Enhanced pollutant photodegradation over nanoporous titanium-vanadium oxides with improved interfacial interactions.

This study addressed the separation problem of colloidal catalytic powder from its solution and pore blockage of traditional metallic oxides by fabricating nanoporous composites of titanium (Ti)-vanadium (V) oxide via magnetron sputtering, electrochemical anodization, and annealing processes. The effect of V-deposited loading on the composite semiconductors was investigated by varying V sputtering power (20-250 W) to correlate their physicochemical properties to the photodegradation performance of methylene blue. The obtained semiconductors revealed circular and elliptical pores (14-23 nm) and formed different metallic and metallic oxide crystalline phases. Within the nanoporous composite layer, V ions substituted Ti4+, leading to Ti3+ formation accompanied by decreased band gap values and higher visible-light absorption. Thus, the band gap of TiO2 was 3.15 eV, while that of Ti-V oxide with the maximum V content (at 250 W) was 2.47 eV. The interfacial separators between clusters in the mentioned composite created traps disrupting the charge carrier movements between crystallites, thereby decreasing the photoactivity. In contrast, the composite prepared with the minimum V content showed approximately 90% degradation efficiency under solar-simulated irradiation resulting from the homogeneous V dispersion and the lower recombination possibility, owing to its p-n heterojunction constituent. The nanoporous photocatalyst layers with their novel synthesis approach and outstanding performance can be applied in other environmental remediation applications.

The Effect of Sanitizing Treatments on Respirator Filtration Performance.

The potential for alcoholic vapors emitted by common sanitizing treatments to deteriorate the (electrostatic) filtration performance of disposable respirator masks has been investigated. Reports in the literature and some standard test methods provide a confusing and ambiguous picture concerning the relevance of this effect. Four different types of exposure were investigated in this study to clarify the effect of alcoholic vapor emissions on respirator masks. These included exposure to saturated vapors, use of hand sanitizers, cleaning of table surfaces and sanitization of masks by spraying them with alcohol-containing solutions. Methods employed were designed to be as real-world oriented as possible while remaining reproducible. Filtration performance and deterioration effects on exposure to the different treatments were determined on three different types of certified commercial respirator masks-a P2 and two KN95 masks. This study provides substantial evidence that disposable respirator masks with an accepted performance rating are seriously compromised from an exposure to saturated alcoholic vapors, can tolerate a one-off spray treatment with an alcoholic solution and retain their attested protection under the influence of alcoholic vapors from the use of hand sanitizer or spray sanitizer. Considering the range of vastly different outcomes obtained from the four treatments investigated, it seems prudent to assess in each case the specific effects of alcoholic solution treatments and vapors on respirator masks before use.

Impact of Wearing on Filtration Performance of Electrostatic Filter Face Masks.

Certified disposable respirators afford important protection from hazardous aerosols but lose performance as they are worn. This study examines the effect of wear time on filtration efficiency. Disposable respirators were worn by CSIRO staff over a period of 4 weeks in early 2020. Participants wore the respirator masks for given times up to eight hours whilst working in laboratory/office environments. At that time COVID-19 precautions required staff to wear surgical (or other) masks and increase use of hand sanitizer from dispenser stations. Results obtained from a test group of ten individuals without health preconditions show an increasing number of masks failing with wear time, while the remainder continue to perform nearly unaffected for up to 8 h. Some masks were found to retain filtration performance better than others, possibly due to the type of challenge they were subjected to by the wearer. However, the rate and extent of decay are expected to differ between environments since there are many contributing factors and properties of the aerosol challenge cannot be controlled in a live trial. Penetration and variability increased during wear; the longer the wear time, the more deleterious to particle removal, particularly after approximately 2 h of wear. This behavior is captured in a descriptive statistical model based on results from a trial with this test group. The effectiveness of the masks in preventing the penetration of KCl particles was determined before and after wearing, with the analysis focusing on the most penetrating particles in a size range of 0.3-0.5 µm diameter where respirator masks are most vulnerable. The basic elements of the study, including the approach to filter testing and sample sanitization, are broadly applicable. Conclusions also have applicability to typical commercially available single-use respirator masks manufactured from melt blown polypropylene as they are reliant on the same physical principles for particle capture and electrostatic enhancement was comparable for the particle size range used for detection.

Gelatin/ß-Cyclodextrin Bio-Nanofibers as respiratory filter media for filtration of aerosols and volatile organic compounds at low air resistance.

Air pollution is a universal concern. The suspended solid/liquid particles in the air and volatile organic compounds (VOCs) are ubiquitous. Synthetic polymer-based air filter media not only has disposal issues but also is a source of air and water pollution at the end of their life cycle. It has been a challenge to filter both particulate matter and VOC pollutants by a common biodegradable filter media having low air resistance. This study reports gelatin/ß-cyclodextrin composite nanofiber mats with dual function air filtration ability at reduced air resistance (148 Pa) and low basis weight (1 g/m²). Gelatin/ß-cyclodextrin nanofibers captured aerosols (0.3-5 µm) with < 95% filtration efficiency at 0.029/Pa quality factor. They adsorbed great amount of xylene (287 mg/g), benzene (242 mg/g), and formaldehyde (0.75 mg/g) VOCs. VOC adsorption of gelatin/ß-cyclodextrin nanofibers is found several times higher than a commercial face mask and pristine powder samples. This study provides a solution for a 'green' dual function respiratory air filtration at low resistance. Gelatin/ß-cyclodextrin nanofibers also have the potential to filter nano-sized viruses.

Flexible and reusable carbon nano-fibre membranes for airborne contaminants capture.

Airborne aerosol pollutants generated from combustion vehicles exhausts, industrial facilities and microorganisms represent serious health challenges. Although membrane separation has emerged as a technique of choice for airborne contaminants removal, allowing for both size exclusion and surface adsorption. Here, electrospun carbon nanofibre mats were formed from poly(acrylonitrile) by systematic stabilization and carbonization processes to generate flexible and self-standing membranes for air filtration. The great mechanical flexibility of the electrospun carbon-nanofibre membranes was achieved through extreme quenching conditions on a carbon fibre processing line, allowing for complete carbonization in just 3 min. The carbonized nanofibre membranes, with fibre diameters in the range of 218 to 565 nm exhibited modulus of elasticity around 277.5 MPa. The samples exhibited air filtration efficiencies in the range of 97.2 to 99.4% for aerosol particle in the size of 300 nm based on face velocity, higher than benchmark commercial glass fibre (GF) air filters. The carbonized electrospun nanofibre membranes also yielded excellent thermal stability withstanding temperatures up to 450 °C, thus supporting the development of autoclavable and recyclable membranes. This significant and scalable strategy provides opportunities to mass-produce reusable air filters suitable for otherwise complex airborne pollutants, including volatile organic carbons and bio-contaminants, such as viruses.

One-pot synthesis of catalytic molybdenum based nanocomposite nano-fiber membranes for aerosol air remediation.

The development of fibrous air filters exhibiting high air filtration efficiency, low energy consumption, and self-cleaning properties is a critical challenge to generate the next generation of resilient air filtration systems. Nano-fibrous mats typically exhibit higher particle capture efficiency but may also lead to higher airflow resistance compared to macro-fibrous materials due to their tighter structure. In this paper, novel catalytic membranes mats were fabricated through a one-pot synthesis from ammonium tetrathiomolybdate (ATTM) doped poly(acrylonitrile) (PAN) nanofibers for sub-micron diameter aerosol particle removal. The presence of ATTM as a dopant in conjunction with a PAN polymeric matrix was found to not only enhance the air filtration performance by increasing aerosol particle removal down to 300 nm, but also increase the photocatalytic properties of the PAN material. The enhanced separation properties compared to bare polymeric PAN nanofibrous membranes were attributed to surface nanotexturation of the fibers, leading to protrusions and pores across the nano-fiber structures, thus leading to more permeable and lightweight membranes with higher particle capture capacities. The samples were benchmarked against commercial glass fiber air filters and found to offer higher filtration efficiency, lower pressure drop, and higher quality factor than the commercial filters. Specifically, the quality factors of the catalytic nano-fiber membranes were found to be up to four times higher than that of the benchmarked commercial air filters for PM2.5 particles, while two times higher for 300 nm sized contaminants. The presence of the ATTM across the PAN matrix was also found to enhance the photocatalytic activity of the membranes by up to 130% compared to the bare PAN reference nanofibers. This novel strategy opens avenues to engineering advanced multifunctional catalytic membranes, to capture toxic particulate matter from air while offering self-cleaning properties when exposed to sunlight.

Mixed Matrix Poly(Vinyl Alcohol)-Copper Nanofibrous Anti-Microbial Air-Microfilters.

Membranes decorated with biocide materials have shown great potential for air sanitization but can suffer from biocide agent leaching by dissolution in water. In order to tackle the diffusion of biocide metal ions from the fiber matrix, composite nanofiber membranes of poly(vinyl alcohol) (PVA) cross-linked with copper (II) acetate have been successfully engineered via sol-gel electrospinning, providing a stable mean for air bactericidal microfiltration. The novelty lies in the bonding strength and homogeneous distribution of the fiber surface biocide, where biocide metals are incorporated as a sol within a polymer matrix. The electrospinning of bead-free composite nanofibers offered over 99.5% filtration efficiency for PM2.5, with a theoretical permeance above 98%. The PVA/copper nanofiber membranes also showed satisfactory anti-bacterial performance against the gram-negative Escherichia coli within 24 h, making them promising materials for the remediation of airborne bacteria. The mechanical and chemical stability of the engineered nanocomposite electrospun nanofiber webs added to the natural biodegradability of the materials, by offering ideal low-cost sanitary solutions for the application of air disinfection in both indoor and outdoor fitting a circular economy strategy where advanced materials are redesigned to be sustainable.

Pore engineering towards highly efficient electrospun nanofibrous membranes for aerosol particle removal.

Electrospun nanofibrous membranes were engineered for aerosol particle removal by controlling the fiber density and alignment across electrospun mats. Electrospun nanofiber membranes were deposited on both, rotatory drum and stationary collectors, to investigate the effect of fiber alignment on filtration performance. Poly(acrylonitrile)/dimethyl formamide (PAN/DMF) solutions were used to produce membranes for applications in air purification. The air filtration performance of as-produced and hot-compacted membranes were systematically evaluated with regard to penetration, pressure drop, and quality factor when subjected to potassium chloride (KCl) aerosol particles in the size-range of 300nm to 12µm. The membranes offered air filtration efficiencies in the range of 77.7% to 99.616% and quality factors between 0.0026 and 0.0204 (1/Pa). The samples were benchmarked against commercial filters and were found to exhibit similar quality factors but higher air filtration efficiencies. These results were correlated to differences in pore morphologies and fiber orientation distributions generated from the different processing techniques, which revealed that the alteration of the fiber density is an effective method for enhancing air filtration performance.

Inorganic Nanoparticles/Metal Organic Framework Hybrid Membrane Reactors for Efficient Photocatalytic Conversion of CO2.

Photocatalytic conversion of carbon dioxide (CO2) to useful products has potential to address the adverse environmental impact of global warming. However, most photocatalysts used to date exhibit limited catalytic performance, due to poor CO2 adsorption capacity, inability to efficiently generate photoexcited electrons, and/or poor transfer of the photogenerated electrons to CO2 molecules adsorbed on the catalyst surface. The integration of inorganic semiconductor nanoparticles across metal organic framework (MOF) materials has potential to yield new hybrid materials, combining the high CO2 adsorption capacity of MOF and the ability of the semiconductor nanoparticles to generate photoexcited electrons. Herein, controlled encapsulation of TiO2 and Cu-TiO2 nanoparticles within zeolitic imidazolate framework (ZIF-8) membranes was successfully accomplished, using rapid thermal deposition (RTD), and their photocatalytic efficiency toward CO2 conversion was investigated under UV irradiation. Methanol and carbon monoxide (CO) were found to be the only products of the CO2 reduction, with yields strongly dependent upon the content and composition of the dopant semiconductor particles. CuTiO2 nanoparticle doped membranes exhibited the best photocatalytic performance, with 7 µg of the semiconductor nanoparticle enhancing CO yield of the pristine ZIF-8 membrane by 233%, and methanol yield by 70%. This work opens new routes for the fabrication of hybrid membranes containing inorganic nanoparticles and MOFs, with potential application not only in catalysis but also in electrochemical, separation, and sensing applications.

Towards Enhanced Performance Thin-film Composite Membranes via Surface Plasma Modification.

Advancing the design of thin-film composite membrane surfaces is one of the most promising pathways to deal with treating varying water qualities and increase their long-term stability and permeability. Although plasma technologies have been explored for surface modification of bulk micro and ultrafiltration membrane materials, the modification of thin film composite membranes is yet to be systematically investigated. Here, the performance of commercial thin-film composite desalination membranes has been significantly enhanced by rapid and facile, low pressure, argon plasma activation. Pressure driven water desalination tests showed that at low power density, flux was improved by 22% without compromising salt rejection. Various plasma durations and excitation powers have been systematically evaluated to assess the impact of plasma glow reactions on the physico-chemical properties of these materials associated with permeability. With increasing power density, plasma treatment enhanced the hydrophilicity of the surfaces, where water contact angles decreasing by 70% were strongly correlated with increased negative charge and smooth uniform surface morphology. These results highlight a versatile chemical modification technique for post-treatment of commercial membrane products that provides uniform morphology and chemically altered surface properties.

Assessing the temporal stability of surface functional groups introduced by plasma treatments on the outer shells of carbon nanotubes.

Plasma treatments are emerging as superior efficiency treatment for high surface to volume ratio materials to tune functional group densities and alter crystallinity due to their ability to interact with matter at the nanoscale. The purpose of this study is to assess for the first time the long term stability of surface functional groups introduced across the surface of carbon nanotube materials for a series of oxidative, reductive and neutral plasma treatment conditions. Both plasma duration dose matrix based exposures and time decay experiments, whereby the surface energy of the materials was evaluated periodically over a one-month period, were carried out. Although only few morphological changes across the graphitic planes of the carbon nanotubes were found under the uniform plasma treatment conditions, the time dependence of pertinent work functions, supported by Raman analysis, suggested that the density of polar groups decreased non-linearly over time prior to reaching saturation from 7 days post treatment. This work provides critical considerations on the understanding of the stability of functional groups introduced across high specific surface area nano-materials used for the design of nano-composites, adsorptive or separation systems, or sensing materials and where interfacial interactions are key to the final materials performance.

Influence of the Sonication Temperature on the Debundling Kinetics of Carbon Nanotubes in Propan-2-ol.

The effect of sonication temperature on the debundling of carbon nanotube (CNT) macro-bundles is reported and demonstrated by analysis with different particle sizing methods. The change of bundle size over time and after several comparatively gentle sonication cycles of suspensions at various temperatures is reported. A novel technique is presented that produces a more homogeneous nanotube dispersion by lowering the temperature during sonication. We produce evidence that temperature influences the suspension stability, and that low temperatures are preferable to obtain better dispersion without increasing damage to the CNT walls.

Small angle X-ray scattering study of carbon nanotube forests densified into long range patterns by controlled solvent evaporation.

Although emergent properties from self-assembly of carbon nanotubes have been described in various forms there is so far no systematic process for the preparation of dense arrays of aligned nanotubes. Here we present a systematic study on the analysis of the alignment of carbon nanotubes within solvent densified carbon nanotube forests. Highly periodic patterns with length scales of the order of the millimetres were generated and characterized by electron and optical micrographs and compared to results from small angle X-ray scattering performed at various incident beam angles. The impact of the different solvents was also discussed in light of the densification process and in relation to solvent properties.

A Preliminary Study on the Effect of Macro Cavities Formation on Properties of Carbon Nanotube Bucky-Paper Composites.

In this study, we focus on processing and characterizing composite material structures made of carbon nanotubes (CNTs) and reproducibly engineering macro-pores inside their structure. Highly porous bucky-papers were fabricated from pure carbon nanotubes by dispersing and stabilizing large 1 µm polystyrene beads within a carbon nanotube suspension. The polystyrene beads, homogeneously dispersed across the thickness of the bucky-papers, were then either dissolved or carbonized to generate macro cavities of different shape and properties. The impact of adding these macro cavities on the porosity, specific surface area and Young's modulus was investigated and some benefits of the macro cavities will be demonstrated.

Control of porosity and pore size of metal reinforced carbon nanotube membranes.

Membranes are crucial in modern industry and both new technologies and materials need to be designed to achieve higher selectivity and performance. Exotic materials such as nanoparticles offer promising perspectives, and combining both their very high specific surface area and the possibility to incorporate them into macrostructures have already shown to substantially increase the membrane performance. In this paper we report on the fabrication and engineering of metal-reinforced carbon nanotube (CNT) Bucky-Paper (BP) composites with tuneable porosity and surface pore size. A BP is an entangled mesh non-woven like structure of nanotubes. Pure CNT BPs present both very high porosity (>90%) and specific surface area (>400 m2/g). Furthermore, their pore size is generally between 20-50 nm making them promising candidates for various membrane and separation applications. Both electro-plating and electroless plating techniques were used to plate different series of BPs and offered various degrees of success. Here we will report mainly on electroless plated gold/CNT composites. The benefit of this method resides in the versatility of the plating and the opportunity to tune both average pore size and porosity of the structure with a high degree of reproducibility. The CNT BPs were first oxidized by short UV/O3 treatment, followed by successive immersion in different plating solutions. The morphology and properties of these samples has been investigated and their performance in air permeation and gas adsorption will be reported.