Development of Novel Polyamide-Imide/DES Composites and Their Application for Pervaporation and Gas Separation.

Novel polymer composites based on polyamide-imide Torlon and deep eutectic solvent (DES) were fabricated and adapted for separation processes. DES composed of zinc chloride and acetamide in a ratio of 1:3 M was first chosen as a Torlon-modifier due to the possibility of creating composites with a uniform filling of the DES through the formation of hydrogen bonds. The structure of the membranes was investigated by scanning electron microscopy and X-ray diffraction analysis; thermal stability was determined by thermogravimetric analysis and mass spectrometry. The surface of the composites was studied by determining the contact angles and calculating the surface tension. The transport properties were investigated by such membrane methods as pervaporation and gas separation. It was found that the inclusion of DES in the polymer matrix leads to a significant change in the structure and surface character of composites. It was also shown that DES plays the role of a plasticizer and increases the separation performance in the separation of liquids and gases. Torlon/DES composites with a small amount of modifier were effective in alcohol dehydration, and were permeable predominantly to water impurities in isopropanol. Torlon/DES-5 demonstrates high selectivity in the gas separation of O2/N2 mixture.

Borehole diameter shrinkage rule considering rheological properties and its effect on gas extraction.

To study the shrinkage rule of borehole diameter and its effect on gas extraction, a visco-elastoplastic model for boreholes considering strain softening and the dilatancy characteristic was established to obtain the expressions of the coal stress, variation in diameter, and pressure relief range. The stress distribution and pressure relief effect of the boreholes in soft and hard coal seams were comparatively analyzed. The shrinkage rule of the borehole diameter was studied. The reasons for the rapid reduction in the extraction concentration of the borehole in soft coal seams were described. A technology of improving the gas extraction effect in soft coal seams was developed. The research results showed that the radius of the plastic softening zone is 0.405 m for a borehole in a soft coal seam and 0.224 m for that in a hard coal seam. This indicates that the borehole in a soft coal seam has a better pressure relief effect. The boreholes in both hard and soft coal seams will incur a shrinkage phenomenon; however, the soft coal seam has low strength and a weak ability to resist damage, and thus the surrounding coal will have a more intense creep deformation, leading to an instability failure during a short period of time and thus, a blocking of the extraction channel, thereby causing a rapid reduction in the gas extraction concentration. The borehole in a hard coal seam also shows a shrinkage phenomenon, but remains in a stable state without a blockage; thus, high-concentration gas can be extracted from this borehole for a long period of time. The geo-stress and coal strength are the two main factors controlling the amplitude of borehole shrinkage. From an increase in stress, the borehole in a hard coal seam shows a more intense creep deformation in a deep mine, which may lead to blockage. The key to improving the gas extraction effect in soft coal seams is to maintain a smooth extraction channel. The full screen pipe is installed through the drill pipe to retain an extraction channel, leading to an average gas extraction increase from 0.043 m3/min to 0.12 m3/min, an increase of 2.77 times. These research results are consistent with actual production, and can provide theoretical guidance for determining the gas extraction parameters.

Key Applications and Potential Limitations of Ionic Liquid Membranes in the Gas Separation Process of CO2, CH4, N2, H2 or Mixtures of These Gases from Various Gas Streams.

Heightened levels of carbon dioxide (CO2) and other greenhouse gases (GHGs) have prompted research into techniques for their capture and separation, including membrane separation, chemical looping, and cryogenic distillation. Ionic liquids, due to their negligible vapour pressure, thermal stability, and broad electrochemical stability have expanded their application in gas separations. This work provides an overview of the recent developments and applications of ionic liquid membranes (ILMs) for gas separation by focusing on the separation of carbon dioxide (CO2), methane (CH4), nitrogen (N2), hydrogen (H2), or mixtures of these gases from various gas streams. The three general types of ILMs, such as supported ionic liquid membranes (SILMs), ionic liquid polymeric membranes (ILPMs), and ionic liquid mixed-matrix membranes (ILMMMs) for the separation of various mixed gas systems, are discussed in detail. Furthermore, issues, challenges, computational studies and future perspectives for ILMs are also considered. The results of the analysis show that SILMs, ILPMs, and the ILMMs are very promising membranes that have great potential in gas separation processes. They offer a wide range of permeabilities and selectivities for CO2, CH4, N2, H2 or mixtures of these gases. In addition, a comparison was made based on the selectivity and permeability of SILMs, ILPMs, and ILMMMs for CO2/CH4 separation based on a Robeson's upper bound curves.

Cellulose-Based Carbon Molecular Sieve Membranes for Gas Separation: A Review.

In the field of gas separation and purification, membrane technologies compete with conventional purification processes on the basis of technical, economic and environmental factors. In this context, there is a growing interest in the development of carbon molecular sieve membranes (CMSM) due to their higher permeability and selectivity and higher stability in corrosive and high temperature environments. However, the industrial use of CMSM has been thus far hindered mostly by their relative instability in the presence of water vapor, present in a large number of process streams, as well as by the high cost of polymeric precursors such as polyimide. In this context, cellulosic precursors appear as very promising alternatives, especially targeting the production of CMSM for the separation of O2/N2 and CO2/CH4. For these two gas separations, cellulose-based CMSM have demonstrated performances well above the Robeson upper bound and above the performance of CMSM based on other polymeric precursors. Furthermore, cellulose is an inexpensive bio-renewable feed-stock highly abundant on Earth. This article reviews the major fabrication aspects of cellulose-based CMSM. Additionally, this article suggests a new tool to characterize the membrane performance, the Robeson Index. The Robeson Index, θ, is the ratio between the actual selectivity at the Robeson plot and the corresponding selectivity-for the same permeability-of the Robeson upper bound; the Robeson Index measures how far the actual point is from the upper bound.

Deep Physical-Chemical Purification of Gas Medium in Artificial Ecosystems.

The results of experiments on application of a newly developed facility for oxidation of volatile organic compounds on a platinum catalyst are presented. The feasibility of using this method in artificial ecosystems as a whole and in mass exchange of closed biological-technical life support systems in particular is shown. The possibility of deep purification of gas emitted from the reactor of physical-chemical processing of organic wastes is demonstrated. Wheat growing experiment on using the facility for oxidation of volatile organic compounds in a sealed chamber was performed. No adverse effect of probable toxic oxidation products on wheat plants during a 4-day experiment was determined.

Biotechnology progress for removal of indoor gaseous formaldehyde.

Formaldehyde is a ubiquitous carcinogenic indoor pollutant. The treatment of formaldehyde has attracted increasing social attention. Over the past few decades, an increasing number of publications have reported approaches for removing indoor formaldehyde. These potential strategies include physical adsorption, chemical catalysis, and biodegradation. Although physical adsorption is widely used, it does not really remove pollution. Chemical catalysis is very efficient but adds the risk of introducing secondary pollutants. Biological removal strategies have attracted more research attention than the first two methods, because it is more efficient, clean, and economical. Plants and bacteria are the common organisms used in formaldehyde removal. However, both have limitations and shortcomings when used alone. This review discusses the mechanisms, applications, and improvements of existing biological methods for the removal of indoor gaseous formaldehyde. A combination strategy relying on plants, bacteria, and physical adsorbents exhibits best ability to remove formaldehyde efficiently, economically, and safely. When this combination system is integrated with a heating, ventilation, air conditioning, and cooling (HVAC) system, a practical combined system can be established in formaldehyde removal. Multivariate interactions of biological and non-biological factors are needed for the future development of indoor formaldehyde removal. KEY POINTS: • Indoor gaseous formaldehyde removal is necessary especially for new residence. • Biological removal strategies have attracted increasing research attentions. • Combined system of plants, bacteria, and physical adsorbents exhibits best efficiency. • Integrated device of biological and non-biological factors will be potential practical.

Insights into the Gas Adsorption Mechanisms in Metal-Organic Frameworks from Classical Molecular Simulations.

Classical molecular simulations can provide significant insights into the gas adsorption mechanisms and binding sites in various metal-organic frameworks (MOFs). These simulations involve assessing the interactions between the MOF and an adsorbate molecule by calculating the potential energy of the MOF-adsorbate system using a functional form that generally includes nonbonded interaction terms, such as the repulsion/dispersion and permanent electrostatic energies. Grand canonical Monte Carlo (GCMC) is the most widely used classical method that is carried out to simulate gas adsorption and separation in MOFs and identify the favorable adsorbate binding sites. In this review, we provide an overview of the GCMC methods that are normally utilized to perform these simulations. We also describe how a typical force field is developed for the MOF, which is required to compute the classical potential energy of the system. Furthermore, we highlight some of the common analysis techniques that have been used to determine the locations of the preferential binding sites in these materials. We also review some of the early classical molecular simulation studies that have contributed to our working understanding of the gas adsorption mechanisms in MOFs. Finally, we show that the implementation of classical polarization for simulations in MOFs can be necessary for the accurate modeling of an adsorbate in these materials, particularly those that contain open-metal sites. In general, molecular simulations can provide a great complement to experimental studies by helping to rationalize the favorable MOF-adsorbate interactions and the mechanism of gas adsorption.

Fabrication of hybrid thin film based on bacterial cellulose nanocrystals and metal nanoparticles with hydrogen sulfide gas sensor ability.

The nanocrystalline structures of bacterial cellulose (BC) are described as "environmentally friendly green nanomaterials". Bacterial cellulose (BC) was produced from Gluconacetobacter xylinus in pellicle form with a large bundle of fibers were acid hydrolyzed to obtain bacterial cellulose nanocrystals (BCNCs). The H2SO4 acid-hydrolyzed BCNCs were evaluated for their smallest crystallite size and hydrodynamic size, highly negative ζ-potential value, and the highest specific surface area to interact with metallic nanoparticles. Hybrid thin film of BCNCs based surface-loaded silver nanoparticles (AgNPs) and alginate-molybdenum trioxide nanoparticles (MoO3NPs) was developed for hydrogen sulfide (H2S) gas sensor. Sensor characteristics were investigated as well as its response with H2S gas. The film was successfully detected H2S gas. The color of the film changed by the shift of oxidation number of MoO3NPs. Once activated by AgNPs, MoO3NPs was readily reduced to a colored sub-oxide by atomic hydrogen that produced and received from reaction of H2S gas.

Recent Advances in Graphene Oxide Membranes for Gas Separation Applications.

Graphene oxide (GO) can dramatically enhance the gas separation performance of membrane technologies beyond the limits of conventional membrane materials in terms of both permeability and selectivity. Graphene oxide membranes can allow extremely high fluxes because of their ultimate thinness and unique layered structure. In addition, their high selectivity is due to the molecular sieving or diffusion effect resulting from their narrow pore size distribution or their unique surface chemistry. In the first part of this review, we briefly discuss different mechanisms of gas transport through membranes, with an emphasis on the proposed mechanisms for gas separation by GO membranes. In the second part, we review the methods for GO membrane preparation and characterization. In the third part, we provide a critical review of the literature on the application of different types of GO membranes for CO2, H2, and hydrocarbon separation. Finally, we provide recommendations for the development of high-performance GO membranes for gas separation applications.

Combined calorimetric gas- and spore-based biosensor array for online monitoring and sterility assurance of gaseous hydrogen peroxide in aseptic filling machines.

A combined calorimetric gas- and spore-based biosensor array is presented in this work to monitor and evaluate the sterilization efficacy of gaseous hydrogen peroxide in aseptic filling machines. H2O2 has been successfully measured under industrial conditions. Furthermore, the effect of H2O2 on three different spore strains , namely Bacillus atrophaeus, Bacillus subtilis and Geobacillus stearothermophilus, has been investigated by means of SEM, AFM and impedimetric measurements. In addition, the sterilization efficacy of a spore-based biosensor and the functioning principle are addressed and discussed: the sensor array is convenient to be used in aseptic food industry to guarantee sterile packages.

Gaseous formaldehyde removal: A laminated plate fabricated with activated carbon, polyimide, and copper foil with adjustable surface temperature and capable of in situ thermal regeneration.

Formaldehyde is one of the most common indoor air pollutants in Chinese residences. This study introduces a novel laminated plate with adjustable surface temperature to remove gaseous formaldehyde. The plate is fabricated with activated carbon, polyimide, and copper foil via thermal compression. The plate can be regenerated in situ by applying a direct current to the copper foil. Adsorption-regeneration cycle tests were conducted to evaluate the plate's formaldehyde removal performance. The overall removal efficiency of the fabricated laminated plate with glue mass fraction of 25% and thickness of 1.5 mm was about 30% at the face velocity of 0.8-1.2 m/s. The pressure drop was about 5 Pa. Its removal ability can be regenerated in situ in 8 minutes by increasing the surface temperature to 80°C. The fabricated laminated plate showed good durability after 52 cycles of adsorption-regeneration tests. The results indicate that the proposed laminated plate can enhance the purifying efficiency and enlarge the life span of ordinary, cheap sorbents. It makes cheap materials with low performance suitable for air purification.

Indicator Layers Based on Ethylene-Vinyl Acetate Copolymer (EVA) and Dicyanovinyl Azobenzene Dyes for Fast and Selective Evaluation of Vaporous Biogenic Amines.

The article presents naked-eye methods for fast, sensitive, and selective detection of isopentylamine and cadaverine vapours based on 4-N,N-dioctylamino-4'-dicyanovinylazobenzene (CR-528) and 4-N,N-dioctylamino-2'-nitro-4'-dicyanovinylazobenzene (CR-555) dyes immobilized in ethylene-vinyl acetate copolymer (EVA). The reaction of CR-528/EVA and CR-555/EVA indicator layers with isopentylamine vapours caused a vivid colour change from pink/purple to yellow/orange-yellow. Additionally, CR-555/EVA showed colour changes upon exposure to cadaverine. The colour changes were analysed by ultraviolet⁻visible (UV/VIS) molecular absorption spectroscopy for amine quantification, and the method was partially validated for the detection limit, sensitivity, and linear concentration range. The lowest detection limits were reached with CR-555/EVA indicator layers (0.41 ppm for isopentylamine and 1.80 ppm for cadaverine). The indicator layers based on EVA and dicyanovinyl azobenzene dyes complement the existing library of colorimetric probes for the detection of biogenic amines and show great potential for food quality control.

A Portable Biosensor for 2,4-Dinitrotoluene Vapors.

Buried explosive material, e.g., landmines, represent a severe issue for human safety all over the world. Most explosives consist of environmentally hazardous chemicals like 2,4,6-trinitrotoluene (TNT), carcinogenic 2,4-dinitrotoluene (2,4-DNT) and related compounds. Vapors leaking from buried landmines offer a detection marker for landmines, presenting an option to detect landmines without relying on metal detection. 2,4-Dinitrotoluene (DNT), an impurity and byproduct of common TNT synthesis, is a feasible detection marker since it is extremely volatile. We report on the construction of a wireless, handy and cost effective 2,4-dinitrotoluene biosensor combining recombinant bioluminescent bacterial cells and a compact, portable optical detection device. This biosensor could serve as a potential alternative to the current detection technique. The influence of temperature, oxygen and different immobilization procedures on bioluminescence were tested. Oxygen penetration depth in agarose gels was investigated, and showed that aeration with molecular oxygen is necessary to maintain bioluminescence activity at higher cell densities. Bioluminescence was low even at high cell densities and 2,4-DNT concentrations, hence optimization of different prototypes was carried out regarding radiation surface of the gels used for immobilization. These findings were applied to sensor construction, and 50 ppb gaseous 2,4-DNT was successfully detected.

A Wireless Gas Sensor Network to Monitor Indoor Environmental Quality in Schools.

Schools are amongst the most densely occupied indoor areas and at the same time children and young adults are the most vulnerable group with respect to adverse health effects as a result of poor environmental conditions. Health, performance and well-being of pupils crucially depend on indoor environmental quality (IEQ) of which air quality and thermal comfort are central pillars. This makes the monitoring and control of environmental parameters in classes important. At the same time most school buildings do neither feature automated, intelligent heating, ventilation, and air conditioning (HVAC) systems nor suitable IEQ monitoring systems. In this contribution, we therefore investigate the capabilities of a novel wireless gas sensor network to determine carbon dioxide concentrations, along with temperature and humidity. The use of a photoacoustic detector enables the construction of long-term stable, miniaturized, LED-based non-dispersive infrared absorption spectrometers without the use of a reference channel. The data of the sensor nodes is transmitted via a Z-Wave protocol to a central gateway, which in turn sends the data to a web-based platform for online analysis. The results show that it is difficult to maintain adequate IEQ levels in class rooms even when ventilating frequently and that individual monitoring and control of rooms is necessary to combine energy savings and good IEQ.

Evaluation of Three Peptide Immobilization Techniques on a QCM Surface Related to Acetaldehyde Responses in the Gas Phase.

The quartz-crystal microbalance is a sensitive and universal tool for measuring concentrations of various gases in the air. Biochemical functionalization of the QCM electrode allows a label-free detection of specific molecular interactions with high sensitivity and specificity. In addition, it enables a real-time determination of its kinetic rates and affinity constants. This makes QCM a versatile bioanalytical screening tool for various applications, with surface modifications ranging from the detection of single molecular monolayers to whole cells. Various types of biomaterials, including peptides mapping the binding sites of olfactory receptors, can be deposited as a sensitive element on the surface of the electrodes. One of key ways to ensure the sensitivity and accuracy of the sensor is provided by application of an optimal and repeatable method of immobilization. Therefore, effective sensors operation requires development of an optimal method of deposition. This paper reviews popular techniques (drop-casting, spin-coating, dip-coating) for coating peptides on piezoelectric crystals surface. Peptide (LEKKKKDC-NH2) derived from an aldehyde binding site in the HarmOBP7 protein was synthesized and used as a sensing material for the biosensor. The degree of deposition of the sensitive layer was monitoring by variations in the sensors frequency. The highest mass threshold for QCM measurements for peptides was approximately 16.43 µg·mm-2 for spin coating method. Developed sensor exhibited repeatable response to acetaldehyde. Moreover, responses to toluene was observed to evaluate sensors specificity. Calibration curves of the three sensors showed good determination coefficients (R² > 0.99) for drop casting and dip coating and 0.97 for the spin-coating method. Sensors sensitivity vs. acetaldehyde were significantly higher for the dip-coating and drop-casting methods and lower for spin-coating one.

Two-Dimensional Metal-Organic Framework Nanosheets: A Rapidly Growing Class of Versatile Nanomaterials for Gas Separation, MALDI-TOF Matrix and Biomimetic Applications.

Two-dimensional (2D) metal-organic framework (MOF) nanosheets, as an emerging type of 2D materials, attract numerous attention due to their unique properties. First, the ultrathin thickness and nanoscale of the materials results in homogeneous dispersion in aqueous solution, giving the materials more opportunities to be utilized in solution chemistry, especially beneficial to the biomimetic catalysis and bio-related analytical applications. Second, the large surface area and accessible active sites of the MOF nanosheets are favorable to the binding between materials and the substrate, leading to their superior performance in catalysis, sensing and enzyme inhibition. Third, the suitable sizes of nanopores on the 2D MOF nanosheets give them the abilities to act as membranes for highly selective and energy-saving gas separation. This minireview covers the synthesis, characterization as well as bio-related and separation applications of 2D MOF nanosheets.

Biofilter treatment of gas phase ß-caryophyllene at an elevated temperature.

Experiments were carried out to test the capacity for a laboratory-scale biofilter operated at an elevated temperature level (∼50°C) to remove an air stream containing ß-caryophyllene, a naturally occurring sesquiterpene of environmental concern emitted from wood-related industrial facilities. A water jacket was used to maintain high temperatures in a laboratory-scale biofilter. Inocula, pollutant loading and nutrient supply rate effects were evaluated over 84 days of biofilter operation. The start-up process took over two months when citrus peels were used as inocula while a relatively short start-up period was achieved after introducing forest compost products. While using a sparged-gas bioreactor to cultivate an enrichment culture for 97 days, removal efficiencies in excess of 80% were observed after 18 days. At empty bed contact times of 50 s and at a pollutant loading rate of 3.05 mg C/L/hr, removal efficiency levels reached 90% and the elimination capacity level reached 2.29 mg C/L/hr, corresponding to an elimination capacity of 2.60 mg ß-caryophyllene/L/hr. Collectively, these results demonstrate that ß-caryophyllene can be successfully removed from contaminated air using a biofilter operated at a high temperature (∼50°C), expanding the temperature range within which biofilters are known to biodegrade sesquiterpenes.

Critical Comparison of Structured Contactors for Adsorption-Based Gas Separations.

Recent advances in adsorptive gas separations have focused on the development of porous materials with high operating capacity and selectivity, useful parameters that provide early guidance during the development of new materials. Although this material-focused work is necessary to advance the state of the art in adsorption science and engineering, a substantial problem remains: how to integrate these materials into a fixed bed to efficiently utilize the separation. Structured sorbent contactors can help manage kinetic and engineering factors associated with the separation, including pressure drop, sorption enthalpy effects, and external heat integration (for temperature swing adsorption, or TSA). In this review, we discuss monoliths and fiber sorbents as the two main classes of structured sorbent contactors; recent developments in their manufacture; advantages and disadvantages of each structure relative to each other and to pellet packed beds; recent developments in system modeling; and finally, critical needs in this area of research.

Carbon Molecular Sieve Membranes Derived from Tröger's Base-Based Microporous Polyimide for Gas Separation.

Carbon molecular sieve (CMS)-based membranes have attracted great attention because of their outstanding gas-separation performance. The polymer precursor is a key point for the preparation of high-performance CMS membranes. In this work, a microporous polyimide precursor containing a Tröger's base unit was used for the first time to prepare CMS membranes. By optimizing the pyrolysis procedure and the soaking temperature, three TB-CMS membranes were obtained. Gas-permeation tests revealed that the comprehensive gas-separation performance of the TB-CMS membranes was greatly enhanced relative to that of most state-of-the-art CMS membranes derived from polyimides reported so far.

Tailoring gas sensor arrays via the design of short peptides sequences as binding elements.

A semi-combinatorial virtual approach was used to prepare peptide-based gas sensors with binding properties towards five different chemical classes (alcohols, aldehydes, esters, hydrocarbons and ketones). Molecular docking simulations were conducted for a complete tripeptide library (8000 elements) versus 58 volatile compounds belonging to those five chemical classes. By maximizing the differences between chemical classes, a subset of 120 tripeptides was extracted and used as scaffolds for generating a combinatorial library of 7912 tetrapeptides. This library was processed in an analogous way to the former. Five tetrapeptides (IHRI, KSDS, LGFD, TGKF and WHVS) were chosen depending on their virtual affinity and cross-reactivity for the experimental step. The five peptides were covalently bound to gold nanoparticles by adding a terminal cysteine to each tetrapeptide and deposited onto 20MHz quartz crystal microbalances to construct the gas sensors. The behavior of peptides after this chemical modification was simulated at the pH range used in the immobilization step. ΔF signals analyzed by principal component analysis matched the virtually screened data. The array was able to clearly discriminate the 13 volatile compounds tested based on their hydrophobicity and hydrophilicity molecules as well as the molecular weight.