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Six N-alkylpyridinium salts [CnPy](2)[MCl4] (n = 4 or 12 and M = Co, Cu, Zn) were synthesized, and their structure and thermal properties were studied. The [C4Py](2)[MCl4] compounds are monoclinic and crystallize in the space group P2(1)/n. The crystals of the longer chain analogues [C12Py](2)[MCl4] are triclinic and crystallize in the space group P (1) over bar. Above the melting temperature, all compounds are ionic liquids (ILs). The derivatives with the longer C12 chain exhibit liquid crystallinity and the shorter chain compounds only show a melting transition. Consistent with single-crystal analysis, electron paramagnetic resonance spectroscopy suggests that the [CuCl4](2-) ions in the Cu-based ILs have a distorted tetrahedral geometry.
Six N-alkylpyridinium salts [CnPy](2)[MCl4] (n = 4 or 12 and M = Co, Cu, Zn) were synthesized, and their structure and thermal properties were studied. The [C4Py](2)[MCl4] compounds are monoclinic and crystallize in the space group P2(1)/n. The crystals of the longer chain analogues [C12Py](2)[MCl4] are triclinic and crystallize in the space group P (1) over bar. Above the melting temperature, all compounds are ionic liquids (ILs). The derivatives with the longer C12 chain exhibit liquid crystallinity and the shorter chain compounds only show a melting transition. Consistent with single-crystal analysis, electron paramagnetic resonance spectroscopy suggests that the [CuCl4](2-) ions in the Cu-based ILs have a distorted tetrahedral geometry.
The synthesis, structure, and photocatalytic water splitting performance of two new titania (TiO2)/gold(Au)/Bombyx mori silk hybrid materials are reported. All materials are monoliths with diameters of up to ca. 4.5 cm. The materials are macroscopically homogeneous and porous with surface areas between 170 and 210 m(2)/g. The diameter of the TiO2 nanoparticles (NPs) - mainly anatase with a minor fraction of brookite - and the Au NPs are on the order of 5 and 7-18 nm, respectively. Addition of poly(ethylene oxide) to the reaction mixture enables pore size tuning, thus providing access to different materials with different photocatalytic activities. Water splitting experiments using a sunlight simulator and a Xe lamp show that the new hybrid materials are effective water splitting catalysts and produce up to 30 mmol of hydrogen per 24 h. Overall the article demonstrates that the combination of a renewable and robust scaffold such as B. mori silk with a photoactive material provides a promising approach to new monolithic photocatalysts that can easily be recycled and show great potential for application in lightweight devices for green fuel production.
The synthesis, structure, and photocatalytic water splitting performance of two new titania (TiO 2 )/gold(Au)/Bombyx mori silk hybrid materials are reported. All materials are monoliths with diameters of up to ca. 4.5 cm. The materials are macroscopically homogeneous and porous with surface areas between 170 and 210 m 2/g. The diameter of the TiO 2 nanoparticles (NPs) – mainly anatase with a minor fraction of brookite – and the Au NPs are on the order of 5 and 7–18 nm, respectively. Addition of poly(ethylene oxide) to the reaction mixture enables pore size tuning, thus providing access to different materials with different photocatalytic activities. Water splitting experiments using a sunlight simulator and a Xe lamp show that the new hybrid materials are effective water splitting catalysts and produce up to 30 mmol of hydrogen per 24 h. Overall the article demonstrates that the combination of a renewable and robust scaffold such as B. mori silk with a photoactive material provides a promising approach to new monolithic photocatalysts that can easily be recycled and show great potential for application in lightweight devices for green fuel production.
We have earlier shown that linear poly(ethylene imine) (LPEI) is an efficient growth modifier for calcium phosphate mineralization from aqueous solution (Shkilnyy et al., Langmuir, 2008, 24 (5), 2102). The current study addresses the growth process and the reason why LPEI is such an effective additive. To that end, the solution pH and the calcium and phosphate concentrations were monitored vs. reaction time using potentiometric, complexometric, and photometric methods. The phase transformations in the precipitates and particle morphogenesis were analyzed by X-ray diffraction and transmission electron microscopy, respectively. All measurements reveal steep decreases of the pH, calcium, and phosphate concentrations along with a rapid precipitation of brushite nanoparticles early on in the reaction. Brushite transforms into hydroxyapatite (HAP) within the first 2 h, which is much faster than what is reported, for example, for calcium phosphate precipitated with poly(acrylic acid). We propose that poly(ethylene imine) acts as a proton acceptor (weak buffer), which accelerates the transformation from brushite to HAP by taking up the protons that are released from the calcium phosphate precipitate during the phase transformation.
Carbon Adsorbents from Spent Coffee for Removal of
Methylene Blue and Methyl Orange from Water
(2021)
Activated carbons (ACs) were prepared from dried spent coffee (SCD), a biological waste product, to produce adsorbents for methylene blue (MB) and methyl orange (MO) from aqueous solution. Pre-pyrolysis activation of SCD was achieved via treatment of the SCD with aqueous sodium hydroxide solutions at 90 °C. Pyrolysis of the pretreated SCD at 500 °C for 1 h produced powders with typical characteristics of AC suitable and effective for dye adsorption. As an alternative to the rather harsh base treatment, calcium carbonate powder, a very common and abundant resource, was also studied as an activator. Mixtures of SCD and CaCO3 (1:1 w/w) yielded effective ACs for MO and MB removal upon pyrolysis needing only small amounts of AC to clear the solutions. A selectivity of the adsorption process toward anionic (MO) or cationic (MB) dyes was not observed.
Carbon Adsorbents from Spent Coffee for Removal of
Methylene Blue and Methyl Orange from Water
(2021)
Activated carbons (ACs) were prepared from dried spent coffee (SCD), a biological waste product, to produce adsorbents for methylene blue (MB) and methyl orange (MO) from aqueous solution. Pre-pyrolysis activation of SCD was achieved via treatment of the SCD with aqueous sodium hydroxide solutions at 90 °C. Pyrolysis of the pretreated SCD at 500 °C for 1 h produced powders with typical characteristics of AC suitable and effective for dye adsorption. As an alternative to the rather harsh base treatment, calcium carbonate powder, a very common and abundant resource, was also studied as an activator. Mixtures of SCD and CaCO3 (1:1 w/w) yielded effective ACs for MO and MB removal upon pyrolysis needing only small amounts of AC to clear the solutions. A selectivity of the adsorption process toward anionic (MO) or cationic (MB) dyes was not observed.
The article describes the surface modification of 3D printed poly(lactic acid) (PLA) scaffolds with calcium phosphate (CP)/gelatin and CP/chitosan hybrid coating layers. The presence of gelatin or chitosan significantly enhances CP co-deposition and adhesion of the mineral layer on the PLA scaffolds. The hydrogel/CP coating layers are fairly thick and the mineral is a mixture of brushite, octacalcium phosphate, and hydroxyapatite. Mineral formation is uniform throughout the printed architectures and all steps (printing, hydrogel deposition, and mineralization) are in principle amenable to automatization. Overall, the process reported here therefore has a high application potential for the controlled synthesis of biomimetic coatings on polymeric biomaterials.
The article describes the surface modification of 3D printed poly(lactic acid) (PLA) scaffolds with calcium phosphate (CP)/gelatin and CP/chitosan hybrid coating layers. The presence of gelatin or chitosan significantly enhances CP co-deposition and adhesion of the mineral layer on the PLA scaffolds. The hydrogel/CP coating layers are fairly thick and the mineral is a mixture of brushite, octacalcium phosphate, and hydroxyapatite. Mineral formation is uniform throughout the printed architectures and all steps (printing, hydrogel deposition, and mineralization) are in principle amenable to automatization. Overall, the process reported here therefore has a high application potential for the controlled synthesis of biomimetic coatings on polymeric biomaterials.
The sensing potential of CuO nanoparticles synthesized via. precipitation from a water/ionic liquid precursor (ILP) mixture was investigated. The particles have a moderate surface area of 66 m(2)/g after synthesis, which decreases upon thermal treatment to below 5 m(2)/g. Transmission electron microscopy confirms crystal growth upon annealing, likely due to sintering effects. The as-synthesized particles can be used for ethanol sensing. The respective sensors show fast response and recovery times of below 10 s and responses greater than 2.3 at 100 ppm of ethanol at 200 degrees C, which is higher than any CuO-based ethanol sensor described so far.
Hexagonal p-type semiconductor CuS nanoplates were synthesized via a hot injection method from bis(trimethylsilyl) sulfide and the ionic liquid precursor bis(N-dodecylpyridinium) tetrachloridocuprate( II). The particles have a broad size distribution with diameters between 30 and 680 nm and well-developed crystal habits. The nanoplates were successfully incorporated into organic photovoltaic (OPV) cells as hole conduction materials. The power conversion efficiency of OPV cells fabricated with the nanoplates is 16% higher than that of a control device fabricated without the nanoplates. (C) 2018 Author(s).
Efficient Removal of Tetracycline and Bisphenol A from Water with a New Hybrid Clay/TiO2 Composite
(2023)
New TiO2 hybrid composites were prepared fromkaolinclay, predried and carbonized biomass, and titanium tetraisopropoxideand explored for tetracycline (TET) and bisphenol A (BPA) removalfrom water. Overall, the removal rate is 84% for TET and 51% for BPA.The maximum adsorption capacities (q (m))are 30 and 23 mg/g for TET and BPA, respectively. These capacitiesare far greater than those obtained for unmodified TiO2. Increasing the ionic strength of the solution does not change theadsorption capacity of the adsorbent. pH changes only slightly changeBPA adsorption, while a pH > 7 significantly reduces the adsorptionof TET on the material. The Brouers-Sotolongo fractal modelbest describes the kinetic data for both TET and BPA adsorption, predictingthat the adsorption process occurs via a complex mechanism involvingvarious forces of attraction. Temkin and Freundlich isotherms, whichbest fit the equilibrium adsorption data for TET and BPA, respectively,suggest that adsorption sites are heterogeneous in nature. Overall,the composite materials are much more effective for TET removal fromaqueous solution than for BPA. This phenomenon is assigned to a differencein the TET/adsorbent interactions vs the BPA/adsorbent interactions:the decisive factor appears to be favorable electrostatic interactionsfor TET yielding a more effective TET removal.
New hybrid clay adsorbent based on kaolinite clay and Carica papaya seeds with improved cation exchange capacity (CEC), rate of heavy metal ion uptake, and adsorption capacity for heavy metal ions were prepared. The CEC of the new material is ca. 75 meq/100 g in spite of the unexpectedly low surface area (approximate to 19 m(2)/g). Accordingly, the average particle size of the hybrid clay adsorbent decreased from over 200 to 100 pm. The hybrid clay adsorbent is a highly efficient adsorbent for heavy metals. With an initial metal concentration of 1 mg/L, the hybrid clay adsorbent reduces the Cd2+, Ni2+, and Pb2+ concentration in aqueous solution to <= 4, <= 7 and <= 20 mu g/L, respectively, from the first minute to over 300 min using a fixed bed containing 2 g of adsorbent and a flow rate of approximate to 7 mL/min. These values are (with the exception of Pb2+) in line with the WHO permissible limits for heavy metal ions. In a cocktail solution of Cd2+, and Ni2+, the hybrid clay shows a reduced rate of uptake but an increased adsorption capacity. The CEC data suggest that the adsorption of Pb2+, Cd2+, and Ni2+ on the hybrid clay adsorbent is essentially due to ion exchange. This hybrid clay adsorbent is prepared from materials that are abundant and by a simple means that is sustainable, easily recovered from aqueous solution, nonbiodegradable (unlike numerous biosorbent), and easily regenerated and is a highly efficient alternative to activated carbon for water treatment.
Functional hybrid materials on the basis of inorganic hosts and ionic liquids (ILs) as guests hold promise for a virtually unlimited number of applications. In particular, the interaction and the combination of properties of a defined inorganic matrix and a specific IL could lead to synergistic effects in property selection and tuning. Such hybrid materials, generally termed ionogels, are thus an emerging topic in hybrid materials research. The current article addresses some of the recent developments and focuses on the question why silica is currently the dominating matrix used for (inorganic) ionogel fabrication. In comparison to silica, matrix materials such as layered simple hydroxides, layered double hydroxides, clay-type substances, magnetic or catalytically active solids, and many other compounds could be much more interesting because they themselves may carry useful functionalities, which could also be exploited for multifunctional hybrid materials synthesis. The current article combines experimental results with some arguments as to how new, advanced functional hybrid materials can be generated and which obstacles will need to be overcome to successfully achieve the synthesis of a desired target material.
Cellulose/calcium phosphate hybrid materials were synthesized via an ionic liquid-assisted route. Scanning electron microscopy, transmission electron microscopy, energy-dispersive X-ray spectroscopy, X-ray diffraction, infrared spectroscopy, and thermogravimetric analysis/differential thermal analysis show that, depending on the reaction conditions, cellulose/hydroxyapatite, cellulose/ chlorapatite, or cellulose/monetite composites form. Preliminary studies with MC3T3-E1 pre-osteoblasts show that the cells proliferate on the hybrid materials suggesting that the ionic liquid-based process yields materials that are potentially useful as scaffolds for regenerative therapies.
New mesoporous silk fibroin (SF)/silica hybrids were processed via a one-pot soft and energy-efficient sol-gel chemistry and self-assembly from a silica precursor, an acidic or basic catalyst, and the ionic liquid 1-butyl-3-methylimidazolium chloride, acting as both solvent and mesoporosity-inducer. The as-prepared materials were obtained as slightly transparent-opaque, amorphous monoliths, easily transformed into powders, and stable up to ca. 300 degrees C. Structural data suggest the formation of a hexagonal mesostructure with low range order and apparent surface areas, pore volumes, and pore radii of 205-263 m(2) g(-1), 0.16-0.19 cm(3) g(-1), and 1.2-1.6 nm, respectively. In all samples, the dominating conformation of the SF chains is the beta-sheet. Cytotoxicity/bioactivity resazurin assays and fluorescence microscopy demonstrate the high viability of MC3T3 pre-osteoblasts to indirect (>= 99 +/- 9%) and direct (78 +/- 2 to 99 +/- 13%) contact with the SF/silica materials. Considering their properties and further improvements, these systems are promising candidates to be explored in bone tissue engineering. They also offer excellent prospects as electrolytes for solid-state electrochemical devices, in particular for fuel cells.
Thirteen N-butylpyridinium salts, including three monometallic [C4Py](2)[MCl4], nine bimetallic [C4Py](2)[(M1-xMxCl4)-M-a-Cl-b] and one trimetallic compound [C4Py](2)[(M1-y-zMyMz (c) Cl4)-M-a-M-b] (M=Co, Cu, Mn; x=0.25, 0.50 or 0.75 and y=z=0.33), were synthesized and their structure and thermal and electrochemical properties were studied. All compounds are ionic liquids (ILs) with melting points between 69 and 93 degrees C. X-ray diffraction proves that all ILs are isostructural. The conductivity at room temperature is between 10(-4) and 10(-8) S cm(-1). Some Cu-based ILs reach conductivities of 10(-2) S cm(-1), which is, however, probably due to IL dec. This correlates with the optical bandgap measurements indicating the formation of large bandgap semiconductors. At elevated temperatures approaching the melting points, the conductivities reach up to 1.47x10(-1) S cm(-1) at 70 degrees C. The electrochemical stability windows of the ILs are between 2.5 and 3.0 V.
Eight d-metal-containing N-butylpyridinium ionic liquids (ILs) with the nominal composition (C4Py)2[Ni0.5M0.5Cl4] or (C4Py)2[Zn0.5M0.5Cl4] (M = Cu, Co, Mn, Ni, Zn; C4Py = N-butylpyridinium) were synthesized, characterized, and investigated for their optical properties. Single crystal and powder X-ray analysis shows that the compounds are isostructural to existing examples based on other d-metal ions. Inductively coupled plasma optical emission spectroscopy measurements confirm that the metal/metal ratio is around 50 : 50. UV-Vis spectroscopy shows that the optical absorption can be tuned by selection of the constituent metals. Moreover, the compounds can act as an optical sensor for the detection of gases such as ammonia as demonstrated via a simple prototype setup.
Eight d-metal-containing N-butylpyridinium ionic liquids (ILs) with the nominal composition (C4Py)2[Ni0.5M0.5Cl4] or (C4Py)2[Zn0.5M0.5Cl4] (M = Cu, Co, Mn, Ni, Zn; C4Py = N-butylpyridinium) were synthesized, characterized, and investigated for their optical properties. Single crystal and powder X-ray analysis shows that the compounds are isostructural to existing examples based on other d-metal ions. Inductively coupled plasma optical emission spectroscopy measurements confirm that the metal/metal ratio is around 50 : 50. UV-Vis spectroscopy shows that the optical absorption can be tuned by selection of the constituent metals. Moreover, the compounds can act as an optical sensor for the detection of gases such as ammonia as demonstrated via a simple prototype setup.
A new solid-state material, N-butyl pyridinium diiodido argentate(I), is synthesized using a simple and effective one-pot approach. In the solid state, the compound exhibits 1D ([AgI2](-))(n) chains that are stabilized by the N-butyl pyridinium cation. The 1D structure is further manifested by the formation of long, needle-like crystals, as revealed from electron microscopy. As the general composition is derived from metal halide-based ionic liquids, the compound has a low melting point of 100-101 degrees C, as confirmed by differential scanning calorimetry. Most importantly, the compound has a conductivity of 10(-6) S cm(-1) at room temperature. At higher temperatures the conductivity increases and reaches to 10(-4 )S cm(-1) at 70 degrees C. In contrast to AgI, however, the current material has a highly anisotropic 1D arrangement of the ionic domains. This provides direct and tuneable access to fast and anisotropic ionic conduction. The material is thus a significant step forward beyond current ion conductors and a highly promising prototype for the rational design of highly conductive ionic solid-state conductors for battery or solar cell applications.