Influence of NiO into the CO2 capture of Li4SiO4 and its catalytic performance on dry reforming of methane.

Carbon capture, utilization, and storage (CCUS) technology offer promising solution to mitigate the threatening consequences of large-scale anthropogenic greenhouse gas emissions. Within this context, this report investigates the influence of NiO deposition on the Li4SiO4 surface during the CO2 capture process and its catalytic behavior in hydrogen production via dry methane reforming. Results demonstrate that the NiO impregnation method modifies microstructural features of Li4SiO4, which positively impact the CO2 capture properties of the material. In particular, the NiO-Li4SiO4 sample captured twice as much CO2 as the pristine Li4SiO4 material, 6.8 and 3.4 mmol of CO2 per gram of ceramic at 675 and 650 °C, respectively. Additionally, the catalytic results reveal that NiO-Li4SiO4 yields a substantial hydrogen production (up to 55 %) when tested in the dry methane reforming reaction. Importantly, this conversion remains stable after 2.5 h of reaction and is selective for hydrogen production. This study highlights the potential of Li4SiO4 both a support and a captor for a sorption-enhanced dry reforming of methane. To the best of our knowledge, this is the first report showcasing the effectiveness of Li4SiO4 as an active support for Ni-based catalysis in the dry reforming of methane. These findings provide valuable insights into the development of this composite as a dual-functional material for carbon dioxide capture and conversion.

High CO2 permeation using a new Ce0.85Gd0.15O2-δ-LaNiO3 composite ceramic-carbonate dual-phase membrane.

This work shows the synthesis, characterization and evaluation of dense-ceramic membranes made of Ce0.85Gd0.15O2-δ-LaNiO3 (CG-LN) composites, where the fluorite-perovskite ratio (CG:LN) was varied as follows: 75:25, 80:20 and 85:15 wt.%. Supports were initially characterized by XRD, SEM and electrical conductivity (using vacuum and oxygen atmospheres), to determine the composition, microstructural and ionic-electronic conductivity properties. Later, supports were infiltrated with an eutectic carbonates mixture, producing the corresponding dense dual-phase membranes, in which CO2 permeation tests were conducted. Here, CO2 permeation experiments were performed from 900 to 700°C, in the presence and absence of oxygen (flowed in the sweep membrane side). Results showed that these composites possess high CO2 permeation properties, where the O2 addition significantly improves the ionic conduction on the sweep membrane side. Specifically, the GC80-LN20 composition presented the best results due to the following physicochemical characteristics: high electronic and ionic conductivity, appropriate porosity, interconnected porous channels, as well as thermal and chemical stabilities between the composite support and carbonate phases.

Enhancing CO2 chemisorption on lithium cuprate (Li2CuO2) at moderate temperatures and different pressures by alkaline nitrate addition.

Lithium, sodium and potassium nitrate-containing Li2CuO2 samples were prepared to analyze the CO2 capture process at moderate temperatures, using different pressure conditions. Initially, in a CO2 saturated atmosphere, all these samples showed high CO2 capture efficiencies between 150 and 350 °C, in comparison to the pristine Li2CuO2 (T≥ 500 °C). These results evidenced that Li-, Na- and K-nitrate addition on Li2CuO2 importantly enhances the whole CO2 capture. These results were corroborated kinetically. Moreover, the effects and reaction mechanism of alkaline nitrate addition were determined by X-ray diffraction, infrared spectroscopy and differential scanning calorimetric analyses. Nitrate anions melt and work as donor/acceptor oxygen anion intermediates during the Li2CuO2 carbonation process. Moreover, the carbonation may be completed (Li2CO3 and CuO production) through Li3Cu2O4 formation. When the CO2 capture process was evaluated using low partial pressures, the results presented similar efficiencies to those obtained using a saturated CO2 condition, showing differences only during the decarbonation process (T > 700 °C), as the CO2 chemisorption-desorption equilibrium was shifted. Finally, pristine Li2CuO2 and alkaline nitrate-containing Li2CuO2 samples were evaluated at high pressures. The pristine Li2CuO2 sample did not show any CO2 capture improvement, while alkaline nitrate-containing Li2CuO2 samples did improve. This was attributed to the alkaline nitrate melting process and the pressure equilibrium conditions.

Evaluation of Fe-containing Li2CuO2 on CO2 capture performed at different physicochemical conditions.

Li2CuO2 and different iron-containing Li2CuO2 samples were synthesized by solid state reaction. On iron-containing samples, atomic sites of copper are substituted by iron ions in the lattice (XRD and Rietveld analyses). Iron addition induces copper release from Li2CuO2, which produce cationic vacancies and CuO, due to copper (Cu2+) and iron (Fe3+) valence differences. Two different physicochemical conditions were used for analyzing CO2 capture on these samples; (i) high temperature and (ii) low temperature in presence of water vapor. At high temperatures, iron addition increased CO2 chemisorption, due to structural and chemical variations on Li2CuO2. Kinetic analysis performed by first order reaction and Eyring models evidenced that iron addition on Li2CuO2 induced a faster CO2 chemisorption but a higher thermal dependence. Conversely, CO2 chemisorption at low temperature in water vapor presence practically did not vary by iron addition, although hydration and hydroxylation processes were enhanced. Moreover, under these physicochemical conditions the whole sorption process became slower on iron-containing samples, due to metal oxides presence.

Synthesis of gamma radiation-induced PEGylated cisplatin for cancer treatment.

The use of poly(ethylene glycol) (PEG) for the development of novel PEGylated biomolecules is playing an increasingly meaningful role in cancer treatment. Cisplatin (CDDP), is a useful chemotherapy drug. However, it is unclear whether PEGylated cisplatin (CDDPPEG) has potential as an alternative therapeutic agent. Here we prepared a PEGylated cisplatin by gamma radiation-induced synthesis, for the first time. PEGylated drugs were characterized using Raman and Fourier transform infrared spectroscopy (FTIR), as well as scanning electron microscopy coupled with Energy Dispersive X-ray (SEM/EDX). The results show that the cisplatin can be successfully PEGylated by this method. Furthermore, we show a proposal for the mechanism of the PEGylation reaction. The novel product exhibits in vitro therapeutic potential comparable to cisplatin at concentrations lower than 23 µM (Pt), causing differences in cell cycle checkpoints, which suggest changes in the signaling pathways that control growth arrest and cause apoptosis of A549 cells.

CO2 capture enhancement in InOF-1 via the bottleneck effect of confined ethanol.

CO2 capture of InOF-1 was enhanced 3.6-fold, at 1 bar and 30 °C, by confining EtOH within its pores. Direct visualisation by single crystal X-ray diffraction revealed that EtOH divides InOF-1 channels in wide sections separated by "bottlenecks" caused by EtOH molecules bonded to the µ2-OH functional groups of InOF-1.

Nanoporous composites prepared by a combination of SBA-15 with Mg-Al mixed oxides. Water vapor sorption properties.

This work presents two easy ways for preparing nanostructured mesoporous composites by interconnecting and combining SBA-15 with mixed oxides derived from a calcined Mg-Al hydrotalcite. Two different Mg-Al hydrotalcite addition procedures were implemented, either after or during the SBA-15 synthesis (in situ method). The first procedure, i.e., the post-synthesis method, produces a composite material with Mg-Al mixed oxides homogeneously dispersed on the SBA-15 nanoporous surface. The resulting composites present textural properties similar to the SBA-15. On the other hand, with the second procedure (in situ method), Mg and Al mixed oxides occur on the porous composite, which displays a cauliflower morphology. This is an important microporosity contribution and micro and mesoporous surfaces coexist in almost the same proportion. Furthermore, the nanostructured mesoporous composites present an extraordinary water vapor sorption capacity. Such composites might be utilized as as acid-base catalysts, adsorbents, sensors or storage nanomaterials.

Inactivation of Ascaris eggs in water using hydrogen peroxide and a Fenton type nanocatalyst (FeOx/C) synthesized by a novel hybrid production process.

Inactivation tests of Ascaris eggs (Ae) were performed using hydrogen peroxide and a Fenton type nanocatalyst supported on activated carbon (AC) (FeOx/C). Blank inactivation tests were also carried out using H2O2 and H2O2/AC as oxidation systems. The FeOx/C nanocatalyst was synthesized through a novel hybrid method developed in this work. The method is based on the incipient impregnation technique, using isopropyl alcohol as dissolvent and chelating agent of the iron salt and the ultrasonic method. The supported nanocatalyst contained 2.61% w/w of total iron and the support 0.2% w/w. Transmission electron microscopy (TEM)-energy dispersive spectrometer (EDS) images permitted verification of the presence of finely dispersed FeOx nanoparticles, with sizes ranging from 19 to 63 nm. SEM-EDS analysis and TEM images also showed good dispersion of iron oxide nanoparticles, most probably maghemite; γ-Fe2O3, able to produce hydroperoxyl radical as reported in the literature. The FeOx/C nanocatalyst-H2O2 system showed an average Ae inactivation efficiency of 4.46% Ae/mg H2O2. This value is significantly higher than the result obtained using the support-H2O2 system and H2O2 alone and it is also better than data reported for the classical Fenton process (homogeneous phase) with or without UV light.

CO2 capture properties of lithium silicates with different ratios of Li2O/SiO2: an ab initio thermodynamic and experimental approach.

The lithium silicates have attracted scientific interest due to their potential use as high-temperature sorbents for CO2 capture. The electronic properties and thermodynamic stabilities of lithium silicates with different Li2O/SiO2 ratios (Li2O, Li8SiO6, Li4SiO4, Li6Si2O7, Li2SiO3, Li2Si2O5, Li2Si3O7, and α-SiO2) have been investigated by combining first-principles density functional theory with lattice phonon dynamics. All these lithium silicates examined are insulators with band-gaps larger than 4.5 eV. By decreasing the Li2O/SiO2 ratio, the first valence bandwidth of the corresponding lithium silicate increases. Additionally, by decreasing the Li2O/SiO2 ratio, the vibrational frequencies of the corresponding lithium silicates shift to higher frequencies. Based on the calculated energetic information, their CO2 absorption capabilities were extensively analyzed through thermodynamic investigations on these absorption reactions. We found that by increasing the Li2O/SiO2 ratio when going from Li2Si3O7 to Li8SiO6, the corresponding lithium silicates have higher CO2 capture capacity, higher turnover temperatures and heats of reaction, and require higher energy inputs for regeneration. Based on our experimentally measured isotherms of the CO2 chemisorption by lithium silicates, we found that the CO2 capture reactions are two-stage processes: (1) a superficial reaction to form the external shell composed of Li2CO3 and a metal oxide or lithium silicate secondary phase and (2) lithium diffusion from bulk to the surface with a simultaneous diffusion of CO2 into the shell to continue the CO2 chemisorption process. The second stage is the rate determining step for the capture process. By changing the mixing ratio of Li2O and SiO2, we can obtain different lithium silicate solids which exhibit different thermodynamic behaviors. Based on our results, three mixing scenarios are discussed to provide general guidelines for designing new CO2 sorbents to fit practical needs.

Structural and thermochemical chemisorption of CO2 on Li(4+x)(Si(1-x)Al(x))O4 and Li(4-x)(Si(1-x)V(x))O4 solid solutions.

Different Li(4)SiO(4) solid solutions containing aluminum (Li(4+x)(Si(1-x)Al(x))O(4)) or vanadium (Li(4-x)(Si(1-x)V(x))O(4)) were prepared by solid state reactions. Samples were characterized by X-ray diffraction and solid state nuclear magnetic resonance. Then, samples were tested as CO(2) captors. Characterization results show that both, aluminum and vanadium ions, occupy silicon sites into the Li(4)SiO(4) lattice. Thus, the dissolution of aluminum is compensated by Li(1+) interstitials, while the dissolution of vanadium leads to lithium vacancies formation. Finally, the CO(2) capture evaluation shows that the aluminum presence into the Li(4)SiO(4) structure highly improves the CO(2) chemisorption, and on the contrary, vanadium addition inhibits it. The differences observed between the CO(2) chemisorption processes are mainly correlated to the different lithium secondary phases produced in each case and their corresponding diffusion properties.

CO2 capture at low temperatures (30-80 °C) and in the presence of water vapor over a thermally activated Mg-Al layered double hydroxide.

The carbonation process of a calcined Mg-Al layered double hydroxide (LDH) was systematically analyzed at low temperatures, varying the relative humidity. Qualitative and quantitative experiments were performed. In a first set of experiments, the relative humidity was varied while maintaining a constant temperature. Characterization of the rehydrated products by thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR) and solid-state NMR revealed that the samples did not recover the LDH structure; instead hydrated MgCO(3) was produced. The results were compared with similar experiments performed on magnesium oxide for comparison purposes. Then, in the second set of experiments, a kinetic analysis was performed. The results showed that the highest CO(2) capture was obtained at 50 °C and 70% of relative humidity, with a CO(2) absorption capacity of 2.13 mmol/g.

Oxygen absorption in free-standing porous silicon: a structural, optical and kinetic analysis.

Porous silicon (PSi) is a nanostructured material possessing a huge surface area per unit volume. In consequence, the adsorption and diffusion of oxygen in PSi are particularly important phenomena and frequently cause significant changes in its properties. In this paper, we study the thermal oxidation of p+-type free-standing PSi fabricated by anodic electrochemical etching. These free-standing samples were characterized by nitrogen adsorption, thermogravimetry, atomic force microscopy and powder X-ray diffraction. The results show a structural phase transition from crystalline silicon to a combination of cristobalite and quartz, passing through amorphous silicon and amorphous silicon-oxide structures, when the thermal oxidation temperature increases from 400 to 900 °C. Moreover, we observe some evidence of a sinterization at 400 °C and an optimal oxygen-absorption temperature about 700 °C. Finally, the UV/Visible spectrophotometry reveals a red and a blue shift of the optical transmittance spectra for samples with oxidation temperatures lower and higher than 700 °C, respectively.

Thermokinetic analysis of the CO2 chemisorption on Li4SiO4 by using different gas flow rates and particle sizes.

Lithium orthosilicate (Li(4)SiO(4)) was synthesized by solid-state reaction and then its CO(2) chemisorption capacity was evaluated as a function of the CO(2) flow rate and particle size. Initially, a Li(4)SiO(4) sample, with a total surface area of 0.4 m(2)/g, was used to analyze the CO(2) chemisorption, varying the CO(2) flow between 30 and 200 mL/min. Results showed that CO(2) flows modify the kinetic regime from which CO(2) capture is controlled. In the first moments and at low CO(2) flows, the CO(2) capture is controlled by the CO(2) diffusion through the gas-film system, whereas at high CO(2) flows it is controlled by the CO(2) chemisorption reaction rate. Later, at larger times, once the carbonate-oxide external shell has been produced the whole process depends on the CO(2) chemisorption kinetically controlled by the lithium diffusion process, independently of the CO(2) flow. Additionally, thermokinetic analyses suggest that temperature induces a CO(2) particle surface saturation, due to an increment of CO(2) diffusion through the gas-film interface. To elucidate this hypothesis, the Li(4)SiO(4) sample was pulverized to increase the surface area (1.5 m(2)/g). Results showed that increasing the surface particle area, the saturation was not reached. Finally, the enthalpy activation (DeltaH(double dagger)) values were estimated for the two CO(2) chemisorption processes, the CO(2) direct chemisorption produced at the Li(4)SiO(4) surface, and the CO(2) chemisorption kinetically controlled by the lithium diffusion, once the carbonate-oxide shell has been produced.

Thermokinetic study of the rehydration process of a calcined MgAl-layered double hydroxide.

The rehydration process of a calcined MgAl-layered double hydroxide (LDH) with a Mg/Al molar ratio of 3 was systematically analyzed at different temperatures and relative humidity. Qualitative and quantitative experiments were done. In the first set of samples, the temperature or the relative humidity was varied, fixing the second variable. Both adsorption and absorption phenomena were present; absorption process was associated to the LDH regeneration. Of course, in all cases the LDH regeneration was confirmed by other techniques such as TGA, solid state NMR, and SAXS. In the second set of experiments, a kinetic analysis was performed, the results allowed to obtain different activation enthalpies for the LDH regeneration as a function of the relative humidity. The activation enthalpies varied from 137.6 to 83.3 kJ/mol as a function of the relative humidity (50 and 80%, respectively). All these experiments showed that LDH regeneration is highly dependent on the temperature and relative humidity.

Thermochemical capture of carbon dioxide on lithium aluminates (LiAlO2 and Li5AlO4): a new option for the CO2 absorption.

Lithium aluminates (LiAlO(2) and Li(5)AlO(4)) were synthesized, characterized, and tested as possible CO(2) captors. LiAlO(2) did not seem to have good qualities for the CO(2) absorption. On the contrary, Li(5)AlO(4) showed excellent behavior as a possible CO(2) captor. Li(5)AlO(4) was thermally analyzed under a CO(2) flux dynamically and isothermically at different temperatures. These results clearly showed that Li(5)AlO(4) is able to absorb CO(2) in a wide temperature range (200-700 degrees C). Nevertheless, an important sintering effect was observed during the thermal treatment of the samples, which produced an atypical behavior during the CO(2) absorption at low temperatures. However, at high temperatures, once the lithium diffusion is activated, the sintering effect did not interfere with the CO(2) absorption. Eyring's model was used to determine the activation enthalpies of the CO(2) absorption (15.6 kJ/mol) and lithium diffusion (52.1 kJ/mol); the last one is the limiting process.

Structural analysis and CO2 chemisorption study on nonstoichiometric lithium cuprates (Li(2+x)CuO(2+x/2)).

Lithium cuprate (Li(2)CuO(2)) was prepared by solid state reaction, using different quantities of lithium excess, which produced nonstoichiometric ceramics, Li(2+x)CuO(2+x/2). These ceramics were characterized by X-ray diffraction, transmission and scanning electron microscopies, solid state nuclear magnetic resonance, and atomic absorption. The results obtained showed that lithium excess is located mainly into the Li(2)CuO(2) interlayers forming nanoparticles of a different phase, perhaps lithium oxide. Additionally, the lithium excess produced morphological changed at a micrometric and nanometric levels. As lithium excess increased, the particle size increased as well and it formed some kind of filament-like structures. It was explained in terms sintering, due to the high mobility of lithium atoms. On the other hand, all these ceramics were tested as CO(2) captors, presenting encouraging properties through a chemisorption process. As expected, the CO(2) absorption increased as a function of total lithium contained into the ceramics. Finally, it was performed a kinetic analysis of the CO(2) absorption.