to elucidate the dissolution efficiency and achieved product distribution. The results indicated fresh birch, 34 wt. % of lignin monomer yield with 84 wt. % delignification efficiency were obtained while extracted wood, 35 wt. % of lignin monomer yield with 78 wt. % delignification efficiency was achieved. The total lignin monomer content extracted from the fresh birch is composed of 76.9 wt. % of dimethoxyphenols and 16.5 wt. % of monomers with the guaiacol structure. Among the dimethoxyphenols, major homosyringaldehyde (61.9 wt. %). Where extracted wood, 93.2 wt. % of dimethoxyphenols (63.6 wt. % homosyringaldehyde) and guaiacol-monomers (6.8 wt. %). It was concluded that the depolymerization occurred via breaking of the ether bonds in lignin, including ether hydrolysis by Lewis acid sites over the solid acid catalyst and with subsequent deoxygenation of monophenols over Pd. In addition, an extraction process was proposed to extract the aromatic fraction from the obtained biocrude.

Hardwood spent mushroom substrate was employed as a carbon precursor to prepare activated biochars using phosphoric acid (H3PO4) as chemical activator. The activation process was carried out using an impregnation ratio of 1 precursor:2 H3PO4; pyrolysis temperatures of 700, 800, and 900 °C; heating rate of 10 °C min−1; and treatment time of 1 h. The specific surface area (SSA) of the biochars reached 975, 1031, and 1215 m2 g−1 for the samples pyrolyzed at 700, 800, and 900 °C, respectively. The percentage of mesopores in their structures was 75.4%, 78.5%, and 82.3% for the samples pyrolyzed at 700, 800, and 900 °C, respectively. Chemical characterization of the biochars indicated disordered carbon structures with the presence of oxygen and phosphorous functional groups on their surfaces. The biochars were successfully tested to adsorb acetaminophen and treat two simulated pharmaceutical effluents composed of organic and inorganic compounds. The kinetic data from adsorption of acetaminophen were fitted to the Avrami fractional-order model, and the equilibrium data was well represented by the Liu isotherm model, attaining a maximum adsorption capacity of 236.8 mg g−1 for the biochar produced at 900 °C. The adsorption process suggests that the pore-filling mechanism mainly dominates the acetaminophen removal, although van der Walls forces are also involved. The biochar produced at 900 °C removed up to 84.7% of the contaminants in the simulated effluents. Regeneration tests using 0.1 M NaOH + 20% EtOH as eluent showed that the biochars could be reused; however, the adsorption capacity was reduced by approximately 50% after three adsorption–desorption cycles.

Herein, we report porous ionic liquids (type-III) designed to utilize microporous ZIF-8 moieties with functional ionic liquids such as 8-(2-methoxyethyl)-1,8-Diazabicyclo[5.4.0]undec-7-en-8-ium, Bis(trifluoromethane)sulfonamide ([MEDBU][TFSI] and Trioctylammonium 4-para-tert-butylbenzoiate [TOAH][PTBBA]). The prepared materials were thoroughly characterized by means of XRD, FT-IR, SEM, TEM, BET, TGA, DSC and viscometry techniques. The idea of combining the intrinsic properties of ionic liquids with microporous architecture to prepare porous ionic liquids yields promising fluidic materials that have received attention in industrial applications such as gas sorption and separation etc. The prepared porous ionic liquids possess unique physico-chemical properties such as low viscosity, high thermal stability, low vapor pressure, reusability and their fluidic nature renders the materials suitable for CO2 capture. Herein introduced porous ionic liquids (ILs) showed enhanced CO2 uptake (0.92 mmol/g in [TOAH][PTBBA]-Z100 and 1.16 mmol/g in [MEDBU][TFSI]-Z200), or in other words, 15–47% higher sorption capacity compared to neat ionic liquids. This concept overcomes the drawbacks of highly viscous ILs and their limited CO2 sorption capacity. Thermodynamic modeling further demonstrated that the enthalpy of sorption is only −9.99 kJ mol−1, indicating that significantly less energy is required for regeneration. This is promising for the potential use of these fluidic materials in continuous separation processes on an industrial scale, as a better alternative to the existing hazardous amine scrubbing.

Herein, we show that textural properties of carbon supports have limited influence on the activity and stability of carbon supported Pd, Pt and Ru catalysts upon decarboxylation of a model triglyceride (tristearin) in the presence of subcritical water (256–326 °C). In contrast, surface acid-base properties of carbon supports were found to have a marked impact on the performance and stability of these catalysts. More precisely, for Pt group (Pt and Pd) a positive correlation could be observed between the concentration of surface basic sites and catalyst deoxygenation activity and durability while acid sites had the opposite effect. On the other hand, the activity of Ru-based catalysts were not analogously affected by the acid-base properties of carbon supports, even so a positive correlation was found between surface basicity and durability (reusability). Further, the activity of metals in decreasing order of TOF was Ru>Pt>Pd, irrespective of carbon support.

Main obstacle for adopting continuous processes as a standard technology for Mizoroki-Heck reaction usually lies in its specific reaction mechanism. Here we present an important step forward answering the challenges unraveled through a comprehensive study that provides deeper understanding on the Mizoroki-Heck reaction, in particular the case when iodobenzene and butyl acrylate react in a continuous packed bed reactor in the presence of a Pd Supported Ionic Liquid Catalyst (SILCA). On-line UV–VIS spectrometry supported by ICP-OES, TEM and XPS measurements were carried out and the catalyst leaching was minimized. Finally, simple continuous flow process was proposed resulting in a high catalytic activity (up to 1470 molArI molPd−1h−1) and reaching productivity in the range of 12,000 to 16,000 molArI molPd−1 thus competing with the performance of commercial catalysts., Volume 433, Part 1.

Mesoporous SBA-15 silicate with a high surface area was prepared by a hydrothermal method, successively modified by organic melamine ligands and then used for deposition of Pd nanoparticles onto it. The synthesized materials were characterized with infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), nitrogen physisorption, scanning electron microscopy (SEM) coupled with energy dispersive X-ray analysis (EDX), transmission electron microscopy (TEM), nuclear magnetic resonance (NMR) and inductively coupled plasma (ICP-OES). The catalyst was effectively used in the Mizoroki–Heck coupling reaction of various reactants in the presence of an organic base giving the desired products in a short reaction time and with small catalysts loadings. The reaction parameters such as the base type, amounts of catalyst, solvents, and the temperature were optimized. The catalyst was easily recovered and reused at least seven times without significant activity losses. Graphic Abstract: [Figure not available: see fulltext.]

In this work, a low-cost, light-weight, highly efficient, and durable electrode in which NiFe-layered double hydroxide is electrodeposited on a carbon nanofiber (CNF) core supported on a carbon foam (CF) is introduced. The resulting 3D NiFe-CNFs-CF electrode shows excellent oxygen evolution reaction and hydrogen evolution reaction performance in alkaline media. When used as an anode and a cathode in the same cell, a current density of 10 mA cm−2 is achieved, at a cell voltage of 1.65 V. Moreover, good stability over a long testing time (50 h) is demonstrated. The ternary hybrid electrode gives rise to an excellent performance-to-weight ratio owing to its very low bulk density (≈34 mg cm−3) inherited from super lightweight components composed of CF and CNFs. The developed electrode can potentially be used in large-scale alkaline water electrolysis, in facilities such as offshore hydrogen production platforms, which can complement the variable renewable energy production of wind farms through hydrogen storage and fuel cells.

Hydrothermal deoxygenation of tall oil fatty acids (TOFA) was investigated in the presence of aqueous formic acid (0.5–7.5 wt%) as a H2 donor in the presence of subcritical H2O pressure (569–599 K). Pd and Ru nanoparticles supported on carbon (5% Pd/CSigma, 5% Ru/CSigma, 10% Pd/CO850_DP, and 5% Ru/COPcomm_DP) were found to be efficient catalysts for deoxygenation of TOFA. The reaction pathway was mainly influenced by the concentration of formic acid and the catalyst. In case of Pd catalysts, in the presence of 0–2.5 wt% formic acid, decarboxylation was the dominant pathway producing n-paraffinic hydrocarbons with one less carbon atom (heptadecane yield up to 94 wt%), while with 5–7.5% formic acid, a hydrodeoxygenation/hydrogenation mechanism was favored producing C18 deoxygenation products octadecanol and octadecane as the main products (yields up to 70 wt%). In contrast, Ru catalysts produced a mixture of C5-C20 (n-and iso-paraffinic) hydrocarbons via decarboxylation, cracking and isomerization (up to 58 wt% C17 yield and total hydrocarbon yield up to 95 wt%) irrespective of formic acid concentration. Kinetic studies showed that the rates of deoxygenation displayed Arrhenius type behavior with apparent activation energies of 134.44 ± 31.36 kJ/mol and 148.92 ± 3.66 kJ/mol, for the 5% Pd/CSigma and 5% Ru/CSigma catalyst, respectively. Furthermore, the experiments with glycerol tristearate, rapeseed oil, sunflower oil, rapeseed biodiesel, and hydrolyzed rapeseed oil produced identical products confirming the versatility of the aforementioned catalytic systems for deoxygenation of C18 feedstocks., Bio4Energy

Dimethyl carbonate (DMC) and glycidol are considered industrially important chemical entities and there is a great benefit if these moieties can be synthesized from biomass-derived feedstocks such as glycerol or its derivatives. In this report, both DMC and glycidol were synthesized in an integrated process from glycerol derived 1,3-dichloro-2-propanol and CO2 through a metal-free reaction approach and at mild reaction conditions. Initially, the chlorinated cyclic carbonate, i.e., 3-chloro-1,2-propylenecarbonate was synthesized using the equivalent interaction of organic superbase 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) and 1,3-dichloro-2-propanol with CO2 at room temperature. Further, DMC and glycidol were synthesized by the base-catalyzed transesterification of 3-chloro-1,2-propylenecarbonate using DBU in methanol. The synthesis of 3-chloro-1,2-propylenecarbonate was performed in different solvents such as dimethyl sulfoxide (DMSO) and 2-methyltetrahydrofuran (2-Me-THF). In this case, 2-Me-THF further facilitated an easy separation of the product where a 97% recovery of the 3-chloro-1,2-propylenecarbonate was obtained compared to 63% with DMSO. The use of DBU as the base in the transformation of 3-chloro-1,2-propylenecarbonate further facilitates the conversion of the 3-chloro-1,2 propandiol that forms in situ during the transesterification process. Hence, in this synthetic approach, DBU not only eased the CO2 capture and served as a base catalyst in the transesterification process, but it also performed as a reservoir for chloride ions, which further facilitates the synthesis of 3-chloro-1,2-propylenecarbonate and glycidol in the overall process. The separation of the reaction components proceeded through the solvent extraction technique where a 93 and 89% recovery of the DMC and glycidol, respectively, were obtained. The DBU superbase was recovered from its chlorinated salt, [DBUH][Cl], via a neutralization technique. The progress of the reactions as well as, Bio4Energy

A microwave assisted reaction protocol for Suzuki–Miyaura cross-coupling has been developed. Substituted arylboronic acids and arylsulfonyl chlorides coupled under microwave irradiation (MWI) to produce cross-biphenyls in high yields under aerobic condition. The principal advantage of this protocol is that formation of cross-biphenyls was achieved within shorter time along with desulfurization of arylsulfonyl chloride. In-situ generated Pd nanoparticles (NPs) act as catalyst in the reaction. Substituents like methyl, halogens, cyano, amino and t-butyl groups in arylboronic acids tolerate the reaction condition. Pd NPs could be reused several times under chosen reaction conditions without losing its activity significantly. The product formation and the role of the catalyst for the cross-coupling reaction has been rationalised with the help of a proposed mechanism. This reaction is one of the examples of In-situ generated Nanoparticles-catalyzed Organic Synthesis Enhancement (i-NOSE) approach. The approach derives its importance in terms of catalyst’s (i) simple preparation method, (ii) stability under the chosen reaction condition, (iii) substrate specificity, (iv) simple filtration to recover the catalyst and (v) easy regeneracy which clearly indicate that the approach could be applicable for various types of catalytic transformations., Bio4Energy

In this study, we report a 3D structured carbon foam electrode assembled from a bi-functional NiCo catalyst, carbon nanotubes (CNT), and a monolith 3D structured carbon foam (CF) as a highly active and stable electrode for oxygen evolution reaction (OER) and methanol oxidation reaction (MOR). When the NiCo@CNTs/CF electrode was used as an anode in OER, after the anodization step, the electrode required a small overpotential of 320 mV to reach the current density of 10 mA cm−2 and demonstrated excellent stability over a long testing time (total 30 h) in 1 M KOH. The as-prepared NiCo@CNTs/CF electrode also exhibited a good performance towards methanol oxidation reaction (MOR) with high current density, 100 mA cm−2 at 0.6 V vs. Ag/AgCl, and good stability in 1 M KOH plus 0.5 M CH3OH electrolyte. The NiCo@CNTs/CF catalyst/electrode provides a potential for application as an anode in water electrolysis and direct methanol fuel cells.

A thorough experimental optimization of supported ionic liquid catalyst (SILCA) was performed in order to obtain a stable and efficient catalyst for the Heck reaction. Out of fifteen proposed structures, propyl imidazolium bromide-tetramethylguanidinium pentanoate modified SiO2 loaded with PdCl2 appeared to be the most stable and to have a good activity in the reaction between butylacrylate and iodobezene, resulting in a complete conversion in 40 min at 100 °C, in four consecutive experiments. This study elucidated on the stability of the catalytic system with an ionic liquid layer during the catalyst synthesis but also under reaction conditions. In the bis-layered catalyst, the imidazolium moiety as a part of internal layer, brought rigidity to the structure, while in external layer pentanoic acid gave sufficiently acidic carboxylic group capable to coordinate 1,1,3,3-tetramethylguanidine (TMG) and thus, allow good dispersion of Pd nanoparticles. The catalyst was characterized by means of XPS, FT-IR, TEM, ICP-OES, ζ-potential, EDX, TGA, and 13C NMR. The release and catch mechanism was observed, whereas Pd re-deposition can be hindered by catalyst poisoning and eventual loss of palladium., Bio4Energy

The presence of pharmaceuticals in surface water, drinking water, and wastewater has attracted significant concern because of the non-biodegradability, resistance, and toxicity of pharmaceutical compounds. The catalytic ozonation of an anti-inflammatory pharmaceutical, ibuprofen was investigated in this work. The reaction mixture was analyzed and measured by high-performance liquid chromatography (HPLC). Liquid chromatography-mass spectrometry (LC-MS) was used for the quantification of by-products during the catalytic ozonation process. Ibuprofen was degraded by ozonation under optimized conditions within 1 h. However, some intermediate oxidation products were detected during the ibuprofen ozonation process that were more resistant than the parent compound. To optimize the process, nine heterogeneous catalysts were synthesized using different preparation methods and used with ozone to degrade the ibuprofen dissolved in aqueous solution. The aim of using several catalysts was to reveal the effect of various catalyst preparation methods on the degradation of ibuprofen as well as the formation and elimination of by-products. Furthermore, the goal was to reveal the influence of various support structures and different metals such as Pd-, Fe-, Ni-, metal particle size, and metal dispersion in ozone degradation. Most of the catalysts improved the elimination kinetics of the by-products. Among these catalysts, Cu-H-Beta-150-DP synthesized by the deposition–precipitation process showed the highest decomposition rate. The regenerated Cu-H-Beta-150-DP catalyst preserved the catalytic activity to that of the fresh catalyst. The catalyst characterization methods applied in this work included nitrogen adsorption–desorption, scanning electron microscopy, transmission electron microscopy, and Fourier-transform infrared spectroscopy. The large pore volume and small metal particle size contributed to the improved catalytic activity., Bio4Energy

In this work, an aqueous pentaethylenehexamine (PEHA) solution was studied for CO2 removal from bio-syngas for the first time. Firstly, pure CO2 absorption in aqueous PEHA solution under different conditions was conducted, and 20 wt% PEHA solution was identified as the best option. Secondly, the capture of CO2 was tested with synthetic syngas from a gas cylinder, and the species other than CO2 showed a negligible impact on CO2 removal. Finally, to evaluate the practical feasibility of using aqueous PEHA solution on the downstream CO2 capture, the pilot experiments of gasification with boreal forest-based biomasses were designed to provide real syngas with a realistic distribution in composition for further testing. The results showed that the operating conditions and the type of feedstocks affected the distribution in the bio-syngas composition. Among these feedstocks, at the optimal oxygen supply, using spruce needles generated the highest yields of CO and H2 and, meanwhile, gave rise to similar yields of other gases such as CO2, CH4, etc. The influence of the species other than CO2 for CO2 removal was negligible. Additionally, aqueous PEHA solution was tested as a biomass pretreatment agent, showing that no significant changes could be identified by the ultimate analysis (except for increased nitrogen content), but the yields of CO were affected negatively. On the other hand, when using the pretreated biomass by the aqueous PEHA solution, the NH3 concentration in bio-syngas reached to the highest (4000 parts per million), which slightly affected the CO2 absorption capacity and initial absorption rate of 20 wt% PEHA solution in a positive way., Bio4Energy

Carbamazepine (CBZ), a widely used pharmaceutical compound, is one of the most detected drugs in surface waters. The purpose of this work was to identify an active and durable catalyst, which, in combination with an ozonation process, could be used to remove CBZ and its degradation products. It was found that the CBZ was completely transformed after ozonation within the first minutes of the treatment. However, the resulting degradation products, 1-(2-benzaldehyde)-4-hydro-(1H,3H)-quinazoline-2-one (BQM) and 1-(2-benzaldehyde)-(1H,3H)-quinazoline-2,4-dione (BQD), were more resistant during the ozonation process. The formation and degradation of these products were studied in more detail and a thorough catalytic screening was conducted to reveal the reaction kinetics of both the CBZ and its degradation products. The work was performed by non-catalytic ozonation and with six different heterogeneous catalysts (Pt-MCM-41-IS, Ru-MCM-41-IS, Pd-H-Y-12-EIM, Pt-H-Y-12-EIM, Pd-H-Beta-300-EIM and Cu-MCM-41-A-EIM) operating at two temperatures 20 °C and 50 °C. The influence of temperature on degradation kinetics of CBZ, BQM and BQD was studied. The results exhibited a notable difference in the catalytic behavior by varying temperature. The higher reactor temperature (50 °C) showed a higher activity of the catalysts but a lower concentration of dissolved ozone. Most of the catalysts exhibited higher removal rate for BQM and BQD compared to non-catalytic experiments in both temperatures. The Pd-H-Y-12-EIM catalyst illustrated a higher degradation rate of by-products at 50 °C compared to other catalysts., Bio4Energy

Herein, we present the C-14 levulinate ester of 2,3-butanediol as the product of sugar fermentation liquors. The designed Brønsted acidic ionic liquid (BAIL) catalysts enable self-induced phase separation with ester products, and the role of anions has been investigated. Esterification reactions were carried out by 2,3-butanediol (2,3-BDO) and levulinic acid in solvent-free media and low temperatures (60–105 °C). For comparison, sulfuric acid, amberlite IR-120, and sulfonic acid-functionalized pyridinium ionic liquids with different anions were utilized as a catalyst upon esterification reaction. The diester product, namely, butane-2,3-diyl bis(4-oxopentanoate), was formed with a good yield (85%) and selectivity (85%) after complete conversion of 2,3-BDO in 24 h at 80 °C. The low yield (8%) of the monoester was observed. The monoester and diester were separated by a liquid–liquid extraction method. The ester products were characterized by various instrumental techniques such as 1H and 13C NMR, GC–FID, LC–MS, and FT-IR spectroscopy. The Hammett acidity functions of BAILs were determined from UV–vis spectroscopy. The catalyst was successfully recycled and reused in the processes. The spent BAILs were reused in six consecutive cycles with only a ∼7% diminished diester yield and selectivity. The produced levulinate ester will be useful as biofuel additives, solvents, plasticizers, and other applications., Bio4Energy

The density, sound velocity, and viscosity of 1-ethyl-3-methylimidazolium chloride [C2mim]Cl in pure water and aqueous solutions of some electrolytes such as potassium chloride, potassium carbonate, and potassium phosphate (weight fraction of salt fixed at ws = 0. 11) have been measured over a wide range of temperatures from 298.15 to 318.15 K. The obtained experimental data have been used to compute various volumetric, compressibility, and viscometric parameters, e.g., apparent molar properties, limiting apparent molar and transfer properties. The co-sphere overlap model was employed to describe the dominant intermolecular interactions in the ternary solutions. Additionally, the structure making/breaking nature of the [C2mim]Cl in the ternary solutions has been discussed in terms of Hepler's constant and the temperature derivative of viscosity B-coefficient (dB/dT). The activation free energy of solvent and solute, activation enthalpy, and activation entropy have been calculated by the application of transition state theory. The calculated parameters have been interpreted in the sense of solvent-solute and solute-solute interactions. The Fourier transform infrared (FTIR) studies also have been done for the studied systems. Volumetric, acoustic, viscometric, and spectroscopic studies can render some evidence and help to understand the aqueous solution behavior of ionic liquids.

Hydrothermal deoxygenation of tall oil fatty acids (TOFA) was investigated in the presence of aqueous formic acid (0.5–7.5 wt%) as a H2 donor in the presence of subcritical H2O pressure (569–599 K). Pd and Ru nanoparticles supported on carbon (5% Pd/CSigma, 5% Ru/CSigma, 10% Pd/CO850_DP, and 5% Ru/COPcomm_DP) were found to be efficient catalysts for deoxygenation of TOFA. The reaction pathway was mainly influenced by the concentration of formic acid and the catalyst. In case of Pd catalysts, in the presence of 0–2.5 wt% formic acid, decarboxylation was the dominant pathway producing n-paraffinic hydrocarbons with one less carbon atom (heptadecane yield up to 94 wt%), while with 5–7.5% formic acid, a hydrodeoxygenation/hydrogenation mechanism was favored producing C18 deoxygenation products octadecanol and octadecane as the main products (yields up to 70 wt%). In contrast, Ru catalysts produced a mixture of C5-C20 (n-and iso-paraffinic) hydrocarbons via decarboxylation, cracking and isomerization (up to 58 wt% C17 yield and total hydrocarbon yield up to 95 wt%) irrespective of formic acid concentration. Kinetic studies showed that the rates of deoxygenation displayed Arrhenius type behavior with apparent activation energies of 134.44 ± 31.36 kJ/mol and 148.92 ± 3.66 kJ/mol, for the 5% Pd/CSigma and 5% Ru/CSigma catalyst, respectively. Furthermore, the experiments with glycerol tristearate, rapeseed oil, sunflower oil, rapeseed biodiesel, and hydrolyzed rapeseed oil produced identical products confirming the versatility of the aforementioned catalytic systems for deoxygenation of C18 feedstocks., Bio4Energy

Herein, we report on the metal-free, one-pot synthesis of industrially important dimethyl carbonate (DMC) from molecular CO2 under ambient conditions. In this process, initially the CO2 was chemisorbed through the formation of a switchable ionic liquid (SIL), [DBUH] [CH3CO3], by the interaction of CO2 with an equivalent mixture of organic superbase 1,8-diazabicyclo-[5.4.0]-undec-7-ene (DBU) and methanol. The obtained SIL further reacted with methyl iodide (CH3I) to form DMC. The synthesis was carried out in both dimethyl sulfoxide (DMSO) and methanol. Methanol is preferred, as it not only served as a reagent and solvent in CO2 capture and DMC synthesis, but it also assisted in controlling the side reactions between chemical species such as CH3I and [DBUH]+ cation and increased the yield of DMC. Hence, the use of methanol avoided the loss of captured CO2 and favored the formation of DMC with high selectivity. Under the applied reaction conditions, 89% of the captured CO2 was converted to DMC. DBU was obtained, achieving 86% recovery of its salts formed during the synthesis. Most importantly, in this report we describe a simple and renewable solvent-based process for a metal-free approach to DMC synthesis under industrially feasible reaction conditions.

The influence of carbonic anhydrase (CA) on the CO2 absorption rate and CO2 load in aqueous blends of the amino acid ionic liquid pentaethylenehexamine prolinate (PEHAp) and methyl diethanolamine (MDEA) was investigated and compared to aqueous monoethanolamine (MEA) solutions. The aim was to identify blends with good enzyme compatibility, several fold higher absorption rates than MDEA and superior desorption potential compared to MEA. The blend of 5% PEHAp and 20% MDEA gave a solvent with approximately five-fold higher initial absorption rate than MDEA and a two-fold higher regeneration compared to MEA. Experiments in a small pilot absorption rig resulted in a mass transfer coefficient (KGa) of 0.48, 4.6, and 15 mol (m3 s mol fraction)−1 for 25% MDEA, 5% PEHAp, 20% MDEA, and 25% MEA, respectively. CA could maintain approximately 70% of its initial activity after 2 h incubation in PEHAp MDEA blends. Integration of CA with amine-based absorption resulted in a 31.7% increase in mass of absorbed CO2 compared to the respective non-enzymatic reaction at the optimal solvent: CA ratio and CA load. Combining novel blends and CA can offer a good compromise between capital and operating costs for conventional amine scrubbers, which could outperform MEA-based systems.

The liquefaction of biomass in ethanol, at the critical point, has high potential due to low temperature and pressure (243 °C, 63 bar) when compared with water (374 °C, 220 bar). The current study deals with the fractionation of birch wood powder which was liquefied under supercritical ethanol over acidic or non-acidic catalysts, 5 wt % Fe-Beta-H-150 and 5 wt % Fe–SiO2, respectively. Based on the results, the reaction mechanism for the formation of lignin degradation products was proposed. The main phenolic product was isoeugenol over 5 wt % Fe-Beta-H-150 while intermediate products, i.e. such as coniferyl, and sinapyl alcohol, 4-propenyl syringol, syringaresinol, as well as syringyldehyde reacted rapidly further. The thermodynamic analysis was performed by Joback approach and using Gibbs-Helmholtz equation supporting the obtained results., Bio4Energy

Herein we report the application of inexpensive mesoporous melamine-formaldehyde resins (MMFR and MMFR250) obtained by a novel template-free and organosolvent-free hydrothermal method as efficient heterogeneous catalysts for direct synthesis of cyclic carbonates from CO2 and epoxides (epichlorohydrin, butylene oxide and styrene oxide). The catalytic activity of the melamine resins was attributed to the abundant Lewis basic N-sites capable of activating CO2 molecules. Based on CO2-Temperature programmed desorption, the concentration of surface basic sites for MMFR and MMFR250 were estimated to be 172 and 56 µmol/g, while the activation energy of CO2 desorption (strength of basic sites) were calculated to be 92.1 and 64.5 kJ/mol. We also observed considerable differences in the catalytic activity and stability of polymeric catalysts in batch and in continuous-flow mode; due to the existence of a synergism between adsorption of CO2 and cyclic carbonates (poison). Our experiments also revealed important role of catalyst surface chemistry and CO2 partial pressure upon catalyst poisoning. Nevertheless, owing to their unique properties (large specific surface area, large mesoporous and CO2 basicity) melamine resins presented excellent activity (turnover frequency 207-2147 h-1), selectivity (>99%) for carbonation of epoxides with CO2 (20 bar initial CO2 or CO2:epoxide mole ratio ~1.5) under solvent-free and co-catalyst-free conditions at 100-120 oC. Most importantly, these low-cost polymeric catalysts were reusable and demonstrated exceptional stability in a flow reactor (tested upto 13 days time on stream, weight hourly space velocity 0.26-1.91 h-1) for continuous cyclic carbonate production from gaseous CO2 with different epoxides (conversion 76-100% and selectivity >99%) under industrially relevant conditions (120 oC, 13 bar, solvent-free/co-catalyst-free) confirming their superiority over the previously reported catalytic materials., Bio4Energy

Magnetic particles were prepared by a hydrothermal method and then successively covered by Metal–Organic-Frameworks MIL-101-NH2 with a high surface area. This was followed by deposition of Pd(OAc)2 on Fe3O4–NH2@MIL-101-NH2 particles. The final catalyst was characterized with FT-IR, nitrogen physisorption, thermogravimetry (TGA), scanning electron microscopy (SEM) combined with energy dispersive X-ray analysis (EDX), transmission electron microscopy (TEM), vibrating sample magnetometry (VSM), wide-angle X-ray diffraction spectroscopy (XRD) and X-ray photoelectron spectroscopy (XPS). The prepared magnetic catalyst was effectively used in the Heck coupling reaction in the presence of an inorganic base. The reaction parameters such as the base type, amounts of catalyst and solvents, temperature, and substrates ratios were optimized. The catalyst was then magnetically separated, washed, and reused 7 times without losing significantly catalytic activity., Bio4Energy

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Bio4Energy

Ionic liquids display good CO2 absorption capacity but poor absorption kinetics and high costs. In the present work, we show that these problems can be solved by impregnating the new low cost ionic liquid pentaethylenehexammonium chloride [PEHA][Cl] and the corresponding amine precursor on a low cost mesoporous microsphere support. Nitrogen adsorption/ desorption, high-resolution SEM and thermogravimetric analysis were employed to analyze the structural and thermal properties of the prepared sorbents. The CO2 adsorption and desorption performance was studied by column experiments and mathematical models were fitted to the data. The results showed that sorbents displayed excellent sorption kinetics and capacity, comparable to the best reports in the literature. In addition, the sorbents could be regenerated and displayed high thermal stability. Finally, the costs of the sorbents developed in the present work is much lower than previously reported sorbents. Therefore this novel supported IL system could be promising for industrial CO2 removal and recovery applications., Bio4Energy

Deep eutectic solvents (DESs) have gained a great interest among researchers owing to their inherent advantages to become an adaptable alternative to ionic liquids (ILs) and common amine solutions for CO2 capture. In the present study, we prepared five new three-component DESs by functionalization of choline chloride-ethanolamine (1,7, mol,mol) DES using different types of amines: diethanolamine (amine type 2), methyldiethanolamine (amine type 3), piperazine (amine type 2) as well as 1-(2-aminoethyl)piperazine (amine type 1 and 2). All of the prepared DESs are liquid at room temperature and their melting points were in the range of 265–276 K. The solubility of CO2 in the studied DESs was measured at pressures up to 2 MPa and 298.15 K. The obtained experimental data were analyzed by the use of generic Redlich-Kwong equation of state (RK-EOS) model and Henry's law constant have been calculated from the obtained experimental data through the EOS correlation. All the studied DESs show chemical absorption of CO2 which can be approved based on the excess enthalpy and Gibbs energy functions. FT-IR spectroscopy and 13C NMR verified the formation of carbamate in the CO2 absorption process which revealed the chemisorption of CO2 in the studied DESs. The ideal association model has been utilized to describe the excess thermodynamic functions and two different types of the chemical association have been detected AB2 and AB, (A refer to DESs and B to CO2). Based on the obtained solubility data, the amines that enhanced the absorption capacity of choline chloride-ethanolamine (1,7) follow the trend as follows: piperazine > aminoethylpiperazine > methyldiethanolamine > diethanolamine. Therefore, piperazine can be considered as an absorption enhancer. The viscosity of DESs before and after CO2 absorption as well as the thermal behavior of the DESs were also investigated., Bio4Energy

About 100 years ago, Zsigmondy and Bachmann invented a new method to induce phase inversion, the so-called vapor induced phase separation (VIPS). Since then many researchers have demonstrated this method in membrane fabrication. Here we present a review on membrane fabrication via VIPS to provide insights into membrane formation parameters in order to achieve desired properties for different applications. The key factors upon membrane preparation including solution parameters (i.e. polymer type and concentration, type of solvent, and additives) as well as operating parameters (i.e. exposure time, relative humidity, dissolution temperature, and vapor temperature) are comprehensively discussed. Furthermore, the design of a fouling-resistance membrane by the VIPS process has recently gained attention and is elaborated in details. The applications of the produced membranes via VIPS in water and wastewater treatment, gas separations, electrochemical applications (i.e. secondary batteries and supercapacitors) as well as in medical and biological applications are summarized and an outlook for future investigation is presented., Bio4Energy

The degradation of the pharmaceutical compound diclofenac in an aqueous solution was studied with an advanced oxidation method, catalytic ozonation. Diclofenac was destroyed in a few minutes by ozonation but several long-lasting degradation by-products were formed. For this reason, the combination of heterogeneous catalysts and ozonation was applied to eliminate them completely. The kinetics of the diclofenac degradation and the formation of by-products were thoroughly investigated. Loading of Pt on the catalysts resulted in an improvement of the activity. The Mesoporous Molecular Sieves (MCM) were one of the promising catalysts for the degradation of organic pollutants. In this study, six heterogeneous catalysts were screened, primarily MCM-22-100 catalysts with different Pt concentrations loaded via the evaporation-impregnation (EIM) method, and they were applied on the degradation of diclofenac. It was found that the presence of Pt improved the degradation of diclofenac and gave lower concentrations of by-products. The 2 wt % Pt-H-MCM-22-100-EIM demonstrated the highest degradation rate compared to the proton form, 1% or 5 wt % Pt concentration, i.e., an optimum was found in between. Pt-H-Y-12-IE and Pt-γ-Al2O3 (UOP)-IMP catalysts were applied and compared with the MCM-22 structure. Upon use of both of these catalysts, an improvement in the degradation of diclofenac and by-products was observed, and the 2 wt % Pt-H-MCM-22-100-EIM illustrated the maximum activity. All important characterization methods were applied to understand the behavior of the catalysts (X-ray powder diffraction, transmission electron microscopy, nitrogen physisorption, scanning electron microscopy, energy dispersive X-ray micro-analyses, pyridine adsorption-desorption with FTIR spectroscopy, X-ray photoelectron spectroscopy). Finally, leaching of Pt and Al were analyzed by inductively coupled optical emission spectrometry., Bio4Energy

Herein, we report the synthesis of a highly active and mesoporous Brønsted acidic NbOPO4/SBA-15 catalyst. The prepared catalysts were thoroughly characterized by means of analytical techniques such as XRD, FT-IR, XPS, NH3-TPD, SEM-EDS, TEM, TGA, 31P-MAS-NMR and N2-physisorption. The H3PO4 free deposition method was found to be effective for preserving the structure of Silica based carrier. In terms of catalytic performance, these materials demonstrated high activity upon C-C coupling of 2-methyl furan with carbonyl compounds and outperforming bulk NbOPO4, Nb2O5/SBA-15 and traditional solid acid catalysts (Al-MCM-41, Si/Al and H-ZSM-5). The NbOPO4/SBA-15 catalysts were stable and maintained high activity upon reuse and continuous operation (∼65 h). Furthermore, the Pd loaded counterparts (Pd/NbOPO4/SBA-15 and Pd/Nb2O5/SBA-15) also functioned as bifunctional catalysts and exhibited excellent activity upon subsequent hydrodeoxygenation of C-C coupling products. Most importantly, in terms of jet-fuel range hydrocarbons selectivity, these catalysts outperformed monofunctional Pd/carbon and aluminosilicate based bifunctional catalysts., Bio4Energy

A critical analysis of the role of Hammett basicity (H−) and aqueous basicity (pKa) in CO2 uptake in deep-eutectic solvents (DESs) suggests that neither H− nor pKa correlates with the CO2 w/w% capacity in the studied DESs. Instead, strong “synergistic interactions” between donor and acceptor moieties satisfactorily relate to the w/w% of CO2 in DESs., Bio4Energy

Rapid methods are very valuable in the determination of the kinetic and mass transfer effects for heterogeneously catalyzed reactions. The total pressure method is a classical tool in the measurement of the kinetics of gas-phase reactions, but it can be successfully applied to the kinetic measurements of gas-phase processes enhanced by solid catalysts. A general theory for the analysis of heterogeneously catalyzed gas-phase kinetics in gradientless batch reactors was presented for the case of intrinsic kinetic control and combined kinetic-diffusion control in porous catalysts. The concept was applied to gas-phase synthesis of methanol from carbon monoxide and hydrogen on a commercial copper-based catalyst (CuO/ZnO/Al2O3 R3-12 BASF). The reaction temperature was 180–210 °C and the initial total pressure was varied between 11 and 21 bar in a laboratory-scale autoclave reactor equipped with a rotating basket for the catalyst particles. The initial molar ratios CO-to-H2 were approximately 1:2, 1:3 and 1:4. The experimental data from methanol synthesis were compared with numerical simulations and a good agreement between the experiments and model simulations was achieved. The predicted equilibrium agrees with previously reported values., Bio4Energy

In this work, CO2 absorption capacities in a series of aqueous N-alkyl-N-methylmorpholinium-based ILs with acetate as the counterpart anion were investigated. Among these ILs, N-butyl-N-methylmorpholinium acetate ([Bmmorp][OAc]) with the highest CO2 absorption capacity was screened for thermodynamic modeling. The non-random two-liquid model and the Redlich–Kwong equation of state (NRTL-RK model) were used to describe the phase equilibria. The CH4 absorption capacity in the aqueous [Bmmorp][OAc] was also measured in order to verify the results predicted from the thermodynamic modeling, and the comparison shows the reliability of the model prediction. The parameters were embedded into the commercial software Aspen Plus. After that, the aqueous [Bmmorp][OAc] solutions with 30–40 wt % of water were selected to carry out process simulation for CO2 separation from biogas, and it was found that using these aqueous [Bmmorp][OAc] gave rise to lower energy usage and smaller size of equipment than other physical solvents. The results suggest that aqueous [Bmmorp][OAc] solution can be used as an alternative to organic solvents and has the potential to decrease the cost of CO2 separation., Bio4Energy

The present invention provides a method for producing hydrocarbons having 6 to 20 carbon atoms, comprising the steps of: a) providing a feedstock comprising saturated fatty acids, and/or derivatives thereof; b) deoxygenating the feedstock in the presence of a metal free hydrogenation and decarboxylation catalyst under low-pressure hydrothermal conditions, wherein the temperature is in the range 350-400 °C and the pressure is in the range 10-30 bar; and wherein the catalyst is a heteroatom-doped carbon material. Furthermore, there is provided a system for preforming the method in a single reactor (R) system comprises a bed of a carbon catalyst facilitating simultaneous hydrogenation and decarboxylation.

Ionic liquids (ILs) have been receiving much attention as solvents in various areas of biochemistry because of their various beneficial properties over the volatile solvents and ILs availability in myriad variants (perhaps as many as 10(8)) owing to the possibility of paring one cation with several anions and vice-versa as well as formulations as zwitterions. Their potential as solvents lies in their tendency to offer both directional and non-directional forces toward a solute molecule. Because of these forces, ionic liquids easily undergo intermolecular interactions with a range of polar/non-polar solutes, including biomolecules such as proteins and DNA. The interaction of genomic species in aqueous/non-aqueous states assists in unraveling their structure and functioning, which have implications in various biomedical applications. The charge density of ionic liquids renders them hydrophilic and hydrophobic, which retain intact over long-range of temperatures. Their ability in stabilizing or destabilizing the 3D-structure of a protein or the double-helical structure of DNA has been assessed superior to the water and volatile organic solvents. The aptitude of an ion in influencing the structure and stability of a native protein depends on their ranking in the Hofmeister series. However, at several instances, a reverse Hofmeister ordering of ions and specific ion-solute interaction has been observed. The capability of an ionic liquid in terms of the tendency to promote the coiling/uncoiling of DNA structure is noted to rely on the basicity, electrostatic interaction, and hydrophobicity of the ionic liquid in question. Any change in the DNA's double-helical structure reflects a change in its melting temperature (T-m), compared to a standard buffer solution. These changes in DNA structure have implications in biosensor design and targeted drug-delivery in biomedical applications. In the current review, we have attempted to highlight various aspects of ionic liquids that