Bilayer versus Polymeric Artificial Water Channel Membranes: Structural Determinants for Enhanced Filtration Performances.

Artificial water channels (AWCs) and their natural aquaporin counterparts selectively transport water. They represent a tremendous source of inspiration to devise biomimetic membranes for several applications, including desalination. They contain variable water-channel constructs with adaptative architectures and morphologies. Herein, we critically discuss the structural details that can impact the performances of biomimetic I quartets, obtained via adaptive self-assembly of alkylureido-ethylimidazoles HC4-HC18 in bilayer or polyamide (PA) membranes. We first explore the performances in bilayer membranes, identifying that hydrophobicity is an essential key parameter to increase water permeability. We compare various I quartets with different hydrophobic tails (from HC4 to HC18), and we reveal that a huge increase in single-channel water permeability, from 104 to 107 water molecules/s/channel, is obtained by increasing the size of the alkyl tail. Quantitative assessment of AWC-PA membranes shows that water permeability increases roughly from 2.09 to 3.85 L m-2 h-1 bar-1, for HC4 and HC6 reverse osmosis membranes, respectively, while maintaining excellent NaCl rejection (99.25-99.51%). Meanwhile, comparable HC8 loading induces a drop of performance reminiscent of a defective membrane formation. We show that the production of nanoscale sponge-like water channels can be obtained with insoluble, low soluble, and low dispersed AWCs, explaining the observed subpar performance. We conclude that optimal solubility enabling breakthrough performance must be considered to not only maximize the inclusion and the stability in the bilayer membranes but also achieve an effective homogeneous distribution of percolated particles that minimizes the defects in hybrid polyamide membranes.

Molecular Chemistry and Engineering of Boron-Modified Polyorganosilazanes as New Processable and Functional SiBCN Precursors.

A series of boron-modified polyorganosilazanes was synthesized from a poly(vinylmethyl-co-methyl)silazane and controlled amounts of borane dimethyl sulfide. The role of the chemistry behind their synthesis has been studied in detail by using solid-state NMR spectroscopy, FTIR spectroscopy, and elemental analysis. The intimate relationship between the chemistry and the processability of these polymers is discussed. Polymers with low boron contents displayed appropriate requirements for facile processing in solution, such as impregnation of host carbon materials, which resulted in the design of mesoporous monoliths with a high specific surface area after pyrolysis. Polymers with high boron content are more appropriate for solid-state processing to design mechanically robust monolith-type macroporous and dense structures after pyrolysis. Boron acts as a crosslinking element, which offers the possibility to extend the processability of polyorganosilazanes and suppress the distillation of oligomeric fragments in the low-temperature region of their thermal decomposition (i.e., pyrolysis) at 1000 °C under nitrogen. Polymers with controlled and high ceramic yields were generated. We provide a comprehensive mechanistic study of the two-step thermal decomposition based on a combination of thermogravimetric experiments coupled with elemental analysis, solid-state NMR spectroscopy, and FTIR spectroscopy. Selected characterization tools allowed the investigation of specific properties of the monolith-type SiBCN materials.

Adsorptive Removal of Rhodamine B Dye Using Carbon Graphite/CNT Composites as Adsorbents: Kinetics, Isotherms and Thermodynamic Study.

The study of the adsorption efficiency of new carbon/CNT composites was undertaken to remove a cationic dye, Rhodamine B (RhB), from dye-contaminated wastewater. Indeed, we investigated the effect of different experimental parameters such as time, initial concentration of dye and temperature on the adsorption of RhB by the carbon composites (KS44-0 and KS44-20). The results showed that the adsorption uptake increased with the initial concentration and solution temperature while maintaining a relatively constant pH. The presence of the carbon nanotubes provided more active sites for dye removal and improved the adsorption behavior of Rhodamine B dye. The analysis of the experimental data was conducted using model equations, such as Langmuir, Freundlich and Temkin isotherms. As regards the Freundlich isotherm model, it was the best fit for the equilibrium data obtained from the experiments. The applicability of the pseudo-second-order equation could be explained assuming that the overall adsorption rate is limited by the rate of adsorbate transport that occurs on the pore surfaces of adsorbents. Furthermore, the intraparticle diffusion and Bangham models were used to investigate the diffusion mechanism of RhB absorption onto carbon composites. They showed that multiple adsorption stages occurred simultaneously via pore surface diffusion. Concerning the thermodynamic parameters (∆G°, ∆H°, and ∆S°), they were calculated and explained in the mean of the chemical structure of the adsorbate. Negative standard Gibbs free energy change values (ΔG°ads) at all temperatures suggested that the adsorption process was spontaneous, and the positive values of the standard enthalpy change of adsorption (∆H°ads) revealed the reaction to be endothermic. The values of standard enthalpy (ΔH°ads) and activation energy (Ea) indicated that the adsorption process corresponds to physical sorption. The mechanisms for the removal of Rhodamine B dye from wastewater using carbon composite were predicted. RhB is a planar molecule that is readily adsorbed, in which adsorbed molecules are bound by hydrophobic or other weak interactions due to the π-π interactions between the dyes' aromatic backbones and the hexagonal skeleton of graphite and carbon nanotubes. Thus, the graphite carbon/carbon nanotube composite is believed to play a major role in organic pollutant reduction.

Enhanced Desalination Polyamide Membranes Incorporating Pillar[5]arene through in-Situ Aggregation-Interfacial Polymerization-isAGRIP.

Membrane-based desalination have an important role in water purification. Inspired by highly performant biological proteins, artificial water channels (AWC) have been proposed as active components to overcome the permeability/selectivity trade-off of desalination processes. Promising performances have been reported with Pillararene crystalline phases revealing impressive molecular-scale separation performances, when used as selective porous materials. Herein, we demonstrate that Pillar[5]arene PA[5] aggregates are in-situ generated and incorporated during the interfacial polymerization, within industrially relevant reverse osmosis polyamide-PA membranes. In particular, we explore the best combination between PA[5] aggregates and m-phenylenediamine (MPD) and trimesoylchloride (TMC) monomers to achieve their seamless incorporation in a defect-free hybrid polyamide PA[5]-PA membranes for enhanced desalination. The performances of the reference and hybrid membranes are evaluated by cross-flow filtration under real reverse osmosis conditions (15.5 bar of applied pressure) by filtration of brackish feed streams. The optimized membranes achieve a ∼40 % improvement, in water permeance of ∼2.76±0.5 L m-2 h-1 bar-1 and high 99.5 % NaCl rejection with respect to the reference TFC membrane and a similar water permeance compared to one of the best commercial BW30 membranes (3.0 L m-2 h-1 bar-1 and 99.5 % NaCl rejection).

Electro-oxidation of organic pollutants by reactive electrochemical membranes.

Electro-oxidation processes are promising options for the removal of organic pollutants from water. The major appeal of these technologies is the possibility to avoid the addition of chemical reagents. However, a major limitation is associated with slow mass transfer that reduces the efficiency and hinders the potential for large-scale application of these technologies. Therefore, improving the reactor configuration is currently one of the most important areas for research and development. The recent development of a reactive electrochemical membrane (REM) as a flow-through electrode has proven to be a breakthrough innovation, leading to both high electrochemically active surface area and convection-enhanced mass transport of pollutants. This review summarizes the current state of the art on REMs for the electro-oxidation of organic compounds by anodic oxidation. Specific focuses on the electroactive surface area, mass transport, reactivity, fouling and stability of REMs are included. Recent advances in the development of sub-stoichiometric titanium oxide REMs as anodes have been made. These electrodes possess high electrical conductivity, reactivity (generation of •OH), chemical/electrochemical stability, and suitable pore structure that allows for efficient mass transport. Further development of REMs strongly relies on the development of materials with suitable physico-chemical characteristics that produce electrodes with efficient mass transport properties, high electroactive surface area, high reactivity and long-term stability.

How To Functionalize Ceramics by Perfluoroalkylsilanes for Membrane Separation Process? Properties and Application of Hydrophobized Ceramic Membranes.

The combination of microscopic (atomic force microscopy and scanning electron microscopy) and goniometric (static and dynamic measurements) techniques, and surface characterization (surface free energy determination, critical surface tension, liquid entry pressure, hydraulic permeability) was implemented to discuss the influence of perfluoroalkylsilanes structure and grafting time on the physicochemistry of the created hydrophobic surfaces on the titania ceramic membranes of 5 kD and 300 kD. The impact of molecular structure of perfluoroalkylsilanes modifiers (possessing from 6 to 12 carbon atoms in the fluorinated part of the alkyl chain) and the time of the functionalization process in the range of 5 to 35 h was studied. Based on the scanning electron microscopy with energy-dispersive X-ray spectroscopy, it was found that the localization of grafting molecules depends on the membrane pore size (5 kD or 300 kD). In the case of 5 kD titania membranes, modifiers are attached mainly on the surface and only partially inside the membrane pores, whereas, for 300 kD membranes, the perfluoroalkylsilanes molecules are present within the whole porous structure of the membranes. The application of 4 various types of PFAS molecules enabled for interesting observations and remarks. It was explained how to obtain ceramic membrane surfaces with controlled material (contact angle, roughness, contact angle hysteresis) and separation properties. Highly hydrophobic surfaces with low values of contact angle hysteresis and low roughness were obtained. These surfaces possessed also low values of critical surface tension, which means that surfaces are highly resistant to wetting. This finding is crucial in membrane applicability in separation processes. The obtained and characterized hydrophobic membranes were subsequently applied in air-gap membrane distillation processes. All membranes were very efficient in MD processes, showing good transport and selective properties (∼99% of NaCl salt rejection). Depending on the membrane pore size and used modifiers, the permeate flux was in the range of 0.5-4.5 kg·m(-2)·h(-1) and 0.3-4.2 kg·m(-2)·h(-1) for 5 kD and 300 kD membranes, respectively.

Highly efficient hydrophobic titania ceramic membranes for water desalination.

Hydrophobic titania ceramic membranes (300 kD) were prepared by grafting of C6F13C2H4Si(OC2H5)3 and C12F25C2H4Si(OC2H5)3 molecules and thus applied in membrane distillation (MD) process of NaCl solutions. Grafting efficiency and hydrophobicity were evaluated by contact angle measurement, atomic force microscopy, scanning electron microscopy, nitrogen adsorption/desorption, and liquid entry pressure measurement of water. Desalination of NaCl solutions was performed using the modified hydrophobic membranes in air gap MD (AGMD) and direct contact MD (DCMD) processes in various operating conditions. High values of NaCl retention coefficient (>99%) were reached. The permeate fluxes were in the range 231-3692 g·h(-1)·m(-2), depending on applied experimental conditions. AGMD mode appeared to be more efficient showing higher fluxes and selectivity in desalination. Overall mass transfer coefficients (K) for membranes tested in AGMD were constant over the investigated temperature range. However, K values in DCMD increased at elevated temperature. The hydrophobic layer was also stable after 4 years of exposure to open air.

Synthesis and performances of bio-sourced nanostructured carbon membranes elaborated by hydrothermal conversion of beer industry wastes.

Hydrothermal carbonization (HTC) process of beer wastes (Almaza Brewery) yields a biochar and homogeneous carbon-based nanoparticles (NPs). The NPs have been used to prepare carbon membrane on commercial alumina support. Water filtration experiments evidenced the quasi-dense behavior of the membrane with no measurable water flux below an applied nitrogen pressure of 6 bar. Gas permeation tests were conducted and gave remarkable results, namely (1) the existence of a limit temperature of utilization of the membrane, which was below 100°C in our experimental conditions, (2) an evolution of the microstructure of the carbon membrane with the operating temperature that yielded to improved performances in gas separation, (3) the temperature-dependent gas permeance should follow a Knudsen diffusion mechanism, and (4) He permeance was increasing with the applied pressure, whereas N2 and CO2 permeances remained stable in the same conditions. These results yielded an enhancement of both the He/N2 and He/CO2 permselectivities with the applied pressure. These promising results made biomass-sourced HTC-processed carbon membranes encouraging candidates as ultralow-cost and sustainable membranes for gas separation applications.

Ion-driven ATP pump by self-organized hybrid membrane materials.

We report new hybrid organic-inorganic materials, based on macrocyclic receptors 1-3 self-organized in tubular superstructures prepared by sol-gel process. Fourier transform infrared (FTIR) and NMR spectroscopic analyses demonstrate that the self-organization by hydrogen bonding of organogel superstructures of 2 and 3 were preserved in the hybrid materials throughout the sol-gel process. The molecular arrangement of heteroditopic receptors defines a particularly attractive functional transport device for both cation (tubular macrocycles) and anion (sandwich-urea) directional-diffusion transport mechanism in the hybrid membrane material. This system has been employed successfully to design a solid dense membrane, functioning as an ion-powered adenosine triphosphate (ATP(2)(-)) pump, and illustrates how a self-organized hybrid material performs interesting and potentially useful functions.