Covalent organic frameworks comprise a unique class of functional materials that has recently emerged as a versatile tool for energy-related, photocatalytic, environmental, and electrochromic device applications. A plethora of structures can be designed and implemented through a careful selection of ligands and functional units. On the other hand, porous materials for heavy metal absorption are constantly on the forefront of materials science due to the significant health issues that arise from the release of the latter to aquatic environments. In this critical review, we provide insights on the correlation between the structure of functional covalent organic frameworks and their heavy metal absorption. The elements we selected were Pb, Hg, Cr, Cd, and As metal ions, as well as radioactive elements, and we focused on their removal with functional networks. Finally, we outline their advantages and disadvantages compared to other competitive systems such as zeolites and metal organic fra... [more]

The demand for electricity is growing rapidly along with economic development and increasing population. At present, its production is mainly based on non-renewable sources, which has negative impacts on the environment and contributes to global warming. A large proportion of the produced electricity is consumed by refrigeration equipment. Climate change and the progress of civilisation are additionally increasing the demand for cooling, with increasing electricity consumption as a consequence. One of the options for obtaining eco-friendly cooling is the use of adsorption chillers. These devices are powered by low-temperature heat and their operation only requires a small amount of electrical energy. The source of low-temperature heat can be, e.g., waste heat generated in many industrial processes. Its use allows one to increase energy efficiency and achieve additional financial benefits. However, adsorption chillers are characterised by low coefficients of performance. This paper pres... [more]

Covalent organic frameworks (COFs) are emerging crystalline polymeric materials with highly ordered intrinsic and uniform pores. Their synthesis involves reticular chemistry, which offers the freedom of choosing building precursors from a large bank with distinct geometries and functionalities. The pore sizes of COFs, as well as their geometry and functionalities, can be pre-designed, giving them an immense opportunity in various fields. In this mini-review, we will focus on the use of COFs in the removal of environmentally hazardous metal ions and chemicals through adsorption and separation. The review will introduce basic aspects of COFs and their advantages over other purification materials. Various fabrication strategies of COFs will be introduced in relation to the separation field. Finally, the challenges of COFs and their future perspectives in this field will be briefly outlined.

We conducted energy and exergy analyses of an adsorption chiller to investigate the effect of recooling-water temperatures on the cooling capacity and Coefficient of Performance (COP) with variable cycle modes. We investigated both the effect of the recooling-water temperature and the dead state temperature on the exergy destruction in the chiller components. Our results show that there is an optimum reheat cycle mode for each recooling-water temperature range. For the basic single stage cycle, the exergy destruction is mainly accrued in the desorber (49%), followed by the adsorber (27%), evaporator (13%), condenser (9%), and expansion valve (2%). The exergy destruction for the preheating process is approximately 35% of the total exergy destruction in the desorber. By contrast, the precooling process is almost 58% of the total exergy destruction in the adsorber. The exergy destruction decreases when increasing the recooling-water and the dead state temperatures, while the exergy effici... [more]

Biomass chemical looping gasification (CLG) is a novel gasification technology for hydrogen production, where the oxygen carrier (OC) transfers lattice oxygen to catalytically oxidize fuel into syngas. However, the OC is gradually reduced, showing different reaction activities in the CLG process. Fully understanding the CLG reaction mechanism of fuel molecules on perfect and reduced OC surfaces is necessary, for which the CLG of ethanol using Fe2O3 as the OC was introduced as the probe reaction to perform density functional theory calculations to reveal the decomposition mechanism of ethanol into the synthesis gas (including H2, CH4, ethylene, formaldehyde, acetaldehyde, and CO) on perfect and reduced Fe2O3(001) surfaces. When Fe2O3(001) is reduced to FeO0.375(001), the calculated barrier energy decreases and then increases again, suggesting that the reduction state around FeO(001) favors the catalytic decomposition of ethanol to produce hydrogen, which proves that the degree of reduct... [more]

We studied the effects of supercritical carbon dioxide (scCO2) on the matrix permeability of reservoir rocks from the Eagle Ford, Utica, and Wolfcamp formations. We measured permeability using argon before exposure of the samples to scCO2 over time periods ranging from days to weeks. We measured permeability (and the change of permeability with confining pressure) when both argon and scCO2 were the pore fluids. In all three formations, we generally observe a negative correlation between initial permeability and carbonate content—the higher the carbonate content, the lower the initial permeability. In clay- and organic-rich samples, swelling of the matrix resulting from adsorption decreased the permeability by about 50% when the pore fluid was scCO2 although this permeability change is largely reversible. In carbonate-rich samples, dissolution of carbonate minerals by carbonic acid irreversibly increased matrix permeability, in some cases by more than one order of magnitude. This dissol... [more]

Strict International Maritime Organization (IMO) rules enable ships to maximize fuel consumption and compliance with the climate. Cooling and heat-pumping technology powered by waste heat makes a substantial contribution to lowering ship gas emissions. This study explores, technically studies, and thermodynamically analyzes the efficiency of ongoing adsorption refrigeration and heating systems using a zeolite−water pair onboard a naval surface ship. An updated Dubin-in-Astakhov equation calculates the equilibrium adsorption potential of the operating pair used in the system. The coefficient of performance (COP) and specific cooling power (SCP)/specific heating power (SHP) values were between 0.109 and 0.384 and between 69.13 and 193.58 W kg−1 for cooling mode, and between 66.16 and 185.26 W kg−1 based on exhaust gas temperature and regeneration, respectively. Up to 27.64% and 52.91% met the cooling and heating load of the case vessel at a full load by the zeolite−water-adsorbed refrige... [more]

This study examined the application of high-gradient magnetic separation (HGMS) for recycling of super-paramagnetic polymer adsorbent (MPA), namely, polyvinyl acetate-iminodiacetic acid. The HGMS can be incorporated with the adsorption and desorption processes (ADPs) with fresh or regenerated desorbed MPAs and exhausted adsorbed MPAs, respectively. This combines the permanent magnet’s advantage of low running costs with the easy operation using the solenoid to flush the filter in place. The effects of the inlet concentration of MPA in solution (CLF) and the fluid velocity (v0) or volumetric flow rate (QLF) on the performance of the recovery of MPA via HGMS were assessed. The results indicated that the separation efficiency (η or P0), breakthrough time (tB) and exhaustion time (tE) of HGMS reduce as CLF, as well as v0, increases. Further, the filter saturated capture capacity (σS) of HGMS also decreases with increasing v0. The effect of v0 on tB proportional to 1/v02 is more significant... [more]

Dyes used in textiles, foods, cosmetics, and chemicals have become a major environmental pollution issue around the world. To address this issue, a number of technologies have been created to remove these pollutants from the environment. Due to their superior properties at nanoscale, numerous nanomaterials have been applied to remove dyes from polluted waters. This research presents the findings of the development of bentonite nano zero-valent iron (B-nZVI) for the treatment of synthetic cationic dyes. This study has three objectives: (i) to produce bentonite nano zero-valence iron (B-nZVI), (ii) to characterize its adsorbents (B-nZVI), (iii) to characterize its adsorption capacity. Four main tests were used for this purpose: (i) a physical test (Brunauer−Emmett−Teller (BET) surface area), (ii) a chemical test (cation exchange capacity (CEC) and X-ray fluorescence (XRF)), (iii) morphology (field emission scanning electron microscopy (FESEM) and (iv) mineralogy (Fourier transform infrar... [more]

Antibiotic pollution has become a serious concern due to the extensive use of antibiotics, their resistance to removal, and their detrimental effects on aquatic habitats and humans. Hence, developing an efficient antibiotic removal process for aqueous solutions has become vital. Amoxicillin (Amox) is one of the antibiotics that has been efficiently removed from an aqueous solution using hydroxyapatite nanoparticles (HAP NPs). The current study synthesizes and utilizes hydroxyapatite nanoparticles as a cost-effective adsorbent. Adsorbent dose, pH solution, initial Amox concentration, equilibrium time, and temperature are among the factors that have an evident impact on Amox antibiotic adsorption. The (200) mg dose, pH (5), temperature (25) °C, and time (120) min are shown to be the best-optimized values. The nonlinear Langmuir’s isotherm and pseudo-second-order kinetic models with equilibrium capacities of 4.01 mg/g are highly compatible with the experimental adsorption data. The experi... [more]

Non-processed kaolin (flint kaolin) from a mine located in the Capim area (Amazon region, northern Brazil), usually considered as waste, was selected as a source of silicon and aluminum in the synthesis of SAPO-34. This is a molecular sieve and cationic exchanger chosen for tests focusing on the removal of methylene blue in aqueous solutions, which is a cationic dye widely used by textile industries in Brazil. The results revealed that the SAPO-34 has been successfully synthesized with typical cubic morphology, good crystallinity (>90%), and thermal stability (~998 °C). Although the oxidized Fe/Ti impurities contained in the flint kaolin affect the degree of crystallinity of the zeolitic product, its adsorptive properties are not significantly affected, which demonstrates the excellent adsorption results (pH = 11; % removal > 90%). It proved to be an adsorbent with considerable adsorption capacity (9.83 mg·g−1). The pH test confirmed the acidic surface characteristics (pH solution 2−4;... [more]

This study provides the engineering science underpinnings for improved characterization and quantification of the interplay of gases with kerogen and minerals in shale. Natural nanoporous media such as shale (i.e., mudstone) often present with low permeability and dual porosity, making them difficult to characterize given the complex structural and chemical features across multiple scales. These structures give nanoporous solids a large surface area for gas to sorb. In oil and gas applications, full understanding of these media and their sorption characteristics are critical for evaluating gas reserves, flow, and storage for enhanced recovery and CO2 sequestration potential. Other applications include CO2 capture from industrial plants, hydrogen storage on sorbent surfaces, and heterogeneous catalysis in ammonia synthesis. Therefore, high-resolution experimental procedures are demanded to better understand the gas−solid behavior. In this study, CT imaging was applied on the sub-millime... [more]

The sample size or particle size of shale plays a significant role in the characterization of pores by various techniques. To systematically investigate the influence of particle size on pore characteristics and the optimum sample size for different methods, we conducted complementary tests on two overmature marine shale samples with different sample sizes. The tests included small-angle neutron scattering (SANS), gas (N2, CO2, and H2O) adsorption, mercury injection capillary pressure (MICP), and field emission-scanning electron microscopy (FE-SEM) imaging. The results indicate that artificial pores and fractures may occur on the surface or interior of the particles during the pulverization process, and some isolated pores may be exposed to the particle surface or connected by new fractures, thus improving the pore connectivity of the shale. By comparing the results of different approaches, we established a hypothetical model to analyze how the crushing process affects the pore structu... [more]

The implementation of carbon capture, use, and storage in the cement industry is a necessity, not an option, if the climate targets are to be met. Although no capture technology has reached commercial scale demonstration in the cement sector yet, much progress has been made in the last decade. This work intends to provide a general overview of the CO2 capture technologies that have been evaluated so far in the cement industry at the pilot scale, and also about the current plans for future commercial demonstration.

Water vapor sorption in salt hydrates is a promising method to realize seasonal solar heat storage. Several of these materials have already shown promising performance for this application. However, a significant bottle neck for applications is the low thermal conductivity. In this study, several fabrication methods of the fixation of salts and their hydrates on metals to overcome the problem are presented. The products are analyzed concerning the hydration states, the corrosion behavior, the chemical compatibility, and the mechanical stability.

This paper presents the design and a short cycle repeatability test of a silica gel-based thermal energy storage system using low grade heat for the desorption phase. The system was designed to test the degradation in the energy storage density of the adsorbent material for a 2 h working period in a short number of cycles (5 cycles). Low grade heat of 70 °C is used for regeneration during the desorption phase in each cycle. It was found that a reduction of 1.6 W/kg per each cycle of energy storage was observed, up to 5 cycles. The maximal heat storage density was 292 kJ/kg at the first cycle and reduced to 225 kJ/kg at the fifth cycle. Furthermore, the total amount of water vapor adsorbed in the silica gel was observed as well. The test of energy storage was performed under a short time period (maximal approx. 165 min).

This study has investigated the selective immobilization of antimony using the brucite (magnesium hydroxide)-rich precipitate (BP) collected from a hypochlorous storage tank in a nuclear power plant of South Korea. The energy dispersive X-ray and X-ray diffraction analyses revealed that the BP mainly consisted of magnesium (72.5%) and its dominant mineral phase was brucite (Mg(OH)2). Therefore, brandholzite (Mg[Sb(OH)6]2·6H2O) was newly formed through the surface-induced precipitation during the adsorption of antimony using the BP. The adsorbed amount of antimony increased with decreasing pH values because of the increased positive surface charge of the BP (pHpzc = 9.6). The maximum adsorption capacity (Qmax) of BP, calculated by Langmuir adsorption isotherm, was 11.02 mg/g. The presence of competitive anions did not significantly affect the adsorption of antimony toward the BP due to its high selectivity. These results suggest that the facile utilization of the BP as a low-cost adsorb... [more]

A new model of adsorption isotherms Type IV and V is proposed as a basis for theoretical calculations and modelling of adsorption systems such as adsorption heat storage and heat pumps. As the current models have decent yet limited applicability, in this work, we present a new combined model with universal use for micro-mesoporous silica/water adsorption systems. Experimental measurement of adsorption isotherm of water onto seven different samples of micro and mesoporous silica and aluminium-silica were used to fit new adsorption models based on a combination of classical theories and a distribution function related to the pore-size distribution of the selected materials. The fitting was conducted through a repeated non-linear regression using Trust Region Reflective algorithm with weighting factors to compensate for the scalability of the adsorption amount at low relative pressure with optimization of the absolute average deviation fitting parameter. The results display a significant... [more]

A model hydrochar was synthesized from glucose at 180 °C and its Cu(II) sorption capacity was studied experimentally and computationally as an example of molecular-level adsorbent design. The sorption capacity of the glucose hydrochar was less than detection limits (3 mg g−1) and increased significantly with simple alkali treatments with hydroxide and carbonate salts of K and Na. Sorption capacity depended on the salt used for alkali treatment, with hydroxides leading to greater improvement than carbonates and K+ more than Na+. Subsequent zeta potential and infrared spectroscopy analysis implicated the importance of electrostatic interactions in Cu(II) sorption to the hydrochar surface. Computational modeling using Density Functional Theory (DFT) rationalized the binding as electrostatic interactions with carboxylate groups; similarly, DFT calculations were consistent with the finding that K+ was more effective than Na+ at activating the hydrochar. Based on this finding, custom-synthes... [more]

In this study, corn cob was used as raw material and modified methods employing KOH and KMnO4 were used to prepare activated carbon with high adsorption capacity for mercury ions. Experiments on the effects of different influencing factors on the adsorption of mercury ions were undertaken. The results showed that when modified with KOH, the optimal adsorption time was 120 min, the optimum pH was 4; when modified with KMnO4, the optimal adsorption time was 60 min, the optimal pH was 3, and the optimal amount of adsorbent and the initial concentration were both 0.40 g/L and 100 mg/L under both modified conditions. The adsorption process conforms to the pseudo-second-order kinetic model and Langmuir model. Scanning electron microscopy and energy-dispersive X-ray spectroscopy (SEM-EDS), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and Zeta potential characterization results showed that the adsorption process is mainly physical adsorption, surface c... [more]

The desorption of heavy oil is one of the important indicators affecting the development efficiency of the remaining oil in nanopores. However, the study of the adsorption and diffusion mechanisms of heavy oil molecules in nanopores remains scarce. In this work, the influences of temperature on the adsorption and diffusion properties of the heavy oil four-fractions in quartz nanopore have been investigated via molecular dynamics simulations. Our results show that the heavy oil molecules will form a denser multilayer adsorption oil layer on the nanopore surface, and high temperature can alter the adsorption behaviors of the heavy oil four-fractions. As the temperature increases, the saturate molecules are desorbed from the nanopore surfaces, but the aromatic, resin, and asphaltene molecules maintain a tendency to aggregate towards the nanopore surface. In particular, the agglomeration behaviors of most saturate, aromatic and asphaltene molecules in nanopore can be suppressed by the conf... [more]

Arsenic contamination of groundwater is still a global problem due to the toxicity at low dose on human health confirmed by epidemiological studies. Magnetic xerogel monoliths (MXs) were synthesized by the sol-gel polymerization using resorcinol, formaldehyde, alkaline catalyst and magnetite. The varying molar ratios of magnetite and resorcinol (M/R) in the gel were evaluated for As(V) removal from groundwater. The surface chemistry, structure and morphology of MXs related to arsenic adsorption were characterized by X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy, Fourier transform infrared spectroscopy and point of zero charge. Batch adsorption experiments were carried out to investigate the effects of Fe contents, initial pH and adsorbent dose on As(V) removal performance. The MXs with molar ratio of M/R at 0.15 gave the maximum As(V) adsorption capacity and removal with values of 62.8 µg/g and 86.7%, respectively. The adsorption data were well d... [more]

Carbon sequestration via the carbon capture and storage (CCS) method is one of the most useful methods of lowering CO2 emissions in the atmosphere. Ethylenediamine (EDA)- and triethylenetetramine (TETA)-modified mesoporous carbon (MC) has been successfully prepared as a CO2 storage material. The effect of various concentrations of EDA or TETA added to MC, as well as activated carbon (AC), on their CO2 adsorption capacity were investigated using high-purity CO2 as a feed and a titration method to quantitatively measure the amount of adsorbed CO2. The results showed that within 60 min adsorption time, MCEDA49 gave the highest CO2 capacity adsorption (19.68 mmol/g), followed by MC-TETA30 (11.241 mol/g). The improvement of CO2 adsorption capacity at low TETA loadings proved that the four amine functional groups in TETA gave an advantage to CO2 adsorption. TETA-functionalized MC has the potential to be used as a CO2 storage material at a low concentration. Therefore, it is relatively benign... [more]

Drift deposition of emerging and carcinogenic contaminant dicamba (3,6-dichloro-2-methoxy benzoic acid) has become a major health and environmental concern. Effective removal of dicamba in aqueous medium becomes imperative. This study investigates the adsorption of a promising adsorbent, MIL-101(Cr) metal-organic framework (MOF), for the removal of dicamba in aqueous solution. The adsorbent was hydrothermally synthesized and characterized using N2 adsorption-desorption isotherms, Brunauer, Emmett and Teller (BET), powdered X-ray diffraction (XRD), Fourier Transformed Infrared (FTIR) and field emission scanning electron microscopy (FESEM). Adsorption models such as kinetics, isotherms and thermodynamics were studied to understand details of the adsorption process. The significance and optimization of the data matrix, as well as the multivariate interaction of the adsorption parameters, were determined using response surface methodology (RSM). RSM and artificial neural network (ANN) were... [more]

This study focuses on using a facile method for the green preparation of activated carbon (AC) from palm tree fiber (PTF) waste. The synthesized cost-effective AC was investigated for the removal of an anionic dye (Congo red, CR) and a cationic dye (Rhodamine B, RhB) from wastewater. The morphological and structural characterization of the synthesized AC were performed by scanning electron microscopy (SEM), transmission electron microscopy (TEM), surface area, Fourier transform infrared spectroscopy (FTIR), total pore volume, average pore diameter and pore size distribution, zeta potential, and zero-point charge. To investigate the adsorption efficiency, different parameters such as adsorbent dosage, solution pH, initial dye concentration, and duration were applied using the batch experiments. Various adsorption isotherm and kinetics models were applied to study the adsorption mechanism and dynamics. The results showed that chemical activation with a weak acid (H3PO4) at 400 °C for 30... [more]