ACS Sustainable Chemistry & Engineering

Efficient separation of CO2 from CO2 /CH4 mixtures using membranes has economic, environmental and industrial importance. Membrane technologies are currently dominated by polymers due to their processing abilities and low manufacturing costs. However, polymeric membranes suffer from either low gas permeabilities or low selectivities. Metal organic frameworks (MOFs) are suggested as potential membrane candidates that offer both high selectivity and permeability for CO2 /CH4 separation. Experimental testing of every single synthesized MOF material as membranes is not practical due to the availability of thousands of different MOF materials...

Hydrodeoxygenation (HDO) of isoeugenol (IE) was investigated using bimetallic iridium-rhenium and platinum-rhenium catalysts supported on alumina in the temperature and pressure ranges of 200-250 °C and 17-40 bar in nonpolar dodecane as a solvent. The main parameters were catalyst type, hydrogen pressure, and initial concentration. Nearly quantitative yield of the desired product, propylcyclohexane (PCH), at complete conversion in 240 min was obtained with Ir-Re/Al2 O3 prepared by the deposition-precipitation method using 0...

In the current study, platinum-present as a negligible component (below 1 ppb, the detection limit of the HR-ICP-MS at the dilutions used) in real industrial hydrometallurgical process solutions-was recovered by an electrodeposition-redox replacement (EDRR) method on pyrolyzed carbon (PyC) electrode, a method not earlier applied to metal recovery. The recovery parameters of the EDRR process were initially investigated using a synthetic nickel electrolyte solution ([Ni] = 60 g/L, [Ag] = 10 ppm, [Pt] = 20 ppm, [H2 SO4 ] = 10 g/L), and the results demonstrated an extraordinary increase of 3 × 105 in the [Pt]/[Ni] on the electrode surface cf...

In this work, the preparation of nanocomposites based on poly(l-lactide) PLLA and graphite nanoplatelets (GNP) was assessed by applying, for the first time, the reactive extrusion (REX) polymerization approach, which is considered a low environmental impact method to prepare polymer systems and which allows an easy scalability. In particular, ad hoc synthesized molecules, constituted by a pyrene end group and a poly(d-lactide) (PDLA) chain (Pyr-d), capable of interacting with the surface of GNP layers as well as forming stereoblocks during the ring-opening polymerization (ROP) of l-lactide, were used...

This research focuses on the preparation of biobased copolyamides containing biacetalized galactaric acid (GalX), namely, 2,3:4,5-di- O -isopropylidene-galactaric acid (GalXMe) and 2,3:4,5-di- O -methylene-galactaric acid (GalXH), in bulk by melt polycondensation of salt monomers. In order to allow the incorporation of temperature-sensitive sugar-derived building blocks into copolyamides at temperatures below the degradation temperature of the monomers and below their melting temperatures, a clever selection of salt monomers is required, such that the sugar-derived salt monomer dissolves in the other salt monomers...

Lignin micro- and nanoparticles (LMNPs) synthesized from side-streams of pulp and paper and biorefinery operations have been proposed for the generation of new, high-value materials. As sustainable alternatives to particles of synthetic or mineral origins, LMNPs viability depends on scale-up, manufacturing cost, and applications. By using experimental data as primary source of information, along with industrial know-how, we analyze dry and spherical LMNPs obtained by our recently reported aerosol/atomization method...

Multifunctional catalytic systems consisting of physical mixtures of Au nanoparticles (2-3 nm) supported on metal oxides and Sn-MCM-41 nanoparticles (50-120 nm) were synthesized and investigated for the selective conversion of glycerol to methyl lactate. The Au catalyst promotes the oxidation of glycerol to trioses, whereas the solid acid Sn-MCM-41 catalyzes the rearrangement of the intermediate trioses to methyl lactate. Among the supported Au nanoparticles, Au/CuO led to the highest yield and selectivity toward methyl lactate, while the Sn-MCM-41 nanoparticles showed much better catalytic performance than a benchmark solid acid catalyst (USY zeolite)...

CO2 -switchable solvents, typically neutral solvents that switch with CO2 into ionic species, were investigated for use as entrainer in fluid separations such as extractive distillation. Their switchable nature was investigated, which may facilitate liquid-liquid extraction or extractive distillation as ionic liquid (IL), whereas during regeneration their decarboxylation into the amine form prevents temperature shoot-up. Studied elements included a property screening and detailed mechanistic and kinetic studies on the switching of 2-ethylhexylamine and N , N- benzyl methylamine...

Cellulose acetate is one of the most important cellulose derivatives. Herein we present a method to access cellulose acetate with a low degree of substitution through a homogeneous reaction in the ionic liquid 1,5-diazabicyclo[4.3.0]non-5-enium acetate ([DBNH][OAc]). This ionic liquid has also been identified as an excellent cellulose solvent for dry-jet wet fiber spinning. Cellulose was dissolved in [DBNH][OAc] and esterified in situ to be immediately spun into modified cellulose filaments with a degree of substitution (DS) value of 0...

The mechanism of lignin nanoprecipitation and subsequent self-assembly was elucidated by studying generation of lignin nanoparticles (LNPs) from aqueous ethanol. LNP formation was found to follow a kinetically controlled nucleation-growth mechanism in which large lignin molecules formed the initial critical nuclei. Using this information, we demonstrate entrapment of budesonide in LNPs and subsequent pH-triggered and surfactant-responsive release of this synthetic anti-inflammatory corticosteroid. Overall, our results not only provide a promising intestinal delivery system for budesonide but also deliver fundamental mechanistic understanding for the entrapment of actives in LNPs with controlled size and release properties...

Metabolic engineering has the potential to steadily enhance product titers by inducing changes in metabolism. Especially, availability of cofactors plays a crucial role in improving efficacy of product conversion. Hence, the effect of certain trace elements was studied individually or in combinations, to enhance butanol flux during its biological production. Interestingly, nickel chloride (100 mg L-1 ) and sodium selenite (1 mg L-1 ) showed a nearly 2-fold increase in solvent titer, achieving 16.13 ± 0.24 and 12...

Fermentation of sugars to the so-called ABE mixture delivers a three component mixture of shorter chain oxygenates: acetone, n -butanol and ethanol. In order to convert these into liquid transportation fuels that are analogous to the currently used fossil energy carriers, novel catalytic chain elongation methods involving C-C bond formation are desired. Herein we report on a simple, non-noble-metal-based method for the highly selective coupling of 1-butanol and acetone into high molecular weight (C7-C11) ketones, as well as ABE mixtures into (C5-C11) ketones using the solid base Mg-Al-PMO in combination with small amount of Raney nickel...

Lignin is the second most abundant biopolymer on the planet. It is a biocompatible, cheap, environmentally friendly and readily accessible material. It has been reported that these biomacromolecules have antimicrobial activities. Consequently, lignin (LIG) has the potential to be used for biomedical applications. In the present work, a simple method to prepare lignin-based hydrogels is described. The hydrogels were prepared by combining LIG with poly(ethylene glycol) and poly(methyl vinyl ether- co -maleic acid) through an esterification reaction...

In recent years, iron-based nanoparticles (FeNPs) have been successfully used in environmental remediation and water treatment. This study examined ecotoxicity of two FeNPs produced by green tea extract (smGT, GTFe) and their ability to degrade malachite green (MG). Their physicochemical properties were assessed using transmission electron microscopy, X-ray powder diffraction, dynamic light scattering, and transmission Mössbauer spectroscopy. Using a battery of ecotoxicological bioassays, we determined toxicity for nine different organisms, including bacteria, cyanobacterium, algae, plants, and crustaceans...

Chain elongation is an open-culture fermentation process that facilitates conversion of organic residues with an additional electron donor, such as ethanol, into valuable n-caproate. Open-culture processes are catalyzed by an undefined consortium of microorganisms which typically also bring undesired (competing) processes. Inhibition of competing processes, such as syntrophic ethanol oxidation, will lead to a more selective n-caproate production process. In this study, we investigated the effect of n-caproate concentration on the specific activity of chain elongation and competing processes using batch inhibition assays...

Nutrient and energy recovery is becoming more important for a sustainable future. Recently, we developed a hydrogen gas recycling electrochemical system (HRES) which combines a cation exchange membrane (CEM) and a gas-permeable hydrophobic membrane for ammonia recovery. This allowed for energy-efficient ammonia recovery, since hydrogen gas produced at the cathode was oxidized at the anode. Here, we successfully up-scaled and optimized this HRES for ammonia recovery. The electrode surface area was increased to 0...

Conversion of vegetable-derived triglycerides to fatty acid methyl esters (FAMEs) is a popular approach to the generation of biodiesel fuels and the basis of a growing industry. Drawbacks of the strategy are that (a) the glycerol backbone of the triglyceride is discarded as waste, and (2) most available natural triglycerides in the U.S. are multi-unsaturated or fully saturated, giving inferior fuel performance and causing engine problems. Here we show that catalysis by iridium complex 1 can address both of these problems through selective reduction of triglycerides high in polyunsaturation...

Wood-derived biopolymers have attracted great attention over the past few decades due to their abundant and versatile properties. The well-separated three main components, i.e., cellulose, hemicelluloses, and lignin, are considered significant candidates for replacing and improving on oil-based chemicals and materials. The production of nanocellulose from wood pulp opens an opportunity for novel material development and applications in nanotechnology. Currently, increased research efforts are focused on developing 3D printing techniques for wood-derived biopolymers for use in emerging application areas, including as biomaterials for various biomedical applications and as novel composite materials for electronics and energy devices...

Divalent cations in feedwater can cause significant decreases in efficiencies for membrane processes, such as reverse electrodialysis (RED). In RED, power is harvested from the mixing of river and seawater, and the obtainable voltage is reduced and the resistance is increased if divalent cations are present. The power density of the RED process can be improved by removing divalent cations from the fresh water. Here, we study divalent cation removal from fresh water using seawater as draw solution in a Donnan dialysis (DD) process...

In this study we describe the synthesis of bis(pyrrolidone) based dicarboxylic acids from itaconic acid and their application in 2-oxazoline resins for fully renewable thermoset materials. The monomers are obtained using a bulk aza-Michael addition of a diamine and two itaconic acid molecules using a catalytic amount of water. The monomers can be isolated in high purity after recrystallization, though their yield proved to be highly dependent on the selected diamine spacer length: In general, only the dicarboxylic acids containing diamines with an even number of methylene spacers are isolated in high yields...