Search Results (11)

This study aimed to investigate the kinetic properties of methylene blue adsorption on carbon cryogel samples and nitrogen-doped and nitrogen-and-sulfur-co-doped carbon cryogel. Nitrogen and sulfur were incorporated into the carbon structure to enhance surface, electronic and textural properties. Methylene blue, a widely utilized dye in the textile industry, has become one of the most commonly detected substances in water systems. Experimental data were fitted with four kinetic models and showed excellent fits with the linear pseudo-second-order model. The results indicated that doping with nitrogen and sulfur did not significantly affect the adsorption of methylene blue. Full article

Pesticides pose a significant threat to nontargeted organisms, and their pervasive use makes avoidance challenging. We employed nitrogen-doped carbon cryogels for the removal of organophosphate pesticides. The materials were synthesized and characterized using SEM, Raman spectroscopy, XPS, and BET analysis. Results revealed mesoporous cryogels with pore diameters ranging from 3 to 13 nm. Interestingly, the specific surface area did not change systematically with increasing nitrogen content. All investigated materials have similar composition and structural disorder. Dimethoate, malathion, and chlorpyrifos removal was investigated under stationary and dynamic conditions. Stationary conditions demonstrated successful removal of aliphatic dimethoate and malathion by all investigated materials. Conversely, the materials with the lowest and highest nitrogen content proved ineffective with aromatic chlorpyrifos. Under dynamic conditions, all materials effectively removed malathion and chlorpyrifos while exhibiting suboptimal performance for dimethoate adsorption. Application of nitrogen-doped carbon cryogels to tap water spiked with pesticides yielded successful results under the same conditions. Toxicity testing of treated samples revealed a consistent decrease in toxicity, indicating that contact with cryogels reduces the initial solution’s toxicity. This result also confirms that material–pesticide interaction does not lead to the formation of more toxic byproducts. The demonstrated efficacy suggests the potential application of these materials in water treatment. Full article

Nowadays, due to the increasing number of diseases and injuries related to bone tissue, there is an acute problem of creating a material that could be incorporated into the bone tissue structure and contribute to accelerated bone regeneration. Such materials can be represented by a polymeric matrix that holds the material in the bone and an inorganic component that can be incorporated into the bone structure and promote accelerated bone regeneration. Therefore, in this work we investigated polyvinyl alcohol-based composite cryogels containing an in situ deposited inorganic filler, hydroxyapatite. The freezing temperature was varied during the synthesis process. The composition of the components was determined by infrared spectroscopy and the phase composition by X-ray phase analysis, from which it was found that the main phase of the composite is hydroxyapatite and that the particle size decreases with increasing freezing temperature. The elemental composition of the surface is dominated by carbon, oxygen, phosphorus and calcium; no impurities of other elements not typical for polyvinyl alcohol/ hydroxyapatite cryogels were found. Higher mechanical properties and melting points were observed at −15 °C. Cryogenic treatment parameters did not affect cell viability; however, cell viability was above 80% in all samples. Full article

Since currently used natural, nonrenewable phosphorus resources are estimated to be depleted in the next 30–200 years, phosphorus recovery from any phosphorus-rich residues has attracted great interest. In this study, phosphorus recovery from complex wastewater samples was investigated using continuous adsorption on cryogel column composited calcium silicate hydrate nanoparticles (CSH columns). The results showed that 99.99% of phosphate was recovered from a synthetic water sample (50 mg L⁻¹) using a 5 cm CSH column with a 5 mL min⁻¹ influent flow rate for 6 h while 82.82% and 97.58% of phosphate were recovered from household laundry wastewater (1.84 mg L⁻¹) and reverse osmosis concentrate (26.46 mg L⁻¹), respectively. The adsorption capacity decreased with an increasing flow rate but increased with increasing initial concentration and column height, and the obtained experimental data were better fitted to the Yoon–Nelson model (R² = 0.7723–0.9643) than to the Adams–Bohart model (R² = 0.6320–0.8899). The adsorption performance of phosphate was decreased 3.65 times in the presence of carbonate ions at a similar concentration, whereas no effect was obtained from nitrate and sulfate. The results demonstrate the potential of continuous-flow phosphate adsorption on the CSH column for the recovery of phosphate from complex wastewater samples. Full article

In this work, we study the influence of reduced graphene oxide (rGO) on the morphology and chemistry of highly porous N,S-doped carbon cryogels. Simultaneously, we propose an easily upscalable route to prepare such carbons by adding graphene oxide (GO) in as-received suspended form to the aqueous solution of the ι-carrageenan and urea precursors. First, 1.25–5 wt% GO was incorporated into the dual-doped polymer matrix. The CO₂, CO, and H₂O emitted during the thermal treatments resulted in the multifaceted modification of the textural and chemical properties of the porous carbon. This facilitated the formation of micropores through self-activation and resulted in a substantial increase in the apparent surface area (up to 1780 m²/g) and pore volume (up to 1.72 cm³/g). However, adding 5 wt% GO led to overactivation. The incorporated rGO has an ordering effect on the carbon matrix. The evolving oxidative species influence the surface chemistry in a complex way, but sufficient N and S atoms (ca. 4 and >1 at%, respectively) were preserved in addition to the large number of developing defects. Despite the complexity of the textural and chemical changes, rGO increased the electrical conductivity monotonically. In alkaline oxygen reduction reaction (ORR) tests, the sample with 1.25 wt% GO exhibited a 4e⁻ mechanism and reasonable stability, but a higher rGO content gradually compromised the performance of the electrodes. The sample containing 5 wt% GO was the most sensitive under oxidative conditions, but after stabilization it exhibited the highest gravimetric capacitance. In Li-ion battery tests, the coulombic efficiency of all the samples was consistently above 98%, indicating the high potential of these carbons for efficient Li-ion insertion and reinsertion during the charge–discharge process, thereby providing a promising alternative for graphite-based anodes. The cell from the 1.25 wt% GO sample showed an initial discharge capacity of 313 mAh/g, 95.1% capacity retention, and 99.3% coulombic efficiency after 50 charge–discharge cycles. Full article

S and N double-doped high surface area biomass-derived carbons were obtained from marine biomass-derived ι-carrageenan. Adding carbon nanoparticles (CNPs), namely graphene oxide (GO) or carbon nanotubes (CNTs), in the early stage of the synthesis leads to a modified porous texture and surface chemistry. The porous textures were characterized by N₂ (−196.15 °C) and CO₂ (0 °C) isotherms. The best GO- and CNT-added carbons had an apparent surface area of 1780 m²/g and 1170 m²/g, respectively, compared to 1070 m²/g for the CNP-free matrix. Analysis of the Raman spectra revealed that CNT was more efficient in introducing new defects than GO. Based on XPS, the carbon samples contain 2–4.5 at% nitrogen and 1.1 at% sulfur. The Dubinin–Radushkevich (DR) and Henry models were used to assess the strength of the interactions between various gases and the surface. The N₂/H₂ and CO₂/CH₄ selectivities were estimated with ideal adsorbed solution theory (IAST). While the CNPs, particularly GO, had a remarkable influence on the porous texture and affected the surface chemistry, their influence on the separation selectivity of these gases was more modest. Full article

A cost-effective and sustainable method is successfully developed to produce lignin-based cryogels with a mechanically robust 3D interconnected structure. A choline chloride–lactic acid (ChCl–LA)-based deep eutectic solvent (DES) is used as a cosolvent to promote the synthesis of lignin–resorcinol–formaldehyde (LRF) gels that can self-assemble a robust string-bead-like framework. The molar ratio of LA to ChCl in DES has a significant influence on the gelation time and properties of the ensuing gels. Moreover, it is discovered that doping the metal–organic framework (MOF) during the sol–gel process can greatly accelerate the gelation of lignin. It takes a mere 4 h to complete the LRF gelation process at a DES ratio of 1:5 combined with 5% MOF. This study yields LRF carbon cryogels doped with copper that exhibit 3D interconnected bead-like carbon spheres with a prominent micropore of 1.2 nm. A specific capacitance as high as 185 F g⁻¹ can be obtained for the LRF carbon electrode at a current density of 0.5 A g⁻¹, and it has an excellent long-term cycling stability. This study provides a novel method of synthesizing high-lignin-content carbon cryogels with promising potential for application in the field of energy storage devices. Full article

In this paper we report the synthesis of a N, S co-doped metal free carbon cryogel obtained from a marine biomass derived precursor using urea as nitrogen source. Natural carrageenan intrinsically contains S and inorganic salt. The latter also serves as an activating agent during the pyrolytic step. The overall 11.6 atomic % surface heteroatom concentration comprises 5% O, 4.6% N and 1% S. The purified and annealed final carbon (CA) has a hierarchical pore structure of micro-, meso- and macropores with an apparent surface area of 1070 m²/g. No further treatment was applied. The gas adsorption potential of the samples was probed with H₂, CO₂ and CH₄, while the electrocatalytic properties were tested in an oxygen reduction reaction. The atmospheric CO₂ and CH₄ storage capacity at 0 °C in the low pressure range is very similar to that of HKUST-1, with the CO₂/CH₄ selectivity below 20 bar, even exceeding that of the MOF, indicating the potential of CA in biogas separation. The electrocatalytic behavior was assessed in an aqueous KOH medium. The observed specific gravimetric capacitance 377 F/g was exceeded only in B, N dual doped and/or graphene doped carbons from among metal free electrode materials. The CA electrode displays almost the same performance as a commercial 20 wt% Pt/C electrode. The oxygen reduction reaction (ORR) exhibits the 4-electron mechanism. The 500-cycle preliminary stability test showed only a slight increase of the surface charge. Full article

Bioremediation is a key process for reclaiming polluted soil and water by the use of biological agents. A commonly used approach aims to neutralise or remove harmful pollutants from contaminated areas using live microorganisms. Generally, immobilised microorganisms rather than planktonic cells have been used in bioremediation methods. Activated carbon, inorganic minerals (clays, metal oxides, zeolites), and agricultural waste products are acceptable substrates for the immobilisation of bacteria, although there are limitations with biomass loading and the issue with leaching of bacteria during the process. Various synthetic and natural polymers with different functional groups have been used successfully for the efficient immobilisation of microorganisms and cells. Promise has been shown using macroporous materials including cryogels with entrapped bacteria or cells in applications for water treatment and biotechnology. A cryogel is a macroporous polymeric gel formed at sub-zero temperatures through a process known as cryogelation. Macroporous hydrogels have been used to make scaffolds or supports for immobilising bacterial, viral, and other cells. The production of composite materials with immobilised cells possessing suitable mechanical and chemical stability, porosity, elasticity, and biocompatibility suggests that these materials are potential candidates for a range of applications within applied microbiology, biotechnology, and research. This review evaluates applications of macroporous cryogels as tools for the bioremediation of contaminants in wastewater. Full article

Nitrogen-containing carbon derivatives were prepared by the carbonization of poly(aniline-co-p-phenylenediamine) cryogels in inert atmosphere. Lower aniline fraction in the comonomer mixture used for preparation of the cryogels led to the decrease of their thermal stability, a consequent increase of carbonization degree, and less defective structure of carbonized materials. The resulting carbonaceous products had up to 4 orders of magnitude higher specific surface area than their respective cryogel precursors, the highest value 931 m² g⁻¹ being achieved for carbonized poly(p-phenylenediamine) cryogel. Electrochemical characterization of the carbon derivatives demonstrated that the decrease in aniline concentration during the synthesis of the precursor cryogels led to higher gravimetric capacitance for corresponding carbonized materials. These materials can potentially be used for energy storage applications. Full article

Chitosan is the N-deacetylated derivative of chitin, a naturally abundant mucopolysaccharide that consists of 2-acetamido-2-deoxy-β-d-glucose through a β (1→4) linkage and is found in nature as the supporting material of crustaceans, insects, etc. Chitosan has been strongly recommended as a suitable functional material because of its excellent biocompatibility, biodegradability, non-toxicity, and adsorption properties. Boosting all these excellent properties to obtain unprecedented performances requires the core competences of materials chemists to design and develop novel processing strategies that ultimately allow tailoring the structure and/or the composition of the resulting chitosan-based materials. For instance, the preparation of macroporous materials is challenging in catalysis, biocatalysis and biomedicine, because the resulting materials will offer a desirable combination of high internal reactive surface area and straightforward molecular transport through broad “highways” leading to such a surface. Moreover, chitosan-based composites made of two or more distinct components will produce structural or functional properties not present in materials composed of one single component. Our group has been working lately on cryogenic processes based on the unidirectional freezing of water slurries and/or hydrogels, the subsequent freeze-drying of which produce macroporous materials with a well-patterned structure. We have applied this process to different gels and colloidal suspensions of inorganic, organic, and hybrid materials. In this review, we will describe the application of the process to chitosan solutions and gels typically containing a second component (e.g., metal and ceramic nanoparticles, or carbon nanotubes) for the formation of chitosan nanocomposites with a macroporous structure. We will also discuss the role played by this tailored composition and structure in the ultimate performance of these materials. Full article