Cellulose Triacetate-Based Mixed-Matrix Membranes with MXene 2D Filler-CO2/CH4 Separation Performance and Comparison with TiO2-Based 1D and 0D Fillers.

Mixed-matrix membranes (MMMs) possess the unique properties and inherent characteristics of their component polymer and inorganic fillers, or other possible types of additives. However, the successful fabrication of compact and defect-free MMMs with a homogeneous filler distribution poses a major challenge, due to poor filler/polymer compatibility. In this study, we use two-dimensional multi-layered Ti3C2Tx MXene nanofillers to improve the compatibility and CO2/CH4 separation performance of cellulose triacetate (CTA)-based MMMs. CTA-based MMMs with TiO2-based 1D (nanotubes) and 0D (nanofillers) additives were also fabricated and tested for comparison. The high thermal stability, compact homogeneous structure, and stable long-term CO2/CH4 separation performance of the CTA-2D samples suggest the potential application of the membrane in bio/natural gas separation. The best results were obtained for the CTA-2D sample with a loading of 3 wt.%, which exhibited a 5-fold increase in CO2 permeability and 2-fold increase in CO2/CH4 selectivity, compared with the pristine CTA membrane, approaching the state-of-the-art Robeson 2008 upper bound. The dimensional (shape) effect on separation performance was determined as 2D > 1D > 0D. The use of lamellar stacked MXene with abundant surface-terminating groups not only prevents the aggregation of particles but also enhances the CO2 adsorption properties and provides additional transport channels, resulting in improved CO2 permeability and CO2/CH4 selectivity.

CO2/CH4 and H2/CH4 Gas Separation Performance of CTA-TNT@CNT Hybrid Mixed Matrix Membranes.

This study explored the underlying synergy between titanium dioxide nanotube (TNT) and carbon nanotube (CNT) hybrid fillers in cellulose triacetate (CTA)-based mixed matrix membranes (MMMs) for natural gas purification. The CNT@TNT hybrid nanofillers were blended with CTA polymer and cast as a thin film by a facile casting technique, after which they were used for single gas separation. The hybrid filler-based membrane depicted a higher CO2 uptake affinity than the single filler (CNT/TNT)-based membrane. The gas separation results indicate that the hybrid fillers (TNT@CNT) are strongly selective for CO2 over CH4 and H2 over CH4. The increment in the CO2/CH4 and H2/CH4 selectivities compared to the pristine CTA membrane was 42.98 from 25.08 and 48.43 from 36.58, respectively. Similarly, the CO2 and H2 permeability of the CTA-TNT@CNT membrane increased by six- and five-fold, respectively, compared to the pristine CTA membrane. Such significant improvements in CO2/CH4 and H2/CH4 separation performance and thermal and mechanical properties suggest a feasible and practical approach for potential biogas upgrading and natural gas purification.

Improved CO2/CH4 Separation Properties of Cellulose Triacetate Mixed-Matrix Membranes with CeO2@GO Hybrid Fillers.

The study of the effects associated with the compatibility of the components of the hybrid filler with polymer matrix, which ultimately decide on achieving mixed matrix membranes (MMMs) with better gas separation properties, is essential. Herein, a facile solution casting process of simple incorporating CeO2@GO hybrid inorganic filler material is implemented. Significant improvements in material and physico-chemical properties of the synthesized membranes were observed by SEM, XRD, TGA, and stress-strain measurements. Usage of graphene oxide (GO) with polar groups on the surface enabled forming bonds with ceria (CeO2) nanoparticles and CTA polymer and provided the homogeneous dispersion of the nanofillers in the hybrid MMMs. Moreover, increasing GO loading concentration enhanced both gas permeation in MMMs and CO2 gas uptakes. The best performance was achieved by the membrane containing 7 wt.% of GO with CO2 permeability of 10.14 Barrer and CO2/CH4 selectivity 50.7. This increase in selectivity is almost fifteen folds higher than the CTA-CeO2 membrane sample, suggesting the detrimental effect of GO for enhancing the selectivity property of the MMMs. Hence, a favorable synergistic effect of CeO2@GO hybrid fillers on gas separation performance is observed, propounding the efficient and feasible strategy of using hybrid fillers in the membrane for the potential biogas upgrading process.

CeO2-Blended Cellulose Triacetate Mixed-Matrix Membranes for Selective CO2 Separation.

Due to the high affinity of ceria (CeO2) towards carbon dioxide (CO2) and the high thermal and mechanical properties of cellulose triacetate (CTA) polymer, mixed-matrix CTA-CeO2 membranes were fabricated. A facile solution-casting method was used for the fabrication process. CeO2 nanoparticles at concentrations of 0.32, 0.64 and 0.9 wt.% were incorporated into the CTA matrix. The physico-chemical properties of the membranes were evaluated by SEM-EDS, XRD, FTIR, TGA, DSC and strain-stress analysis. Gas sorption and permeation affinity were evaluated using different single gases. The CTA-CeO2 (0.64) membrane matrix showed a high affinity towards CO2 sorption. Almost complete saturation of CeO2 nanoparticles with CO2 was observed, even at low pressure. Embedding CeO2 nanoparticles led to increased gas permeability compared to pristine CTA. The highest gas permeabilities were achieved with 0.64 wt.%, with a threefold increase in CO2 permeability as compared to pristine CTA membranes. Unwanted aggregation of the filler nanoparticles was observed at a 0.9 wt.% concentration of CeO2 and was reflected in decreased gas permeability compared to lower filler loadings with homogenous filler distributions. The determined gas selectivity was in the order CO2/CH4 > CO2/N2 > O2/N2 > H2/CO2 and suggests the potential of CTA-CeO2 membranes for CO2 separation in flue/biogas applications.

Interfacial Design of Mixed Matrix Membranes via Grafting PVA on UiO-66-NH2 to Enhance the Gas Separation Performance.

In this study, defect-free facilitated transport mixed matrix membrane (MMM) with high loading amount of UiO-66-NH2 nanoparticles as metal-organic frameworks (MOFs) was fabricated. The MOFs were covalently bonded with poly (vinyl alcohol) (PVA) to incorporate into a poly (vinyl amine) (PVAm) matrix solution. A uniform UiO-66-NH2 dispersion up to 55 wt.% was observed without precipitation and agglomeration after one month. This can be attributed to the high covalent interaction at interfaces of UiO-66-NH2 and PVAm, which was provided by PVA as a functionalized organic linker. The CO2 permeability and CO2/N2 and selectivity were significantly enhanced for the fabricated MMM by using optimal fabrication parameters. This improvement in gas performance is due to the strong impact of solubility and decreasing diffusion in obtained dense membrane to promote CO2 transport with a bicarbonate reversible reaction. Therefore, the highest amount of amine functional groups of PVAm among all polymers, plus the abundant amount of amines from UiO-66-NH2, facilitated the preferential CO2 permeation through the bicarbonate reversible reaction between CO2 and -NH2 in humidified conditions. XRD and FTIR were employed to study the MMM chemical structure and polymers-MOF particle interactions. Cross-sectional and surface morphology of the MMM was observed by SEM-EDX and 3D optical profilometer to detect the dispersion of MOFs into the polymer matrix and explore their interfacial morphology. This approach can be extended for a variety of polymer-filler interfacial designs for gas separation applications.

Microwave hydrothermal synthesis and upconversion properties of BiVO4 nanoparticles.

Nanomaterials are the subject of extensive investigations due to their applications in medicine, multimodal imaging, volumetric displays, and photonics. Here, lanthanide-doped bismuth vanadate (BiVO4) upconverting nanoparticles (UCNPs) have been reported. The nanoparticles have been synthesized by a microwave hydrothermal method. As-synthesized nanoparticles are highly crystalline in the tetragonal zircon phase with particles about 200 nm in size. Under 980 nm excitation, intense multicolor visible and near-infrared upconversion emissions are observed. Moreover, broadband infrared downshifting emissions are also observed. Time-resolved emission measurements have been carried out to investigate the involved upconversion and energy transfer mechanism. The BiVO4-based UCNPs may provide a new class of nanomaterials for multifunctional applications.

Understanding the multifunctionality in Cu-doped BiVO4 semiconductor photocatalyst.

A visible light-induced, Cu-doped BiVO4 photocatalyst was synthesized by a microwave hydrothermal method. The photocatalytic efficiency was investigated in the degradation of model water pollutants like Methylene Blue (dye) and ibuprofen (pharmaceuticals), as well as the inactivation of Escherichia coli (bacteria). The Cu-doped BiVO4 samples showed better efficiency than undoped BiVO4, and the 1wt.% Cu-doped BiVO4 sample showed the best efficiency. The degradation of Methylene Blue reached 95%, while the degradation of ibuprofen reached 75%, and the inactivation of E. coli reached 85% in irradiation with visible light. The appearance of additional absorption band shoulders and widening of the optical absorption in the visible range makes the prepared powder an efficient visible light-driven photocatalyst. Moreover, the formation of an in-gap energy state just above the valance band as determined by density functional theory (DFT) first principle calculation, facilitates the wider optical absorption range of the doped system. Similarly, this in-gap energy state also acts as an electron trap, which is favorable for the efficient separation and photoexcited charge carriers' transfer process. The formation of oxygen vacancies due to doping also improved the separation of the charge carrier, which promoted the trapping of electrons and inhibited electron hole recombination, thus increasing the photocatalytic activity. No decrease in the efficiency of the 1wt.% Cu-doped BiVO4 photocatalyst in the degradation of ibuprofen over three consecutive cycles revealed the stability of the photocatalyst towards photocorrosion. These findings highlight the multifunctional applications of Cu-doped BiVO4 in wastewater containing multiple pollutants.

Understanding Mechanism of Photocatalytic Microbial Decontamination of Environmental Wastewater.

Several photocatalytic nanoparticles are synthesized and studied for potential application for the degradation of organic and biological wastes. Although these materials degrade organic compounds by advance oxidation process, the exact mechanisms of microbial decontamination remains partially known. Understanding the real mechanisms of these materials for microbial cell death and growth inhibition helps to fabricate more efficient semiconductor photocatalyst for large-scale decontamination of environmental wastewater or industries and hospitals/biomedical labs generating highly pathogenic bacteria and toxic molecules containing liquid waste by designing a reactor. Recent studies on microbial decontamination by photocatalytic nanoparticles and their possible mechanisms of action is highlighted with examples in this mini review.

Microwave hydrothermal synthesis and upconversion properties of Yb3+/Er3+ doped YVO4 nanoparticles.

Yb3+ and Er3+ doped YVO4 (Yb3+/Er3+:YVO4) nanoparticles with highly efficient near-infrared to visible upconversion properties have been synthesized by microwave hydrothermal process. Uniform-sized Yb3+/Er3+:YVO4 nanoparticles were synthesized within 1 h at 140 °C which is relatively faster than the conventional hydrothermal process. Under 980 nm laser excitation, strong green and less strong red emissions are observed which are attributed to 2H11/2, 4S3/2 to 4I15/2 and 4F9/2 to 4I15/2 transitions of Er3+ respectively. The emission intensity is found to depend strongly on the concentration of Yb3+. The quadratic dependence of upconversion intensity on the excitation power indicates that the upconversion process is governed by two-photon absorption process.

Fabrication of Ag-decorated BiOBr-mBiVO4 dual heterojunction composite with enhanced visible light photocatalytic performance for degradation of malachite green.

A visible light active Ag-decorated BiVO4-BiOBr dual heterojunction photocatalyst was prepared using a facile hydrothermal method, followed by the photodeposition of Ag. The photocatalytic activity of the synthesized samples was investigated by monitoring the change in malachite green (MG) concentration upon visible light irradiation. The synthesized sample was highly effective for the degradation of non-biodegradable MG. The enhanced activity observed was ascribed to the efficient separation and transfer of charge carriers across the dual heterojunction structure as verified by photoluminescence measurements. The removal of MG was primarily initiated by hydroxyl radicals and holes based on scavenger's effect. To gain insight into the degradation mechanism, both high performance liquid chromatography and high resolution-quantitative time of flight, electrospray ionization mass spectrometry measurements during the degradation process were carried out. The degradation primarily followed the hydroxylation and N-demethylation process. A possible reaction pathway is proposed on the basis of all the information obtained under various experimental conditions.

Visible-light-induced Ag/BiVO4 semiconductor with enhanced photocatalytic and antibacterial performance.

An Ag-loaded BiVO4 visible-light-driven photocatalyst was synthesized by the microwave hydrothermal method followed by photodeposition. The photocatalytic performance of the synthesized samples was evaluated on a mixed dye (methylene blue and rhodamine B), as well as bisphenol A in aqueous solution. Similarly, the disinfection activities of synthesized samples towards the Gram-negative Escherichia coli (E. coli) in a model cell were investigated under irradiation with visible light (λ ≥ 420 nm). The synthesized samples have monoclinic scheelite structure. Photocatalytic results showed that all Ag-loaded BiVO4 samples exhibited greater degradation and a higher mineralization rate than the pure BiVO4, probably due to the presence of surface plasmon absorption that arises due to the loading of Ag on the BiVO4 surface. The optimum Ag loading of 5 wt% has the highest photocatalytic performance and greatest stability with pseudo-first-order rate constants of 0.031 min-1 and 0.023 min-1 for the degradation of methylene blue and rhodamine B respectively in a mixture with an equal volume and concentration of each dye. The photocatalytic degradation of bisphenol A reaches 76.2% with 5 wt% Ag-doped BiVO4 within 180 min irradiation time. Similarly, the Ag-loaded BiVO4 could completely inactivate E. coli cells within 30 min under visible light irradiation. The disruption of the cell membrane as well as degradation of protein and DNA exhibited constituted evidence for antibacterial activity towards E. coli. Moreover, the bactericidal mechanisms involved in the photocatalytic disinfection process were systematically investigated.