Photoswitchable nonlinear optical properties of azobenzene-based supramolecular complexes: insights from density functional theory.

Density functional theory (DFT) calculations were performed for a series of supramolecular assemblies containing azobenzene (Azo-X where X = I, Br and H) and alkoxystilbazole subunits to evaluate their electronic, linear and nonlinear optical properties. These assemblies are derivatives of azobenzene, obtained by the substitution of electron-withdrawing and electron-donating groups onto the molecular skeleton. The interaction energies (Eint) of all the designed supramolecular complexes (IA-IF, IIA-IIF and IIIA-IIIF) range from -1.0 kcal mol-1 to -7.7 kcal mol-1. The electronic properties of these hydrogen/halogen bond driven supramolecular assemblies such as vertical ionization energies (VIE), HOMO-LUMO energy gap (GH-L), excitation energies, density of states (DOS) and natural population (NPA) analyses were also computed. The non-covalent interaction index (NCI) and quantum theory of atoms in molecules (QTAIM) analyses were also performed to validate the nature of inter- and intra-molecular interactions in these complexes. A substantial enhancement in the first hyperpolarizability (ß0) values of the designed supramolecular complexes was observed, which is driven by the charge transfer from the pyridyl moiety of alkoxystilbazole to Azo-X. The highest ß0 value of 1.3 × 104 au was observed for the supramolecular complex of p-nitro substituted azobenzene with alkoxystilbazole (ID complex). Moreover, the results show that the substitution of electron-withdrawing groups on Azo-X can also bring larger ß0 values for such complexes. It was confirmed on a purely theoretical basis that both the types of noncovalent interactions present and the substituent group incorporated influence the nonlinear optical (NLO) response of the systems. Furthermore, the ß0 values of the E (trans) and Z (cis) forms were compared to demonstrate the two-way photoinduced switching mechanism.

Enhancing CO2 separation from N2 mixtures using hydrophobic porous supports immobilized with tributyl-tetradecyl-phosphonium chloride [P44414][Cl].

The main obstacles in adopting solvent-based CO2 capture technology from power plant flue gases at the industrial scale are the energy requirements for solvent regeneration and their toxicity. These challenges can be overcome using new green and more stable ionic liquids (ILs) as solvents for post-combustion CO2 capture. In the current study, tributyl-tetradecyl-phosphonium chloride [P44414][Cl] as an IL, was immobilized on hydrophobic porous supports of polypropylene (PP), polyvinylidene fluoride (PVDF), and polytetrafluoroethylene (PTFE) at 298 ± 3 K and pressures up to 2 bar. The surface morphology indicated homogenous immobilization of the IL on the membrane support. Supported ionic liquid membranes (SILMs) were tested for CO2 permeability and CO2/N2 selectivity. None of the SILMs exhibited IL leaching up to 2 bar. The PTFE-based SILM performed better than other supports with minimum loss in water contact angle (WCA) and achieved good antiwetting with a maximum CO2 permeability and selectivity over N2 of 2300 ± 139 Barrer and 31.60 ± 2.4, respectively. This work achieves CO2 permeability about two-fold more than other works having CO2/N2 selectivity range of 25-35 in similar SILMs. The diffusivity of CO2 and N2 in [P44414][Cl] was measured as 3.64 ± 0.18 and 2.01 ± 0.09 [10-8 cm2 s-1] and CO2 and N2 solubility values were 9.79 ± 0.47 and 0.19 ± 0.001 [10-2 cm3(STP) cm-3 cmHg-1], respectively. The high values of Young's modulus and tensile strength of the PTFE support-based SILM (234 ± 12 MPa and 6.07 ± 0.31 MPa, respectively) indicated the long-term application of SILM in flue gas separation. The results indicated phosphonium chloride-based ILs could be better solvent candidates for CO2 removal from large volumes of flue gases than amine-based ILs.

Recent progress in integrated fixed-film activated sludge process for wastewater treatment: A review.

Integrated fixed-film activated sludge (IFAS) process is considered as one of the leading-edge processes that provides a sustainable solution for wastewater treatment. IFAS was introduced as an advancement of the moving bed biofilm reactor by integrating the attached and the suspended growth systems. IFAS offers advantages over the conventional activated sludge process such as reduced footprint, enhanced nutrient removal, complete nitrification, longer solids retention time and better removal of anthropogenic composites. IFAS has been recognized as an attractive option as stated from the results of many pilot and full scales studies. Generally, IFAS achieves >90% removals for combined chemical oxygen demand and ammonia, improves sludge settling properties and enhances operational stability. Recently developed IFAS reactors incorporate frameworks for either methane production, energy generation through algae, or microbial fuel cells. This review details the recent development in IFAS with the focus on the pilot and full-scale applications. The microbial community analyses of IFAS biofilm and floc are underlined along with the special emphasis on organics and nitrogen removals, as well as the future research perspectives.

Hybrid Membrane Distillation and Wet Scrubber for Simultaneous Recovery of Heat and Water from Flue Gas.

Flue gas contains high amount of low-grade heat and water vapor that are attractive for recovery. This study assesses performance of a hybrid of water scrubber and membrane distillation (MD) to recover both heat and water from a simulated flue gas. The former help to condense the water vapor to form a hot liquid flow which later used as the feed for the MD unit. The system simultaneously recovers water and heat through the MD permeate. Results show that the system performance is dictated by the MD performance since most heat and water can be recovered by the scrubber unit. The scrubber achieved nearly complete water and heat recovery because the flue gas flows were supersaturated with steam condensed in the water scrubber unit. The recovered water and heat in the scrubber contains in the hot liquid used as the feed for the MD unit. The MD performance is affected by both the temperature and the flow rate of the flue gas. The MD fluxes increases at higher flue gas temperatures and higher flow rates because of higher enthalpy of the flue gas inputs. The maximum obtained water and heat fluxes of 12 kg m-2 h-1 and 2505 kJm-2 h-1 respectively, obtained at flue gas temperature of 99 °C and at flow rate of 5.56 L min-1. The MD flux was also found stable over the testing period at this optimum condition. Further study on assessing a more realistic flue gas composition is required to capture complexity of the process, particularly to address the impacts of particulates and acid gases.

Development of novel hydrophilic ionic liquid membranes for the recovery of biobutanol through pervaporation.

This paper aims to develop novel hydrophilic ionic liquid membranes using pervaporation for the recovery of biobutanol. Multiple polyvinyl alcohol (PVA) membranes based on three commercial ionic liquids with different loading were prepared for various experimental trials. The ionic liquids selected for the study include tributyl (tetradecyl) phosphonium chloride ([TBTDP][Cl]), tetrabutyl phosphonium bromide ([TBP][Br]) and tributyl methyl phosphonium methylsulphate ([TBMP][MS]). The synthesized membranes were characterized and tested in a custom-built pervaporation set-up. All ionic liquid membranes showed better results with total flux of 1.58 kg/m2h, 1.43 kg/m2h, 1.38 kg/m2h at 30% loading of [TBP][Br], [TBMP][MS] and [TBTDP][Cl] respectively. The comparison of ionic liquid membranes revealed that by incorporating [TBMP]MS to PVA matrix resulted in a maximum separation factor of 147 at 30 wt% loading combined with a relatively higher total flux of 1.43 kg/m2h. Density functional theory (DFT) calculations were also carried out to evaluate the experimental observations along with theoretical studies. The improved permeation properties make these phosphonium based ionic liquid a promising additive in PVA matrix for butanol-water separation under varying temperature conditions.

Optimal balance: alkali metal-doped boron carbide nanosheets achieve superior stability and nonlinear optical responsiveness.

Nonlinear optical (NLO) materials play a vital role in various technological domains, including optoelectronics and photonic devices. Designing NLO materials, particularly inorganic ones, that strike a compromise between nonlinear optical sensitivity and stability has always been a difficult task. In order to improve the stability and NLO responsiveness, we propose and examine alkali metal-doped boron carbide nanosheets (M@BCNs) in this study. Calculated interaction energies (E int), which span from -65.5 to -94.9 kcal mol-1, show the stability of the M@BCN complexes. The first hyperpolarizability value has also increased, to a maximum of 3.11 × 105 au, indicating improved nonlinear optical characteristics. QTAIM (quantum theory of atoms in molecules) and NCI (non-covalent interactions) analyses demonstrate the validity of the interactions. According to NBO (natural bond orbital) analysis, the alkali metals gain almost +1 charge. Due to the low transition energies and considerable charge transfer between the alkali metals and nanosheet, the nonlinear optical response is significantly improved. The M@BCN complexes also show transparency in the ultraviolet region, with absorption maxima ranging from 917 to 2788 nm. This study proposes a viable approach for developing alkali metal-doped boron carbide nanosheets with improved NLO response and stability.

Enhancing Water Purification by Integrating Titanium Dioxide Nanotubes into Polyethersulfone Membranes for Improved Hydrophilicity and Anti-Fouling Performance.

Water pollution remains a critical concern, one necessitated by rapidly increasing industrialization and urbanization. Among the various strategies for water purification, membrane technology stands out, with polyethersulfone (PES) often being the material of choice due to its robust mechanical properties, thermal stability, and chemical resistance. However, PES-based membranes tend to exhibit low hydrophilicity, leading to reduced flux and poor anti-fouling performance. This study addresses these limitations by incorporating titanium dioxide nanotubes (TiO2NTs) into PES nanofiltration membranes to enhance their hydrophilic properties. The TiO2NTs, characterized through FTIR, XRD, BET, and SEM, were embedded in PES at varying concentrations using a non-solvent induced phase inversion (NIPS) method. The fabricated mixed matrix membranes (MMMs) were subjected to testing for water permeability and solute rejection capabilities. Remarkably, membranes with a 1 wt% TiO2NT loading displayed a significant increase in pure water flux, from 36 to 72 L m2 h-1 bar-1, a 300-fold increase in selectivity compared to the pristine sample, and a dye rejection of 99%. Furthermore, long-term stability tests showed only a slight reduction in permeate flux over a time of 36 h, while dye removal efficiency was maintained, thus confirming the membrane's stability. Anti-fouling tests revealed a 93% flux recovery ratio, indicating excellent resistance to fouling. These results suggest that the inclusion of TiO2 NTs offers a promising avenue for the development of efficient and stable anti-fouling PES-based membranes for water purification.

Macroalgal biochar synthesis and its implication on membrane fouling mitigation in fluidized bed membrane bioreactor for wastewater treatment.

The intensification of biochar into fluidized bed membrane bioreactor was investigated to mitigate membrane fouling. Different biochars from algal biomass were produced and used as biomaterials for wastewater treatment. In this study, different macroalgal biochar was synthesized at different pyrolysis temperatures and characterized using Scanning Electron Microscopy (SEM), X-ray Diffraction (XRD), Brunauer Emmett-Teller (BET) and Fourier transform infrared spectroscopy (FTIR) techniques to implicate their effect on membrane fouling reduction in fluidized bed membrane bioreactor. The combined effect of macroalgal biochars and biocarriers with gas sparging was evaluated for fouling mitigation. Macroalgal biochar curtailed membrane fouling effectively at low gas sparging rate. Transmembrane pressure (TMP) was reduced to 0.053 bar; under the fluidization of biochar-650 and biocarriers with gas sparging; from 0.27 bar (gas sparging only). Combined effect of gas sparging, biocarriers and biochar-650 instigated 92.1% fouling reduction in comparative to gas sparging alone. Mechanical scouring driven by biocarriers could reduce fouling due to removing surface deposit of foulants from membrane surface effectively and biochar can efficiently adsorb foulants because of its active functional groups resulting in reduction of colloidal fouling. The addition of divalent ions (Ca2+) further enhanced the fouling reduction in fluidized bed membrane bioreactor.

Task-specific polymeric membranes to achieve high gas-liquid mass transfer.

In the current study, Polyimide (P84)-based polymeric membranes were fabricated and used as spargers in the bubble column reactor (BCR) to get a high gas-liquid mass transfer (GL-MT) rate of oxygen in water. Different polymeric membranes were fabricated by incorporating polyvinyl pyrrolidone (PVP) as a porogen and a Zeolitic Imidazolate Framework (ZIF-8) to induce high porosity and hydrophobicity in the membranes. The GL-MT efficiency of membranes was evaluated by measuring the overall volumetric mass transfer coefficient (kLa) of oxygen in air. The kLa of O2 (in air) was measured by supplying the gas through a fixed membrane surface area of 11.94 cm2 at a fixed gas flow rate of 3L/min under atmospheric pressure. The results revealed that adding porogen and ZIF-8 increased the porosity of the membranes compared to the pure polymeric membranes. In comparison, the ZIF-8 (3 wt%) based membrane showed the highest porosity (80%), hydrophobicity (95° contact angle) and kLa of oxygen in air (241.2 h-1) with 78% saturation in only 60 s. ZIF-8 based membranes showed the potential to increase the amount of dissolved oxygen in BCR by reducing the bubble size, increasing the number of bubbles, and improving the hydrophobicity. The study showed that ZIF-8 based membrane diffusers are expected to produce high GL-MT in microbial syngas fermentation. To the best of our knowledge, this is the first study on the fabrication and application of polymeric membranes for GL-MT applications. Further research should be conducted under real fermentation conditions to assess the practicality of the system to support substrate utilization, microbial growth, and product formation.

Photocatalytic degradation of industrial dye using hybrid filler impregnated poly-sulfone membrane and optimizing the catalytic performance using Box-Behnken design.

Mixed Matrix Membranes have gained significant attention over the past few years due to their diverse applications, unique hybrid inorganic filler and polymeric properties. In this article, the impregnation of nano-hybrid filler (polyoxometalates (∼POMs) encapsulated into the metal-organic framework (MOF) âˆ¼ PMOF) on the polysulfone membrane (∼PSF) was done, resulting in a mix matrix membrane (∼PMOF@PSF). The developed structure was characterized by Fourier transform infrared (FT-IR), powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and transmission electron microscopes (TEM). The results confirmed that the nano-hybrid filler was successfully fabricated on the surface of PSF. Different loading ratios of nano-hybrid filler (5%, 10%, 20%, 30%, and 40%) were used for impregnation. The study's objective was to enhance catalytic performance using optimization curves designed using a three-level Box-Behnken Design (BBD) simulation. The photodegradation of Methylene Blue (∼MB) was studied against PMOF@PSF30% and was found to perform optimally when the concentration of catalyst, time of degradation, and temperature were 0.05-0.15 gm, 40-120 min, and 30-70 °C respectively. These experiments were replicated 15 times, and obtained results were further processed using a two-quadratic polynomial model to develop response surface methodology (RSM), which allowed for a functional relationship between the decolorization and experimental parameters. The optimal performance of the reaction mixture was calculated to be 0.15 gm for concentration, 70 °C for temperature, with an 80 min reaction time. Under these optimal conditions, the predicted decolorization of MB was 98.09%. Regression analysis with R2 > 0.99 verified the fit of experimental results with predicted values. The PMOF@PSF PSF30% demonstrated excellent reusability as its dye degradation properties were significantly unaffected after ten cycles.

Exploring the potential of highly selective deep eutectic solvents (DES) based membranes for dehydration of butanol via pervaporation.

N-butanol has unique physicochemical and combustion properties, similar to gasoline, which makes it an environmentally friendly alternative to conventional fuels. To improve the efficiency, the dehydration of butanol is necessary. This paper aims to investigate the performance of Deep Eutectic Solvents (DESs) based membranes for the dehydration of n-butanol by the pervaporation process. Three DES with different combinations of hydrogen bond donors and acceptors, i.e., DL-menthol: Lauric acid (DES), DL-menthol-Palmitic acid (DES), and [TETA] Cl: Thymol (DES), were used. We hypothesized that (i) incorporation of hydrophobic DES would increase the hydrophobicity of the membranes; (ii) specific functional groups (phenolic group, amine group) in DESs would enhance the butanol-philic character of membranes, and (iii) hydrophobic DESs would increase the butanol separation efficiency and permeability of membranes. FTIR analysis and physicochemical parameters of the resultant liquid mixture validated the DESs' production. The DESs were then filled into the permeable support, resulting in supported liquid membranes (SLMs). An additional layer of polydimethylsiloxane (PDMS) was coated directly on the DES-PSf layer to prevent leaching out of DES. A feed containing a 6 wt % aqueous solution of butanol under varying temperatures was studied. The results showed that among all membranes, [TETA] Cl: Thymol DES-based membrane showed the highest sorption of 36% at room temperature. The introduction of DES in membranes resulted in a remarkable increase in the separation factor while sustaining a reasonable flux. Among all the membranes, the DL-menthol: Lauric acid (DES) based membrane exhibited the highest separation factor of 57 with a total flux of 0.11 kg/m2. h. Significantly high butanol-water separation was attributed to the low viscosity and high butanol solubility of the chosen DES, which makes it a suitable substitute to conventional ILs.

One pot synthesis of UiO-66@IL composite for fabrication of CO2 selective mixed matrix membranes.

In this study, a facile and extensible one pot approach was utilized to synthesize ionic liquid inside a porous metal organic framework (UiO-66). Different characterization techniques were used to confirm the successful synthesis of UiO-66@IL composite. The MMMs were characterized and tested for CO2 separation from CH4 or N2 at ambient and elevated temperatures. SEM images exhibited well dispersion of the filler particles with no notable defect even at high loadings. Single and mixed gas permeation results indicated significant performance (CO2 permeability: 143 Barrer and CO2/CH4, CO2/N2 selectivity: 28.32, 61.11 respectively) by enhancing the permeability of CO2 by 74% and selectivity to 31% and 26% for CO2/CH4 and CO2/N2 compared with neat Pebax®1657 membrane.

Development of highly permselective Mixed Matrix Membranes comprising of polyimide and Ln-MOF for CO2 capture.

Mixed Matrix Membranes (MMMs) with hybrid organic-inorganic characteristics offer a strong alternative to traditional polymer-based membranes to reduce the trade-off between gas permeability and selectivity. This work incorporated lanthanum-Metal Organic Frameworks in the Matrimid to fabricate MMMs. To understand the effects of nano-filler on membranes' morphology, porosity, thermal stability, and chemical composition, MMMs were fabricated with three different loadings of nano-filler, i.e., 10, 20 and 30 wt%. The selectivity and permeability of CH4, CO2, and N2 gases through MMMs were investigated at 10 bar pressure and temperatures ranging from 25 to 55 °C. All MMMs exhibited enhanced CO2 permeation with increased nano-filler loading because the porous nano-filler provided additional channels and fractional free volume in the polymer matrix. The 30 wt% loaded membrane showed a 183% increase in permeability of CO2 than neat membrane. With increasing nano-filler loading, the selectivity of MMMs increased from 34.1 to 48.45 for CO2/N2 and from 36.2 to 54.67 for CO2/CH4, confirming the absence of membrane defects, improved filler/polymer interface, and excellent dispersion of nano-filler in the polymer matrix. The results proved that these membranes could be further used for gas separation industrial applications.

Controlled Covalent Functionalization of ZIF-90 for Selective CO2 Capture & Separation.

Mixed Matrix Membranes (MMM) with enhanced selectivity and permeability are preferred for gas separations. The porous metal-organic frameworks (MOFs) materials incorporated in them play a crucial part in improving the performance of MMM. In this study, Zeolitic imidazolate frameworks (ZIF-90) are selected to fabricate Polyetherimide (PEI) MMMs owing to their lucrative structural and chemical properties. This work reports new controlled post-synthetic modifications of ZIF-90 (50-PSM-ZIF-90) with ethanolamine to control the diffusion and uptake of CO2. Physical and chemical properties of ZIF-90, such as stability and presence of aldehyde functionality in the imidazolate linker, allow for easy modulation of the ZIF-90 pores and window size to tune the gas transport properties across ZIF-90-based membranes. Effects of these materials were investigated on the performance of MMMs and compared with pure PEI membranes. Performance of the MMMs was evaluated in terms of permeability of different gases and selective separation of CO2 and H2 gas. Results presented that the permeability of all membranes was in the following order, i.e., P(H2) > P(CO2) > P(O2) > P(CH4) > P(C2H6) > P(C3H8) > P(N2), demonstrating that kinetic gas diffusion is the predominant gas transport mode in these membranes. Among all the membranes, permeability of pure PEI membrane was highest for all gases due to the uniform porous morphology. The pure PEI membrane showed highest permeability of H2, which is 486.5 Barrer, followed by 49 Barrer for O2, 29 Barrer for N2, 142 Barrer for CO2, 41 Barrer for CH4, 40 Barrer for C2H6 and 39.6 Barrer for C3H8. Results also confirm the superiority of controlled PSM-ZIF-90-PEI membrane over the pure PEI and ZIF-90-PEI membranes in CO2 and H2 separation performance. The 50-PSM-ZIF-90 PEI membrane exhibited a 20% increase in CO2 separation from methane and a 26% increase over nitrogen compared to the ZIF-90-PEI membrane. The 50-PSM-ZIF-90 PEI membrane showed 15% more H2/O2 separation and 9% more H2/CH4 separation than ZIF-90 PEI membrane. Overall, this study represents the role of controlled PSM in enhancing the property of new materials like ZIF and its application in MMMs fabrication to develop a promising approach for the CO2 capture and separation.

Functionalized organic filler based integrated membranes for environmental remediation.

Mixed matrix membranes (MMMs) are synthesized for efficient CO2 separation released from various anthropogenic sources, which are due to global environmental concerns. The synergetic effect of porous nitrogen-rich, CO2-philic filler and polymer in mixed matrix-based membranes (MMMs) can separate CO2 competent. The development of various loadings of porphyrin poly(N-isopropyl Acryl Amide) (P-NIPAM)as functionalized organic fillers (5-20%) in polysulfone (PSU) through solution casting is carried out followed by the various characterizations including field emission scanning electron microscopy (FESEM), X-ray diffraction analysis (XRD), Fourier Transform Infrared Spectrometer(FT-IR) analysis and pure and mixed gas permeations ranging from 2 to 10 bar feed pressure. Due to both organic species interactions in the matrix, well-distributed fillers and homogenous surfaces, and cross-sectional structures were observed due to π-π interactions and Lewis's basic functionalities. The strong affinity of porous nitrogen-rich and CO2-philic fillers through gas permeation analysis showed high CO2/CH4 and CO2/N2 gas performance that surpassed Robeson's upper bound limit. Comparatively, MMMs showed improved CO2/CH4 permeabilities from 87.5 ± 0.5 Barrer to 88.2 ± 0.9 Barrer than pure polymer matrix. For CO2/N2, CO2 permeabilities improved to 75 ± 0.8 Barrer than pure polymer matrix. For both gas pairs (CO2/CH4, CO2/N2), respective pureselectivities (84%; 86%) and binary selectivities (85% and 85%)were improved. Various theoretical gas permeation models were used to predict CO2 permeabilities for MMMs from which the modified Maxwell-Wagner-Sillar model showed the least AARE% of 0.87. The results showed promising results for efficient CO2 separation due to exceptional functionalized P-PNIPAM affinitive properties. Finally, cost analysis reflected the inflated cost of membranes production for industrial setup using indigenous resources.

CO2 separation by supported liquid membranes synthesized with natural deep eutectic solvents.

Betaine-based natural deep eutectic solvents (NADESs), a new class of green solvents, were immobilized into a porous polyvinylidene fluoride (PVDF) support and evaluated for the separation of CO2 from CO2/N2 and CO2/CH4 mixtures. Two types of NADESs were synthesized by mixing betaine (hydrogen bond acceptor-HBA) with malic acid and tartaric acid (hydrogen bond donors-HBD) respectively. FTIR and Raman spectroscopy were studied to confirm the synthesis and purity of the NADESs. The thermal strength of the NADESs was investigated using thermogravimetric analysis. The gas permeation results of the fabricated NADES-based-supported liquid membranes (NADES-SLMs) showed that the permeability of CO2 increased from 25.55 to 29.33 Barrer on substitution of hydrogen bond donor from tartaric acid to malic acid. Similarly, the ideal CO2/CH4 selectivity varied from 51.1 to 56.4 as tartaric acid was replaced by malic acid as the HBD. The performance of NADES-SLMs was compared with the competing imidazolium-based-supported ionic liquid membranes, and proved NADES-SLMs as a promising alternative considering their green potential and comparable gas separation performance. The current effort for the exploitation of NADESs into PVDF membranes in this study is expected to open new routes for the efficient separation of CO2 from the industrial gas mixture.

Sustainable mixed matrix membranes containing porphyrin and polysulfone polymer for acid gas separations.

The synergetic effect of nitrogen-rich and CO2-philic filler and polymer in mixed matrix-based membranes (MMMs) can separate CO2 competently. The introduction of well-defined nanostructured porous fillers of pores close to the kinetic diameter of the gas molecule and polymer matrix compatibility is a challenge in improving the gas transportation characteristics of MMMs. This study deals with the preparation of porphyrin filler and the polysulfone (PSf) polymer MMMs. The fillers demonstrated uniform distribution, uniformity, and successful bond formation. MMMs demonstrated high thermal stability with a glass transition temperature in the range of 480-610 °C. The porphyrin filler exhibited microporous nature with the presence of π-π bonds and Lewis's basic functionalities between filler-polymer resulted in a highly CO2-philic structure. The pure and mixed gas permeabilities and selectivity were successfully improved and surpass the Robeson's upper bound curve's tradeoff. Additionally, the temperature influence on CO2 permeability revealed lower activation energies at higher temperatures leading to the gas transport facilitation. This can be granted consistency and long-term durability in polymer chains. These results highlight the unique properties of porphyrin fillers in CO2 separation mixed matrix membranes and offer new knowledge to increase comprehension of PSf performance under various contents or environments.

CO2 from waste to resource by developing novel mixed matrix membranes.

Mixed matrix membranes (MMMs) were fabricated by the hydrothermal synthesis of ordered mesoporous KIT-6 type silica and incorporating in polyimide (P84). KIT-6 and MMMs were characterized to evaluate morphology, thermal stability, surface area, pore volume, and other characteristics. SEM images of synthesized MMMs and permeation data of CO2 suggested homogenous dispersion of mesoporous fillers and their adherence to the polymer matrix. The addition of KIT-6 to polymer matrix improved the permeability of CO2 due to the increase in diffusivity through porous particles. The permeability was 3.2 times higher at 30% loading of filler. However, selectivity showed a slight decrease with the increase in filler loadings. The comparison of gas permeation results of KIT-6 with the well-known MCM-41 revealed that KIT-6 based MMMs showed 14% higher permeability than that of MMMs composed of mesoporous MCM-41. The practical commercial viability of synthesized membranes was examined under different operating temperatures and mixed gas feeds. Mesoporous KIT-6 silica is an attractive additive for gas permeability enhancement without compromising the selectivity of MMMs. Graphical abstract.

Ultra low-pressure filtration system for energy efficient microalgae filtration.

Microalgae-based products have gained growing interest leading to an increase in large-scale cultivation. However, the high energy associated with microalgae harvesting becomes one of the bottlenecks. This study evaluated an energy-efficient microalga harvesting via ultra-low-pressure membrane (ULPM) filtration (<20 kPa) in combination with aeration. ULPM offered various benefits especially in terms of reducing the energy consumption due to it operated under low transmembrane pressure (TMP). High TMP often associated with high pumping energy hence would increase the amount of energy consumed. In addition, membrane with high TMP would severely affect by membrane compaction. Results showed that membrane compaction leads to up to 66 % clean water permeability loss when increasing the TMP from 2.5 to 19 kPa. The Chlorella vulgaris broth permeabilities decreased from 1660 and 1250 to 296 and 251 L/m2hrbar for corresponding TMPs for system with and without aeration, respectively. However, it was found that membrane fouling was more vulnerable at low TMP due to poor foulant scouring from a low crossflow velocity in which up to 56 % of permeability losses were observed. Membrane fouling is the biggest drawback of membrane system as it would reduce the membrane performance. In this study, aeration was introduced as membrane fouling control to scour-off the foulant from membrane surface and pores. In terms of energy consumption, it was observed that the specific energy consumption for the ULPM were very low of up to 4.4 × 10-3 kWh/m3. Overall, combination of low TMP with aeration offers lowest energy input.

Mixed-Matrix Membranes Comprising of Polysulfone and Porous UiO-66, Zeolite 4A, and Their Combination: Preparation, Removal of Humic Acid, and Antifouling Properties.

High-performance Mixed-Matrix Membranes (MMMs) comprising of two kinds of porous fillers UiO-66 and Zeolite 4Aand their combination were fabricated with polysulfone (PSf) polymer matrix. For the very first time, UiO-66 and Zeolite 4A were jointly used as nanofillers in MMMs with the objective of complimenting synergistic effects. The individual and complimentary effects of nanofillers were investigated on membrane morphology and performance, pure water flux, humic acid rejection, static humic acid adsorption, and antifouling properties of membranes. Scanning Electron Microscopy (SEM) analysis of membranes confirmed that all MMMs possessed wider macrovoids with higher nanofiller loadings than neat PSf membranes and the MMMs (PSf/UiO-66 and PSf/Zeolite 4A-UiO-66) showed tendency of agglomeration with high nanofiller loadings (1 wt% and 2 wt%). All MMMs exhibited better hydrophilicity and lower static humic acid adsorption than neat PSf membranes. Pure water flux of MMMs was higher than neat PSf membranes but the tradeoff between permeability and selectivity was witnessed in the MMMs with single nanofiller. However, MMMs with combined nanofillers (PSf/Zeolite 4A-UiO-66) showed no such tradeoff, and an increase in both permeability and selectivity was achieved. All MMMs with lower nanofiller loadings (0.5 wt% and 1 wt%) showed improved flux recovery. PSf/Zeolite 4A-UiO-66 (0.5 wt%) membranes showed the superior antifouling properties without sacrificing permeability and selectivity.