Monolithic Adsorbents Research Articles

Structural and functional design of CTAB-geopolymer adsorbents for rapid removal of tetracycline: A comparative study

A powder, inorganic membrane and 3D printing cetyltrimethylammonium bromide (CTAB)-geopolymer adsorbents system for adsorbing tetracycline (TC) was developed. And the adsorption properties, adsorption mechanism, adsorption cycle application based on the dynamic pH of adsorption system were systematically investigated by experiment, characterization and density functional theory (DFT) calculation. The introduction of CTAB significantly increased the adsorption response to TC in the high alkaline environment caused by spontaneous alkali release of geopolymer. The adsorption of CTAB-geopolymer for TC was most efficient in the dynamic pH range corresponding to TC- species. The predominant influencing mechanism between CTAB-geopolymer with TC was electrostatic interaction assisted by the hydrogen bonding and n-π interaction. The powder adsorbent with 11 wt% CTAB can capture 92.38 % TC at 2 min and fitted the pseudo-second-order model, and was also suitable for adsorption of trace TC. Although the extension of the diffusion path of the monolithic adsorbents limited the adsorption rate, the 3D printed adsorbent showed an adsorption efficiency of 84.20 % at 302 min. The outstanding adsorption (4 times)-desorption (3 times) cycle properties of 11 %CT-GA (81.15 % at 24 min, 4th adsorption) and cycle cumulative adsorption efficiency of 11 %CT-3DP (59.23 % at 120 min, 4th adsorption) adsorbent were exhibited. Furthermore, a high accuracy performance prediction model with the mean R2 value tended to 1 and the low root mean square error (0.0747) was provided, which can provide theoretical and technical reference for the subsequent industrial application of CTAB-geopolymer adsorbents.

3D-printed zeolite 13X gyroid monolith adsorbents for CO2 capture

Self-standing 3D-printed gyroid monoliths of zeolite 13X were fabricated for the first time for carbon dioxide adsorption. Gyroid sheet-based triply periodic minimal surface (TPMS) lattices provide high surface area per unit volume, smooth surfaces with no discontinuities, and low pressure drop compared to powder and beads, which are essential in gas adsorption. A photopolymer resin and zeolite 13X powder slurry was 3D-printed by digital light processing followed by debinding to remove the polymer and sintering to diffuse and consolidate the zeolite 13X particles. The sintered adsorbents were mechanically stable, and structural and morphological analyses revealed the interconnected nature of the gyroid cells permitting CO2 molecules to easily diffuse into the printed structure, thus ensuring sufficient adsorbent/adsorbate contact. The gyroid zeolite monoliths reached an equilibrium adsorption capacity of 3.5 mmol g−1 in 77 min at 25 °C and 1 bar, whereas the beads and powder required 96 and 100 min, respectively, while after 20 pressure swing adsorption (PSA) cycles, the zeolite monolith showed sustainable performance compared to the powder. The CO2/N2 selectivity ranged from 328 (at 50 mbar) to 51 (at 1 bar) at 25 °C for the zeolite monolith, whereas the powder exhibited selectivity values in the range of 294 (at 50 mbar) to 33 (at 1 bar). Dynamic breakthrough experiments using CO2/N2 mixtures confirmed the fast kinetics and separation performance of the monoliths, while the pressure drop was also significantly lower than the powder and the beads. The novel topology of the developed self-standing gyroid zeolite monoliths eliminate the need for structuring of powdered adsorbents and exhibit competitive performance, enhanced kinetics and cyclability, and reduced pressure drop toward large-scale carbon capture application.

Assembly of 3D printed N-doped biochar as impeller with CaCO3 as sacrificial pore generator for enhanced dye adsorption

Three-dimensional (3D) printed monolithic catalysts/adsorbents have attracted much attention due to their excellent properties. Herein, the rice husk-derived nitrogen-doped biochar (using urea as the nitrogen dopant) was printed into monolithic adsorbents using direct ink writing technology, and then assembled as agitating paddles for organic dye adsorption. To reduce the over-embedding of active sites in the polymeric matrix, CaCO3 particles in nano-sized or micron-sized were added as sacrificial pore generators to form macropores and expose active sites, leading to an enhanced mass transfer efficiency. Material characterization results confirm the self-sacrificial role of CaCO3. The 3D-printed adsorbents with micron-sized CaCO3 (denoted as 3D-HRSCCm) possessed excellent adsorption performance, as evidenced by a high adsorption capacity and kinetics study. Meanwhile, 3D-HRSCCm adsorbents were mounted as agitating impellers which demonstrated excellent reusability with the adsorption efficiency remaining above 90% after ten cycles. Furthermore, the 3D-HRSCCm exhibited excellent adsorption properties for various dyes such as methylene blue, rhodamine B, crystal violet, and malachite green. Moreover, the numerical simulation confirms that the introduction of CaCO3 as a pore generator improved diffusion by providing wider channels and facilitated the mass transfer that accelerated the adsorption rates.

Integrating direct air capture with algal biofuel production to reduce cost, energy, and GHG emissions

We investigate the potential to reduce costs and greenhouse gas emissions of the utilization of direct air capture of CO2 (DAC) for the production of algal biofuel. We examine four integrated designs for a DAC system comprised of solid amine monolith adsorbents delivering CO2 at the required level for algae cultivation with a photobioreactor (PBR)-based fuel production facility. We show that the integration of DAC with this biofuel production facility provides cost and greenhouse gas emissions benefits. Heat integration decreases operating expenses by reducing energy demand for heating requirements. Mass integration, utilizing flue gas CO2 as a carbon source for the PBRs, decreases the DAC system scale, resulting in both capital and operating cost savings. The most advantageous option depends on the interplay of heat and mass integration while matching the diurnal rhythm of algal growth with the inherently steady pace and energy requirements of the DAC system and fuel production. For these technologies, the DAC-PBR mass and energy integration provides an 18 % cost reduction and a 50 % reduction in greenhouse gas emissions for the current state of the technology.

Dry-gel conversion synthesis sponge-based MIL-160 monolith adsorbent at low temperature for water adsorption

The facile synthesis MOFs monolith adsorbent is highly imperative for the economically friendly development of water adsorption. Herein, metal-organic framework material MIL-160 monolith was synthesized by the dry-gel conversion method at low temperature. The effects of curing conditions, dry-gel composition and crystallization temperature on crystal structure, porosity, microstructure and water vapor adsorption/desorption properties were studied. XRD results showed that the MIL-160 powder and monolith adsorbent can be synthesized under the condition that the molar ratio of dry-gel was Al3+: FDCA: NaOH = 1:1:2 at 60 °C (FDCA is the abbreviation of 2,5-Furandicarboxylicacid). The water vapor saturation adsorption capacity and water vapor desorption activation energy of the powder and monolith adsorbent were 0.310, 0.231 g/g at 20 % RH and 72.3, 62.4 kJ/mol, respectively. The convenient dry-gel conversion synthesis of MIL-160 monolith may provide a guidance for the manufacture of high-performance water harvest device.

An Ultramicroporous Graphene-Based 3D Structure Derived from Cellulose-Based Biomass for High-Performance CO2 Capture.

The use of powered activated carbon is often limited by inconsistent particle sizes and porosities, leading to reduced adsorption efficiencies. In this study, we demonstrated a practical and environmentally friendly method for creating a 3D graphene nanostructure with highly uniform ultramicropores from wood-based biomass through a series of delignification, carbonization, and activation processes. In addition, we evaluated the capture characteristics of this structure for CO2, CH4, and N2 gases as well as its selectivity for binary-mixture gases. Based on textural and chemical analyses, the delignified monolith had a lamellar structure interconnected by cellulose-based fibers. Interestingly, applying the KOH vapor activation technique solely to the delignified samples led to the formation of a monolithic 3D network composed of interconnected graphene sheets with a high degree of crystallinity. Especially, the Act. 1000 sample exhibited a specific surface area of 1480 m2/g and a considerable pore volume of 0.581 cm3/g, featuring consistently uniform ultramicropores over 90% in the range of 3.5-11 Å. The monolithic graphene-based samples, predominantly composed of ultramicropores, demonstrated a notably heightened capture capacity of 6.934 mol/kg at 110 kPa for CO2, along with favorable selectivity within binary gas mixtures (CO2/N2, CO2/CH4, and CO2/CH4). Our findings suggest that this biomass-derived 3D structure has the potential to serve as a monolithic adsorbent in gas separation applications.

Oxidation of Supported Amines for CO2 Direct Air Capture: Assessing Impact on Physical Properties and Mobility via NMR Relaxometry

AbstractAminopolymer‐based adsorbents are commonly investigated for CO2 direct air capture (DAC). In the presence of high temperature and oxygen, which can occur during adsorption‐regeneration cycles, oxidative degradation can significantly reduce adsorbent lifetime. Degradation is typically measured using adsorption performance metrics or chemical characterization. This work demonstrates that the polymer's physical properties, as measured via nuclear magnetic resonance (NMR) relaxometry and differential scanning calorimetry, can be used to quantitatively track degradation. The extent of oxidation of an alumina‐poly(ethylenimine) sample, measured by reductions in amine efficiency (A.E.), is correlated with proton T2 relaxation times. This work hypothesizes that T2 relaxation accurately tracks oxidative degradation in aminopolymers due to the reduction in polymer mobility occurring during the oxidation process. The ability to use NMR relaxometry as a noninvasive technique to probe degradation is demonstrated on a 1‐inch square‐channel monolith adsorbent exposed to actual DAC service conditions. This highlights the potential for relaxometry to evaluate the state of the adsorbent accurately and rapidly compared to typical analytical methods.

Advancements in gas phase pollutant removal: A comprehensive study on the sorption of CO2 and SO2 on modified carbon monoliths

The synthesis of carbon monoliths using activated carbon treated with phenol-formaldehyde resin has been identified as a promising approach for the removal of pollutants from the gas phase. Monolithic adsorbents were synthesised and modified by adding silica, acid etching, and high temperature activation with CO2. Sorption capacities were determined by CO2 and SO2 adsorption tests. Preliminary findings indicated that the unmodified monoliths exhibited limited porosity. The activation process significantly altered the textural parameters, resulting in an increase in surface area and adsorption and desorption capacity. The modification yielded a monolith with a specific surface area of 598 m2/g and a pore volume of 438 mm3/g. The sorption capacity of the monoliths towards CO2 and SO2 was 1.64 mmol/g and 3.93 mmol/g, respectively. The modifications introduced developed the sorption capacity of the monoliths, enabling the regeneration process and its further use in subsequent measurement cycles.

Simple synthesis of acyl coupling conjugated microporous polymers monolithic material for synergistic capture of PM and CO2 in flue gas and process simulation

Adsorption and separation technologies based on physical adsorbents have the advantages of simple operation, low heat of adsorption and easy regeneration. They have received much attention for the capture of CO2 and PM from flue gases. However, the inherent “trade-off” between adsorption capacity and adsorption selectivity, as well as the high gas permeation resistance after powder processing and shaping, severely limit the prospects for industrial applications. Here, acyl functional groups were strategically introduced into polymer frameworks to successfully synthesize monolithic adsorbents (AC-CMPs) with a hierarchical pore structure for PM capture and CO2/N2 selective adsorption. The three-dimensional network structure composed of aligned hollow nanotubes effectively enhances the dispersion and mass transfer of gas flow per unit volume. Based on the porous media, multiphase flow model and discrete phase model, the gas flow process of PM trapped by AC-CMPs was simulated using Fluent. The simulation dynamically revealed the relationship between permeability resistance and filtration efficiency. The highly delocalized π-π conjugated porous skeleton linked by continuous covalent bonds endowed AC-CMPs with good stability, which prevented them from degrading in humid and high-temperature environments, thus keeping the adsorption capacity unchanged. The high polarity environment generated by the open oxygen atoms within the AC-CMPs framework, along with a high micro/mesopore ratio, enable it to achieve a CO2 adsorption capacity of 2.07 mmol/g at 273 K and 1 bar. Ideal adsorption solution theory calculations (IAST) and CO2/N2 column breakthrough experiments confirmed the excellent CO2 selectivity of AC-CMPs under realistic carbon capture conditions.

In-situ synthesis Al-fumarate on polyurethane foam as a monolithic desiccant for adsorption heat pump systems

Metal-organic framework (MOF) is considered the most promising adsorbent in adsorption heat pump (AHP) systems, owing to its high water-harvesting capacity and rapid adsorption kinetics. However, the practical implementation of powdery MOF usually suffers from poor recovery and easy agglomeration. In this work, a novel Al-fumarate loaded on polyurethane (PU) foam (PU/Al-fumarate) to construct a monolithic desiccant was designed using an in-situ synthetic self-assembly technology. Two synthesis strategies including mixed solvent thermal method (M method) and low-temperature solution method (L method) were implemented and compared. The influences of different synthesis methods on the MOF loading rate, crystal phase, chemical composition, pore structure, microscopic morphology, and the adsorption/desorption performance of monolithic desiccants were systematically discussed. The results showed that the two synthesis methods had no fundamental effects on the composition and crystal phase of PU/Al-fumarate. However, the M-method design strategy possessed a better MOF loading rate (71.76 %), higher specific surface area (722.15 m2·g−1), and more excellent water-adsorption capacity (0.333 g·g−1) as compared with the monolithic adsorbent synthesized by L-method technology. Furthermore, the resulting monolithic desiccant designed by the M-method strategy showed low desorption activation energy and good cyclic stability. Therefore, this novel PU foam-based Al-fumarate synthesized by M-method as monolithic desiccant will provide a potential candidate for AHP system.

Experimental kinetics and thermodynamics investigation: Chemically activated carbon-enriched monolithic reduced graphene oxide for efficient CO2 capture

In this research, we have developed solid MGOs by self-assembled reduction process of GO at 90 °C with different weight ratios of oxalic acid (1:1, 1:0.500, and 1:0.250). The as-synthesized monoliths were carbonized (at 600 °C) and chemically activated with varying proportions of NaOH (1:1, 1:2, and 1:3). This materials offer the CO2 adsorption effect under dynamic conditions, fast mass transfer, easy handling, and outstanding stability throughout the adsorption-desorption cycle. FE-SEM, and HR-TEM analyses confirmed the porous nature and shape of the adsorbents, while XPS examination revealed the presence of distinct functional groups on the surface of the monolith. By increasing the mass ratios (MGO:NaOH) from 1:1 to 1:2, the surface areas increased by approximately 2.6 times, ranging from 520.8 to 753.9 m2 g⁻1 (surface area of the untreated MGO was 289.2 m2 g⁻1). Consequently, this resulted in a notable enhancement of 2.10 mmol g⁻1 in dynamic CO2 capture capacity. The assessment encompassed the evaluation of production yield, selectivity, regenerability, kinetics, equilibrium isotherm, and isosteric temperatures of adsorption (Qst). The decrease in CO2 capture effectiveness with rising adsorption temperature indicated an exothermic and physisorption process. The regenerability of 99.1 % at 100 °C and excellent cyclic stability with efficient CO2 adsorption make this monolithic adsorbent appropriate for post-combustion CO2 capture. The significant Qst lend support to the heterogeneity of the adsorbent's surface, and the pseudo-second-order kinetic model along with the Freundlich isotherm model emerged as the most fitting. Therefore, the current investigation shows that the carbon-enriched adsorbents enhance the CO2 adsorption capacity. It may be used as a low-cost pretreatment method on an industrial scale before carbon capture.

Fabrication of a bio-based polymer adsorbent and its application for extraction and determination of glycosides from Huangqi Liuyi Decoction

Huangqi Liuyi Decoction, a famous classical Chinese prescription, shows significant curative effect on diabetes and its complications, in which calycosin-7-glucoside, liquiritin and glycyrrhizic acid are the main components that playing these mentioned pharmacological activity, under the synergistic action of various other ingredients in the decoction. However, there are significant differences in the content of active compounds in Chinese medicinal materials, which mainly due to origin, picking seasons, and processing methods. Hence, the accurate content of the glycosides is the prerequisite for ensuring the pharmacological efficacy. Aiming at establishing an efficient extraction and determination method for accurate quantitative analysis of calycosin-7-glucoside, liquiritin and glycyrrhizic acid in Huangqi Liuyi Decoction, an on line solid-phase extraction-high-performance liquid chromatography method was developed, using a homemade bio-based monolithic adsorbent. The bio-based adsorbent was prepared in a stainless steel tube, using bio-monomers of methyleugenol and S-allyl-L-cysteine, which effectively reduced the dependence of the polymer field on non-renewable fossil resources and reduced carbon emissions. Furthermore, the prepared adsorbent owned abundant chemical groups, which can produce interactions of hydrogen bond, dipole-dipole, π-π and hydrophobic force with the target glycosides, thus improving the specific recognition ability of the adsorbent. The experiments were carried out on an LC-3000 HPLC instrument with a six-way valve. Methodology validation indicates that the recovery is in the range of 97.0%-103.4% with the RSD in the range of 1.6%-4.0%, due to the specific selectivity of the bio-based monolithic adsorbent for these three glycosides, and good matrix-removal ability for Huangqi Liuyi decoction. The limit of detection is 0.17, 0.50 and 0.33μg/mL for calycosin-7-glucoside, liquiritin and glycyrrhizic acid, respectively, and the limit of quantitation is 0.50, 1.50 and 1.00μg/mL, respectively, with the linear range of 2-200μg/mL for calycosin-7-glucoside, and 5-500μg/mL for liquiritin and glycyrrhizic acid. The present work provided a simple and efficient method for the extraction and determination of glycosides in complex medicinal plants.

Low-resistance and high-tolerance monolithic spiro-bifluorene-based conjugated microporous polymer for co-capture of PM and CO2 in waste gas

The utilization of solid adsorbents for the co-capture of harmful particulate matter (PM) and carbon dioxide (CO2) in industrial exhaust streams represents a crucial component within the emerging field of waste gas terminal treatment technologies. Extensive research has focused on particulate or powdered adsorbents rather than monolithic materials, whereas monolithic adsorbents exhibit superior advantages in practical industrial applications. Herein, a monolithic spiro-bifluorene-based conjugated micro-porous polymer (DS-CMPs) with hierarchical porous and functionalized hollow nanotube structures was proposed. The favorable characteristics exhibited by DS-CMPs encompass a highly delocalized π-π conjugated skeleton, permanent porosity, unique thermal and chemical stability, precisely defined chemical composition, and excellent water vapor tolerance. These inherent qualities guarantee that DS-CMPs employed for the co-capture of PM and CO2 from exhaust gases exhibit exceptional capture efficiency, low permeation resistance, favorable isosteric heat of adsorption (Qst), and recyclability. The reasons behind the high capture efficiency and low permeation resistance of monolithic DS-CMPs were analyzed through mechanistic exploration and Electrostatic Surface Potential (ESP) calculations. Moreover, the stability inherent in the framework structure and physicochemical properties of DS-CMPs can surmount the notable decline in the capturing capability of porous materials utilized within damp and elevated temperature surroundings. Following exposure to elevated humidity (RH = 86 ± 1 %) and high-temperature (500 ℃) conditions, DS-CMPs exhibited a remarkable capture efficiency exceeding 99.00 % for PM2.5. The self-assembly of monolithic DS-CMPs into a smooth array of nanotube bundles effectively reduces the friction between airflow and material, enhances airflow dispersion, and achieves a minimum permeability resistance of only 8 Pa. At a pressure of 1 bar and temperature of 273 K, the CO2 adsorption capacity of DS-CMPs amounts to 2.72 mmol/g. The high absorption capacity for CO2 is primarily attributed to the presence of a significant microporous/mesoporous ratio and notable surface charge differences. In contrast to powdered adsorbents plagued by sample elution and gas pressure drop issues, the monolithic DS-CMPs showcases good mechanical properties, rendering them readily applicable within industrial bed circulation systems to achieve the co-capture of PM and CO2.

Support Platform of Functionalized Sustainable Cellulose Self-Entanglement Monolithic Adsorbents for Efficient Adsorption of Cadmium(II) Ions.

Serious water contamination induced by massive discharge of cadmium(II) ions is becoming an emergent environmental issue due to high toxicity and bioaccumulation; thus, it is extremely urgent to develop functional materials for effectively treating with Cd2+ from wastewater. Benefiting from abundant binding sites, simple preparation process, and adjustable structure, UiO-66-type metal-organic frameworks (MOFs) had emerged as promising candidates in heavy metal adsorption. Herein, monolithic UiO-66-(COOH)2-functionalized cellulose fiber (UCLF) adsorbents were simply fabricated by incorporating MOFs into cellulose membranes through physical blending and self-entanglement. A two-dimensional structure was facilely constructed by cellulose fibers from sustainable biomass agricultural waste, providing a support platform for the integration of eco-friendly UiO-66-(COOH)2 synthesized with lower temperature and toxicity solvent. Structure characterization and bath experiments were performed to determine operational conditions for the maximization of adsorption capacity, thereby bringing out an excellent adsorption capacity of 96.10 mg/g. UCLF adsorbent holding 10 wt % loadings of UiO-66-(COOH)2 (UCLF-2) exhibited higher adsorption capacity toward Cd2+ as compared to other related adsorbents. Based on kinetics, isotherms, and thermodynamics, the adsorption behavior was spontaneous, exothermic, as well as monolayer chemisorption. Coordination and electrostatic attraction were perhaps mechanisms involved in the adsorption process, deeply unveiled by the effects of adsorbate solution pH and X-ray photoelectron spectroscopy. Moreover, UCLF-2 adsorbent with good mechanical strength offered a structural guarantee for the successful implementation of practical applications. This study manifested the feasibility of UCLF adsorbents used for Cd2+ adsorption and unveiled a novel strategy to shape MOF materials for wastewater decontamination.

Eco-friendly hydrophobic ZIF-8/sodium alginate monolithic adsorbent: An efficient trap for microplastics in the aqueous environment

Microplastics (MPs), a newly emerging class of environmental contaminants, pose a severe threat to the entire ecosystem. The development of efficient and environmentally responsible adsorbents for removing the MPs is a particularly urgent research. Herein, a kind of monolithic ZIF-8 based adsorbents featuring stable hydrophobicity and micropore-mesopore-macropore hierarchical porous structure were fabricated by in situ growth of ZIF-8 nanoparticles on sodium alginate (SA) framework, and using polydimethylsiloxane (PDMS) as a hydrophobic agent. The monolithic nature of ZIF-8/SA allowed an easy solid–liquid separation process for adsorbents from water environment compared to powdered materials. The hierarchical porous structure ensures a remarkable MPs removal performance. The ZIF-8/SA showed high adsorption capacities of 594, 585, and 282 mg/g for polymethyl methacrylate (PMMA), poly (vinylidene difluoride) (PVDF), and polyvinyl chloride (PVC) respectively, and rapid adsorption kinetic progress within 120 min. The ZIF-8/SA adsorbents also exhibited excellent stability in the presence of interfering ions, acid/alkali, and humic acid, and displayed adsorption performance of > 70 % even in actual aquatic environment such as tap water, river water, and seawater. The results of characterizations showed that the synergistic effect of electrostatic interaction, hydrogen bonding, hydrophobic force, and van der Waals force was the main adsorption mechanism. The well-designed hydrophobic ZIF-8/SA monolithic materials would be promising to rapidly remove the MPs from the water environment.

Development of a three-dimensional porous ionic liquid-chitosan-graphene oxide aerogel for efficient extraction and detection of polyhalogenated carbazoles in sediment samples

The three-dimensional porous ionic liquid-chitosan-graphene oxide aerogel (IL–CS–GOA) monolithic adsorbent with a through-hole structure was prepared using natural chitosan (CS) as the skeletal framework, graphene oxide (GO) as the support to provide mechanical strength, and ionic liquid (IL) as the porogen and modifier. The resulting IL–CS–GOA demonstrated a fluffy and porous structure with various pore sizes and excellent regeneration capability (over six cycles). Its specific surface area exceeded that of CS-GOA and IL-GOA by more than 7 times, enhancing its polyhalogenated carbazoles (PHCZs) adsorption capacity. Within 5 min, IL–CS–GOA (1.0 mg) exhibited adsorption amounts of 539 ng mg−1 for 3-bromocarbazole (3-BCZ), 716 ng mg−1 for 2,7-dibromocarbazole (2,7-BCZ), and 798 ng mg−1 for 1,3,6,8-tetrabromocarbazole (1,3,6,8-BCZ), showcasing its rapid mass transfer and high adsorption capabilities. IL–CS–GOA was utilized as the adsorbent for glass dropper extraction (GDE) in conjunction with gas chromatography-mass spectrometry (GC-MS/MS), to develop a highly efficient and accurate method for determining PHCZs in sediments. Under optimal conditions, the established method exhibited a wide linear range (0.4–250 ng g−1, r ≥ 0.9990), low detection limits (0.04–0.24 ng g−1), and satisfactory recoveries (80.5 %–93.8 %), enabling the accurate and rapid detection of PHCZs in sediment samples. This study presents a novel approach for creating three-dimensional porous aerogels, introduces a new form of sample pretreatment using GDE with a monolithic adsorbent, and offers a new method for the determination of PHCZs in environmental matrices.

Experimental and modeling study of volatile organic compounds adsorption over zeolitic monolith adsorbent

In this study, a coupled mass and momentum model is developed and solved to describe the dynamic adsorption of a single adsorbate over honeycomb structured zeolite under industrial operating conditions. The Linear Driving Force approximation was used to predict the kinetics of adsorption to the solid-phase mass transfer and Navier Stokes equations were solved both radially and axially under laminar flow conditions through the honeycomb channels. To investigate the effect of key input parameters on model results, a sensitivity analysis was performed. Modeling and experimental results compared the effects of different initial concentrations and gas stream face velocities under a range of conditions to determine adsorption capacity, removal efficiency, and the 5% breakthrough time. Overall, the model output was in good agreement (less than 5% mean absolute relative error in concentration) with the experimental results under industrially relevant operating conditions. Modeling results illustrated that the radial velocity distribution over the monolith channels has an important effect on the shape of the breakthrough curve as well as the 5% breakthrough time. Both experimental results and modeling predictions showed that the long tails of the adsorption breakthroughs were the result of the non-uniform flow distribution, which resulted in delayed saturation of the outer honeycomb channels.

Fabrication of a biochar-doped monolithic adsorbent and its application for the extraction and determination of coumarins from Angelicae Pubescentis Radix

A monolithic adsorbent was designed aiming to the structure of osthole and columbianadin, and fabricated using diallyl phthalate as the monomer and ethylene dimethacrylate as the crosslinker with the addition of bamboo biochar, via polymerization reaction in a stainless-steel tube. The prepared composite adsorbent packed in the tube was used as a solid-phase extraction column for the extraction and determination of two coumarins (osthole and columbianadin) in Angelicae Pubescentis Radix, combing with a C18 analytical column through an HPLC instrument, which show excellent matrix-removal ability and good selectivity to osthole and columbianadin. Furthermore, the present adsorbent shows good applicability, which was used for the extraction of osthole from Duhuo Jisheng Pill. Compared to the commercial C18 and phenyl adsorbent, the present adsorbent own better selectivity and higher resolution. These results attributed to the enhanced specific surface area (141 m2/g) and enriched interaction sites of the resulting composite adsorbent, due to the doping of bamboo biochar, which can produce hydrogen bond, dipole-dipole, π-π and hydrophobic force interactions with the osthole and columbianadin. The methodology validation indicated that the present method showed good precision and good accuracy, and the composite adsorbent showed good preparative repeatability, which can be reused for no less than 100 times with the relative standard deviation ≤4.6 % (n = 100). The present work provided a simple and efficient method for the extraction and determination osthole and columbianadin from Angelicae Pubescentis Radix.

On-line extraction and determination of coumarins compounds from mouse plasma based on a homemade phenyl-hybrid monolithic adsorbent

A phenyl-hybrid monolithic adsorbent was prepared using an organic monomer of ethylene glycol phenyl ether acrylate and inorganic monomers of tetramethoxysilane and vinyltrimethoxysilane, via polycondensation and polymerization in a stainless-steel column, which shows porous structure and multiple functional groups, according to the measurements of scanning electron microscopy, nitrogen adsorption-desorption method and infrared spectroscopy. The resulting hybrid phenyl-based monolith was used as a solid-phase extraction column, combining with an analytical column in conjunction with high-performance liquid chromatography system for the on-line extraction and determination of coumarins (praeruptorin A and praeruptorin B) in Peucedani Radix from mouse plasma. The homemade hybrid monolithic solid-phase extraction column exhibits good removal ability for the sample matrices, as well as unique selectivity for the two praeruptorins. Methodology validation results indicate that the present method is applicable for the on-line extraction and quantitative analysis of praeruptorin A and praeruptorin B in Peucedani Radix from mouse plasma with a limit of quantitation 0.06 μg/mL and a linear range 0.06–5 μg/mL (r＞0.999), thus indicating the present method is a promising and alternative method for the quantitative determination of similar target components with micro or trace concentration from complex extract solution and plasma.

Amorphous Fe–Mn binary oxides nanoparticles decorating waste bamboo biomass-based monolith for efficient arsenic removal with column adsorption

The removal of naturally occurring arsenic from aqueous media remains a challenging endeavor for the protection of public health and ecosystems. Herein, we devised a workable fresh-biomass-based monolith adsorbent by in situ generation of amorphous Fe–Mn binary oxides nanoparticles (Fe–Mn–O) on a waste bamboo biomass (MB) via a simple procedure of pre-oxidation plus co-precipitation. In the pre-oxidation process of MB, the surface underwent roughening and the manganese ions permeated deeply inside the biomass, both of which facilitated the loading of Fe–Mn–O (25.06 wt%). As a result, the Fe–Mn–O/MB had outstanding adsorption capacities of 33.41 and 36.88 mg g−1 for As(III) and As(V), respectively. XRD and FTIR analyses show that the amorphous structure of Fe–Mn–O with low-coordinated active centers provides numerous hydroxyl functional groups that enhance arsenic adsorption, moreover, oxidation of As(III) was realized. In different water matrix, the Fe–Mn–O/MB composite exhibited a retention of 87.33 % and 89.53 % of its original adsorption capacity for As(III) and As(V) after five cycles of reuse as well as enabled continuous operation in a fixed-bed system with a bed volume of around 1150. Therefore, this work provides a promising approach for efficient abatement of inorganic arsenic-caused water pollution.