Additive manufacturing is gaining increasing interest in the field of catalysis and gas separation applications due to the geometric flexibility for a wide range of materials. However, this process typically demands the use of a combination of organic and inorganic binders such as clays, silica or alumina to ensure mechanical integrity. As a result, these types of structures often are...
Adsorption is a promising technique for CO2 capture, and improving adsorbent properties is crucial for enhancing CO2 selectivity. This study compares the efficiency and differences between two modification methods: physical treatment to increase mesopore volume and active sites, and chemical impregnation with triethylamine (TEA) for CO2 capture in a fixed-bed adsorption system. N2 isotherm...
The use of oxygen-enriched air with high oxygen concentration is expected to reduce fuel consumption in industrial furnaces. The pressure swing adsorption method was used for the air separation. However, temperature swing adsorption (TSA) using combustion exhaust heat is expected to save more energy. To achieve highly efficient air separation by introducing TSA, a molecular sieve adsorbent...
In recent years, extensions of the cubic equations of state for fluids confined in different geometries have been developed based on the Generalized van der Waals Theory. These equations make it possible to describe the Helmholtz energy as a function of temperature, volume, and number of components, from which expressions for all other thermodynamic properties can be derived. Extending the...
Fluid adsorption and transport in nanoporous materials are at the heart of efficient technologies impacting our economy/ecology: energy storage/conversion, environment protection, health/human welfare, agribusiness/food science, etc. In particular, nanoporous solids shaped as membranes are expected to play a leading role in the “seven key chemical separations to change the world”1 but also to...
Large-scale hydrocarbon separation technologies are largely thermally driven phase-change based processes and account for roughly 45% of production energy in downstream petrochemical and manufacturing processes. Adsorptive separation has a great potential as disruptive separation technology to enable sustainable, economically advantaged, low carbon footprint production of strategic hydrocarbon...
The development of adsorbent materials for CO2 capture from the atmosphere is the focus of this study. There is a widespread agreement among scientists that greenhouse gases (GHGs) are responsible for trapping heat in the atmosphere. The concentration of CO2 in the atmosphere grew from 320 to 425 parts per million by volume (ppmv) between 1960 and 2024. According to NASA, this rise contributed...
Chemical warfare agents (CWAs), such as sarin and sulfur mustard, VX chemical components lead to death with only traces of a few micrograms. The use of rapid decontamination of these compounds under harsh conditions remains a great technological challenge. Adsorption is still considered one of the most efficient methods that can be chosen to adsorb such compounds. Metal–Organic Frameworks...
The reliable measurement of the specific surface area of many modern materials – porous or non-porous – is of vital importance both in research and industry. To date, the most commonly used method for the determination of the specific surface area of any material is based on the BET (Brunauer-Emmet-Teller) method that relies on the physisorption of gas molecules at the sample surface. The BET...
Carbon dioxide (CO2) capture is a subject of extensive research, particularly with Carbon Capture and Storage (CCS) methods gaining attention, notably those based on gas-solid adsorption. However, there is a notable gap in the literature concerning the impact of contaminants present in gaseous streams, particularly sulfur and nitrogen oxides, on CO2 adsorption. This study evaluated the effect...
Carbon dioxide (CO2) adsorption at high pressures by alkali-impregnated activated carbons were studied in this presentation. Four types of activated carbon were prepared with two-step activation method and activation combined with oxidation method [1] and then impregnated in different concentration of alkali solution of 1, 4, 7 and 10%. The results of CO2 adsorption at 0 ̊C up to saturated...
In this study, we delve into the intricacies of gas adsorption behavior within nanoporous materials, specifically focusing on the competitive adsorption of CH4 and H2O molecules under clathrate hydrate formation conditions. We aim to elucidate how the presence of water or humidity affects the total gas adsorption capacity of these materials.
Under low-temperature hydrate formation...
Zeolites are crystalline aluminosilicates that have a wide range of applications, including solid catalysts, adsorbents, and separation membranes. In zeolites, hydroxyl groups exist in various forms, including Brønsted acid sites (BAS), isolated hydroxyl groups, and hydroxyl groups in defects (Fig. 1a). Despite their significant impact on zeolite performance, it has been challenging to...
Conventional leather is a product that has been used for millennia. Unfortunately, it suffers from a significant carbon footprint due to its livestock source and tanning (the process of converting hides to leather). In addition, there are ethical issues regarding the consumer use of animal-derived products [1,2]. To mitigate these issues, engineering sustainable bio-based leather substitutes...
Traditional methods of characterization of nanoporous carbons are based on the use of a simulated kernel of isotherms obtained by classical density functional theory (cDFT) in a series of independent slit or cylindrical pore models to compute the pore size distribution. This approach cannot describe the structure's asymmetry, a feature characteristic of these materials. Vallejos et al. [1]...
Metal hydrides for on-board hydrogen storage play a key role in future conversion of the world to a “hydrogen economy”. Nano-structuring these materials proves an effective strategy which can simultaneously enhance their ab/de-sorption thermodynamics and kinetics. However, strategies to combine catalysis and nanoconfinement for controlling factors governing their interfacial hydrogen uptake...
Since 2013, the amount of scrap tire waste generated in the U.S. has increased by over 32%, while the utilization of materials derived from tire waste has decreased by over 25%. This has led to an increase in land disposal of tire waste by 123%. This trend necessitates the development of new methods and markets for processing and recycling scrap tires. One possibility, based on the...
Transitioning to a sustainable energy source is the first and most crucial step in combating climate change. The critical bottleneck to using hydrogen (H2), an energy carrier, as a stationery and transportation fuel has been the development of materials capable of providing a viable storage capacity. Metal-organic frameworks are a class of crystalline materials composed of metal ions or...
Physical adsorption is one of the most widely used techniques to characterize porous materials because of being reliable and able to assess micro- and mesopores within one approach. However, challenges and open questions persist in characterizing disordered and hierarchically structured porous materials. This study introduces a pore network model aiming to enhance the textural characterization...
This study presents the synthesis of Porous Geopolymer Monoliths (PGMs) through the utilization of metakaolin (MK) and oil shale (OS) as raw materials. MK contributed aluminosilicates, while OS played a multifaceted role, acting as a pore-forming agent upon mixing with phosphoric acid, enhancing the selectivity of geopolymers towards organic pollutants and heavy metals, and aiding in the...
The relationship between the microstructure of porous media and their permeation properties is a problem that has been addressed in many instances. Experimental measurement of intrinsic permeability remains a challenge, especially for tight materials, and several approaches have been proposed in the literature to directly compute the transport property of a porous medium (e.g. network models...
In this work, a commercial zeolite, in two states of fresh and aged, is considered for investigation. The aged sample obtained from an industrial natural gas (NG) dehydration plant was used as a reference. The effect of the aging process on the sample structure and the capability to perform the adsorption/desorption process were assessed using different characterization methods. Analytical and...
Cellulose, which is the most prevalent polymer on the planet, usually organizes into hierarchical fiber form. Cellulose chains crystallize into 3-5 nm elementary fibrils, which cluster into macrofibrils that are wound and stacked into the layers of the cell wall of plant-based fibers. Cellulosic fibers, often derived from wood (pulp fibers), are a primary building block of many renewable...
A continuum in the chemical space linking molecules and materials encompasses promising physical and chemical properties that both extremes do not and cannot display. As we consider transitioning from well-defined structures and compositions toward materials, their surfaces, and grain boundaries through nanoparticles, new chemical reactivity, catalytic properties, and unique chemical functions...
The diffusion of molecules within the confines of a materials pores remains a relatively poorly understood research area. This is despite the diffusion process playing critical role in many adsorption phenomena such as adsorbate selectivity and uptake kinetics. As such, in this work a new model for the analysis of diffusion constants, obtained using a chromatographic Zero-Length Column method,...
Metal-organic framework (MOF)/polymer composites provide the possibility of combining the desired reactive and sorptive properties of highly porous MOFs with the desired mechanical properties of polymers to develop novel functional materials. Both MOF and polymer chemistries are complex leading to various degrees of material compatibility. It is desired to develop a facile measurement of the...
Nitrogen-doped (N-doped) carbon materials are attracting attention in various fields, such as catalysis for oxygen reduction reaction. CHN elemental analysis and XPS were conventionally used for analysis of N species, but their measurement accuracy is about 0.1 wt%. Thus, a technique for detailed qualitative and quantitative analysis of N species is desired. Temperature-programmed desorption...
Fuel cell vehicles hold significant promise for decreasing both energy consumption and carbon dioxide emissions. Hydrogen storage is the key technology towards the hydrogen society [1]. Vehicular hydrogen has been stored in special tanks at very high pressures (700 bar) with obvious disadvantages in the energy cost of compression and safety. The use of adsorbed H2 instead of compressed H2 can...
The robustness and reactivity of a metal-organic frameworks depend on metal-ligand interactions, where the metal-containing clusters may be vulnerable to ligand substitution by water, leading to the framework collapse upon exposure to moist air. This instability limits the practical uses of many MOFs. In order to further enhance the stability of the framework, many different approaches. One of...
Advanced oxidation processes driven by natural sunlight are the key to the next generation of water treatment technologies. Photocatalysis using semiconductor materials constitutes a promising approach to degrade organic contaminants in wastewater with minimal generation of secondary pollutants. In this scenario, carbon-based nanomaterials have emerged as promising modifying co-catalysts. The...
Porous materials stand at the forefront of adsorption research, offering versatile applications in separation processes and catalysis for both fundamental research and industrial purposes. Among the numerous applications, methanol separation through adsorption mechanisms is an interesting topic due to the high-value accessible derivatives (purified methanol, hydrocarbons, olefins). Therefore,...
Gas adsorption is commonly used to characterize the surface area, pore volume and pore size distribution of porous materials, as well as to assess adsorbents for use in gas storage and separation applications. Adsorption isotherms – plots of uptake versus pressure – can be measured using the volumetric and gravimetric techniques, and commercial instruments are widely available for this...
Compliant MOFs are known to respond to external stimuli, such as pressure, temperature, and adsorbed guests by undergoing remarkable structural changes [1]. Here, the coupling of two or more stimuli presents the opportunity of tuning a process like gas separation, affording control over the underlying framework’s state [2]. However, structural information of materials undergoing combined guest...
Fluids exhibit different thermodynamic properties in confinement compared to their bulk state. Their boiling and melting temperatures shift, their densities are lower than their bulk phase, and their mechanical properties, such as the elastic modulus, alter depending on the pore size [1]. These phenomena have been analyzed previously through computational models, such as molecular simulations,...
Among theoretical developments, the molecular density functional theory (DFT) has emerged as one of the most powerful and convenient molecular approach for the description of the thermodynamic properties of inhomogeneous fluids. The development of DFT for classical fluids originates in the late 70’s [1] and its use is nowadays widespread for the description of fluid interfaces or fluids...
The assessment of specific surface area and adsorption properties in advanced functional materials is a key task for the characterization of porous materials such as activated carbons, porous polymers, metal-organic frameworks, zeolites, nanoparticles and catalysts. The characterization of porous materials by nitrogen Physisorption at 77 K and gravimetric methods is widely used. However, a...
The separation of propane and propylene remains a challenging seperation process, due to the similar boiling points and size of both molecules. LTA zeolites have been shown to be promising adsorbents, but a systematic study of the effect of the extra-framework cations on propylene and propane adsorption is lacking.
In this work, we prepared LTA zeolites exchanged with different cations...
Adsorption of fluids in porous media causes mechanical stress which results in deformation [1,2]. This phenomenon is ubiquitous, but challenging to predict quantitatively due to numerous factors (pore size and geometry, adsorbent/adsorbate combination, temperature, etc.) affecting its manifestation. Since many industrial and real-world processes occur far from thermodynamic equilibrium it is...
Atmospheric soot is a major air pollutant and a powerful warming agent. Nanoparticles comprising soot are branched fractal aggregates of near-spherical carbon monomers with a diameter of 10-40 nanometers. When exposed to condensable vapors, either at the combustion source or in the atmosphere, soot aggregates undergo morphological transformations, such as collapsing into globules[1-3]. The...
MOFs are excellent candidates for the capture of CO2, in particular for the environmental control for life support systems in space suits and onboard the space shuttle. Traditionally, beads of lithium hydroxide, zeolites or polyamines have been employed for CO2 removal for the aforementioned applications. However, the use of beads can generate unfavorable large pressure drops. By employing a...
In light of the current environmental situation, reduction of anthropogenic CO2 emissions from carbon-intensive industries like power plants, cement, steel, or petrochemical industries become one of the most pressing issues to combat global warming. Shifting towards a low-carbon economy requires cost-effective carbon capture utilization or sequestration (CCUS) technology to be developed....
Predicting adsorption on nanoporous carbonaceous materials is important for developing various adsorption and membrane separations, as well as for oil and gas recovery from shale reservoirs. Here, we explore the capabilities of 3D molecular models of disordered carbon structures to reproduce the morphological and adsorption features of practical adsorbents. Using grand canonical Monte Carlo...
Shale gas reservoirs plays a pivotal role in natural gas production in the United States. Organic part of shale is both a source and reservoir of hydrocarbons. Kerogen, an insoluble organic part of shale, exhibits an amorphous structure, and its composition and mechanical properties depend on the level of maturity. It has been shown the kerogen matrix swells upon gas adsorption. It is critical...
ABSTRACT: Lyophobic nanoporous particle suspensions are being explored as promising materials for energy absorption and storage. In these systems, known as nanoscale energy absorption systems (NEAS), the non-wetting solvent intrudes into nanopores when subjected to mechanical compression, converting and storing the impact energy that can be further released upon solvent extrusion when the...
Even in 21st century, chemical warfare agents (CWA) remain a threat, and a lot of research and development is aiming to advance protection from CWA. Experiments with CWAs are dangerous and are typically reduced to a minimum. Most of experiments are done on simulants – chemicals which have similar structure, but much lower toxicity. For sarin simulants include dimethyl methylphosphonate (DMMP),...
Classical liquid chromatography is one of the most used techniques in the field of nanoparticle separation. This is achieved by driving the nanoparticle containing liquid through a column densely packed with meso- and nanoporous particles. Separation efficiency can be improved through optimizing the interactions between the particles, the solvent and the pore surface using directed surface...
Given the current environmental problems, renewable energy resources (such as photovoltaics or wind power) are now an absolute necessity. However, the intermittency of these resources in the production of electricity is a key factor and energy storage and efficient energy conversion systems are required. In this context, hydrogen could be used as a vector energy for renewable energy. Indeed,...
Metal-Organic Frameworks (MOFs) stand out as a prominent class of nanoporous materials, known for their stability and customizable pore sizes and chemistry, particularly for gas storage and separations. Notably, certain MOFs exhibit pH sensitivity, rendering them excellent candidates for drug delivery applications. The precise characterization of MOFs is of paramount importance for effective...
Copolymers have a microstructure defined by their constituent monomers’ sequence. This microstructure can have a wide-ranging impact on its structure-function properties and is often difficult to control during polymerization, thus is crucial to understand. Quantification of synthetic copolymer microstructure is challenging due to the large heterogeneity of molecular species and the limited...
Given that chemical separations account for 15% of the world’s total energy consumption, it is critical to design energy-efficient pathways for the purification of chemical mixtures.1 Membrane separations and adsorption processes are promising nonthermal alternatives to energy-intensive separation technologies, as they separate molecules by size or chemical affinity. Metal–organic frameworks...
The ubiquitous nature of water makes understanding its effects on the chemical structure and properties of materials important to the development, processing, and applications of materials associated with food production, pharmaceuticals, construction, separation processes, sorbent-based industries, and emerging water sorption applications such as water harvesting and thermal energy...
Abstract attached below.
“Molecular sieving”-based separation of similar-sized gases (e.g., CO2, N2, and CH4) is desirable but challenging as the “sieve” (adsorbent) with the right pore size that readily allows for exclusive admission is difficult to obtain. The “molecular trapdoor effect” can help solve this challenge, instead of relying on size-sieving, by realizing exclusive admission based on the difference in the...
We consider deformation of nanoporous carbons during adsorption of mixtures, focusing on the specific context of carbon dioxide displacement of natural gas from coal and shale reservoirs. Density functional theory calculations augmented by the perturbed chain statistical associating fluid theory (SAFT-DFT) are employed to model adsorption of fluid mixtures on carbon slit pores at geologically...
In this talk we present a scalable solution for continuous heterogeneous catalysis, such as hydrogenation reactions. First, we discuss the Gore Structured Catalyst, a 3-dimensional PTFE mesh-based structure embedded with particles of supported catalyst. This 3-dimensional structure has tunable properties, such as porosity and catalyst loading, thus allowing for the construction of a structure...
Nanoporous carbons gather much attentions as a key material for the achievement of Sustainable Development Goals (SDGs), because of the high volumetric capacities and the molecular sieving characters for industrially important gas molecules, like CH4 and CO2. Recently, the synthesis of various types of nanoporous carbons has been reported, including top-down synthesis by activation of...
This study reports on the low-pressure supercritical Hydrogen (H2) and Deuterium (D2) adsorption in a nanoporous activated carbon cloth, investigated by small-angle neutron scattering (SANS) to elucidate pore size dependent adsorbate densification [1]. The changes of the SANS signal resulting from the physisorption of adsorbate molecules in the pore space are described by analytical pore...
Hydrogen, lauded for its potential as a clean energy carrier, occupies a pivotal position in the quest for sustainable energy solutions. Yet, the challenges tied to its safe and efficient storage persist, rendering conventional methods less suitable due to inherent safety risks and high operating pressures. An innovative avenue emerges in solid-state storage within nanoporous materials, which...
Information about the porous nature of adsorbents is important for understanding the pore structure of solids. Adsorption is widely used as a probe for pore structure. The measured adsorption behavior of a sample reflects, in an aggregated manner, the adsorption behavior of individual pores. Sulfur hexafluoride (SF6) and SO2 are industrial gases used in various applications. Compared to CO2,...
Many studies have proven that elastic properties of fluids confined in nanopores deviate from the values observed in bulk [1]. Interactions between the solids (pore wall) and fluids, and pore geometry are the key factors that determine the deviation in the elasticity of nanoconfined fluids. Therefore, experimental measurements of elastic properties of confined fluids can provide information...
The in-pore crystallization of salts is considered one of the major sources of degradation of construction materials, geomaterials, and built heritage. When crystallizing, salts may exert mechanical pressure against the surface of the pore, which can damage materials. Crystallization within the porous network remains one of the most misunderstood phenomena in porous media mechanics. We propose...
Porous materials play a vital role in industrial and environmental systems due to their diverse applications. The adsorption capacity and associated heat during this process are crucial parameters for evaluating the performance of these materials. Achieving high sensitivity and accuracy is of utmost importance in adsorption and microcalorimetry instruments. As a result, researchers...
The exploration of metal–organic frameworks (MOFs) in the adsorption of phosphate is a growing research area. However, the manufacturing and processability of MOFs for practical applications are often hindered by their cost and their powder form. This study pioneers the use of water-soluble organic ligands, specifically disodium terephthalate (DST) sourced from waste plastic, in the design and...
The exploration of metal-organic frameworks (MOFs) in the adsorption of phosphate is a growing research area. However, the manufacturing and processability of MOFs for practical applications are often hindered by their cost and their powder form. This study pioneers the use of water-soluble organic ligands, specifically disodium terephthalate (DST) sourced from waste plastic, in the design and...
Hierarchical mesoporous-macroporous silica materials (HS-PEG) were prepared via a one-pot hydrothermal synthesis method using tetraethyl orthosilicate (TEOS) as the silica source, NH4OH as condensation catalyst, and a combination of alkylammonium bromide surfactants (CnTAB) and different polyethylene glycols (PEG) as structure directing agents (SDAs). Once the SDAs were removed by calcination...
Metal-organic frameworks (MOFs) are highly porous materials with tunable pore characteristics, making them attractive for applications in gas storage, separation, and catalysis [1]. Their unique properties have garnered significant attention in water vapor adsorption technology, crucial for humidity control, air conditioning, and heat pump systems. The Leibniz Supercomputing Center, in...
Critical materials such as lithium, nickel, and cobalt play an important role in the sustainable development of society. However, establishing a reliable supply of these critical materials has been a challenge for the USA. Meanwhile, electronic waste (E-waste) has become a societal burden due to the quick spread of electronic devices and electric cars. E-waste contains a large amount of...
Due to global warming and the high global demand for energy, the research and development of sustainable
energy storage systems is of great interest. The photoswitchable phase change material 4-methoxyazobenzene
(4-MeO-Azo) allows simultaneous storage of two different forms of energy which can be
released after an external trigger, shown in Fig. [1]. Herein, we report the change of the...
Jakub Szczurowski1, Adrian Lubecki1, Patryk Bartulik1, Katarzyna Zarębska2
1 Faculty of Energy and Fuels, AGH University of Science and Technology, Al. Mickiewicza 30, 30-059 Cracow, Poland; szczurow@agh.edu.pl
2 Faculty of Environmental Engineering, Geomatics and Renewable Energy, Kielce University of Technology, 25-314 Kielce, Poland; kzarebska@tu.kielce.pl
In response to the high...
The concentration of CO2, the primary anthropogenic greenhouse gas (GHG) responsible for global warming and climate change, has experienced a rapid increase since the Industrial Revolution. The present levels of CO2 surpass any recorded in human history, indicating a global average concentration of 425 parts per million by volume (ppmv) in 2024, as opposed to 315 ppmv in 1958. Additionally,...
While imbibition kinetics are well-understood in nanoporous materials [1], their drying dynamics are still under investigation [2]. In this study, we present time-dependent macroscopic dilatometry experiments on the deformation of nanoporous monoliths upon spontaneous, capillarity-driven infiltration of water as well as drying. During both processes, we find characteristic dynamical regimes...
In this study, we used mesoporous silica MCM-41 as the vessel of the micro-solution, dibenzyl as solute, and water and diethyl ether as solvents. The water adsorption isotherm of dibenzyl pre-adsorbed MCM-41 (MCM-Dib) shows a new type of isotherm shape which not classified by IUPAC. The water adsorption amount is independent of the amount of dibenzyl (ϕ_Dib) and agreed with the pore capacity...
For porous carbons, which typically have hierarchical structures, the pore size distribution (PSD) is one of the most important characteristics and is currently evaluated by using kernel fitting methods represented by non-local density functional theory. Herein, we present new kernels for N2 and Ar adsorption at 77 K and 87 K, respectively, derived from Monte Carlo (MC) simulations based on a...
