Iron-Carbon Nanospheres as Promising Material for Magnetic Assisted Adsorption and Separation of Impurities from a Liquid Phase.

The composites containing various iron compounds and highly microporous carbon spheres were produced and investigated for structural and magnetic properties. Iron citrate, nitrate and chloride were used to prepare samples and the obtained products contained iron, iron carbide or magnetite. All the produced samples were characterized by high porosity and good magnetic properties. The coupling of the high porosity of carbon spheres with magnetic properties of iron compounds provides a potential application of the composites to removal of impurities from water, followed by a magnetic separation of the sorbent.

On the Selectivity of Simultaneous CO2 and N2 Reduction Using TiO2/Carbon Sphere Photocatalysts Prepared by Microwave Treatment and Mounted on Silica Cloth.

This paper presents new photocatalysts obtained by treating carbon spheres (CS) and TiO2 in a microwave reactor at a pressure of 20 atm and a temperature of up to 300 °C for 15 min and then depositing TiO2/CS composites on glass fibre cloths. Such highly CO2-adsorbing photocatalysts showed photoactivity in the simultaneous water-splitting process, generating H2, reducing CO2 to CO and CH4, and reducing N2 to NH3. In addition, calculations of the hydrogen balance involved in all reactions were performed. Adding 1 g of carbon spheres per 1 g of TiO2 maintained the high selectivity of nitrogen fixation at 95.87-99.5%, which was continuously removed from the gas phase into the water as NH4+ ions.

DFT Calculation of Carbon-Doped TiO2 Nanocomposites.

Titanium dioxide (TiO2) has been proven to be an excellent material for mitigating the continuous impact of elevated carbon dioxide concentrations. Carbon doping has emerged as a promising strategy to enhance the CO2 reduction performance of TiO2. In this study, we investigated the effects of carbon doping on TiO2 using density functional theory (DFT) calculations. Two carbon doping concentrations were considered (4% and 6%), denoted as TiO2-2C and TiO2-3C, respectively. The results showed that after carbon doping, the band gaps of TiO2-2C and TiO2-3C were reduced to 1.58 eV and 1.47 eV, respectively, which is lower than the band gap of pure TiO2 (2.13 eV). This indicates an effective improvement in the electronic structure of TiO2. Barrier energy calculations revealed that compared to pure TiO2 (0.65 eV), TiO2-2C (0.54 eV) and TiO2-3C (0.59 eV) exhibited lower energy barriers, facilitating the transition to *COOH intermediates. These findings provide valuable insights into the electronic structure changes induced by carbon doping in TiO2, which can contribute to the development of sustainable energy and environmental conservation measures to address global climate challenges.

Influence of Potassium-Based Activation on Adsorptive Properties of Carbon Spheres Modified with Iron(III) Citrate.

Composites synthesized from iron(III) citrate and carbon spheres, and activated with potassium compounds were prepared and then characterized using XRD, SEM, and low-temperature nitrogen adsorption methods. The adsorption properties of the composites toward carbon dioxide were assessed using CO2 uptake measurement, as well as by measuring their selectivity toward carbon dioxide, given their further application as photocatalysts for the reduction of this gas. The effect of changing preparation conditions on the structural and adsorption properties of the material was assessed. The potential strength of such material is a synergistic effect between the high adsorption capacity related to the microporosity of carbon spheres combined with the catalytic properties of iron particles.

CO2 Sorbents Based on Spherical Carbon and Photoactive Metal Oxides: Insight into Adsorption Capacity, Selectivity and Regenerability.

This work aimed to obtain hybrid composites based on photoactive metal oxide and carbon having adsorption properties. The materials, composed of titanium dioxide or zinc oxide and spherical carbon, were obtained from resorcinol-formaldehyde resin, treated in a solvothermal reactor heated with microwaves and then subjected to carbonization, were received. The functional groups of pure carbon spheres (unsaturated stretching C=C, stretching C-OH and C-H bending vibrations), CS/ZnO and CS/TiO2 samples were determined by FT-IR analysis. The characteristic bands for ZnO and TiO2 were observed below 1000 cm-1. The thermal oxidative properties are similar for TiO2- and ZnO-modified carbon spheres. We have observed that the increased carbon sphere content in nanocomposites results in starting the decomposition process at a lower temperature, therefore, nanocomposites have a broader combustion temperature range. The effect of the oxides' addition to carbon spheres on their adsorption properties was evaluated in detail by examining CO2 adsorption from the gas phase. The selectivity of CO2 over N2 at a temperature of 25 °C and pressure of 1 bar (a novelty in testing CS-based sorbents) calculated for 3.00 CS/TiO2 and 4.00 CS/ZnO was 15.09 and 16.95, respectively. These nanocomposites exhibit excellent cyclic stability checked over 10 consecutive adsorption-desorption cycles.

CO2 Adsorption Study of Potassium-Based Activation of Carbon Spheres.

The adsorption properties of microporous spherical carbon materials obtained from the resorcinol-formaldehyde resin, treated in a solvothermal reactor heated with microwaves and then subjected to carbonization, are presented. The potassium-based activation of carbon spheres was carried out in two ways: solution-based and solid-based methods. The effect of various factors, such as chemical agent selection, chemical activating agent content, and the temperature or time of activation, was investigated. The influence of microwave treatment on the adsorption properties was also investigated and described. The adsorption performance of carbon spheres was evaluated in detail by examining CO2 adsorption from the gas phase.

New Insight on Carbon Dioxide-Mediated Hydrogen Production.

A new approach to hydrogen production from water is described. This simple method is based on carbon dioxide-mediated water decomposition under UV radiation. The water contained dissolved sodium hydroxide, and the solution was saturated with gaseous carbon dioxide. During saturation, the pH decreased from about 11.5 to 7-8. The formed bicarbonate and carbonate ions acted as scavengers for hydroxyl radicals, preventing the recombination of hydroxyl and hydrogen radicals and prioritizing hydrogen gas formation. In the presented method, not yet reported in the literature, hydrogen production is combined with carbon dioxide. For the best system with alkaline water (0.2 m NaOH) saturated with CO2 under UV-C, the hydrogen production amounted to 0.6 µmol h-1 during 24 h of radiation.

Magnetic Resonance Studies of Hybrid Nanocomposites Containing Nanocrystalline TiO2 and Graphene-Related Materials.

Nanocomposites based on nanocrystalline titania modified with graphene-related materials (reduced and oxidized form of graphene) showed the existence of magnetic agglomerates. All parameters of magnetic resonance spectra strongly depended on the materials' modification processes. The reduction of graphene oxide significantly increased the number of magnetic moments, which caused crucial changes in the reorientation and relaxation processes. At room temperature, a wide resonance line dominated for all nanocomposites studied and in some cases, a narrow resonance line derived from the conduction electrons. Some nanocomposites (samples of titania modified with graphene oxide, prepared with the addition of water or butan-1-ol) showed a single domain magnetic (ferromagnetic) arrangement, and others (samples of titania modified with reduced graphene oxide) exhibited magnetic anisotropy. In addition, the spectra of EPR from free radicals were observed for all samples at the temperature of 4 K. The magnetic resonance imaging methods enable the capturing of even a small number of localized magnetic moments, which significantly affects the physicochemical properties of the materials.

The Effect of the Modification of Carbon Spheres with ZnCl2 on the Adsorption Properties towards CO2.

Zinc chloride and potassium oxalate are often applied as activating agents for carbon materials. In this work, we present the preparation of ZnO/carbon spheres composites using resorcinol-formaldehyde resin as a carbon source in a solvothermal reactor heated with microwaves. Zinc chloride as a zinc oxide source and potassium oxalate as an activating agent were applied. The effect of their addition and preparation conditions on the adsorption properties towards carbon dioxide at 0 °C and 25 °C were investigated. Additionally, for all tested sorbents, the CO2 sorption tests at 40 °C, carried out utilizing a thermobalance, confirmed the trend of sorption capacity measured at 0 and 25 °C. Furthermore, the sample activated using potassium oxalate and modified using zinc chloride (a carbon-to-zinc ratio equal to 10:1) displayed not only a high CO2 adsorption capacity (2.69 mmol CO2/g at 40 °C) but also exhibited a stable performance during the consecutive multicycle adsorption-desorption process.

Changes in Porous Parameters of the Ion Exchanged X Zeolite and Their Effect on CO2 Adsorption.

Zeolite 13X (NaX) was modified through ion-exchange with alkali and alkaline earth metal cations. The degree of ion exchange was thoroughly characterized with ICP, EDS and XRF methods. The new method of EDS data evaluation for zeolites was presented. It delivers the same reliable results as more complicated, expensive, time consuming and hazardous ICP approach. The highest adsorption capacities at 273 K and 0.95 bar were achieved for materials containing the alkali metals in the following order K < Na < Li, respectively, 4.54, 5.55 and 5.94 mmol/g. It was found that it is associated with the porous parameters of the ion-exchanged samples. The Li0.61Na0.39X form of zeolite exhibited the highest specific surface area of 624 m2/g and micropore volume of 0.35 cm3/g compared to sodium form 569 m2/g and 0.30 cm3/g, respectively. The increase of CO2 uptake is not related with deterioration of CO2 selectivity. At room temperature, the CO2 vs. N2 selectivity remains at a very high stable level prior and after ion exchange in co-adsorption process (XCO2 during adsorption 0.15; XCO2 during desorption 0.95) within measurement uncertainty. Additionally, the Li0.61Na0.39X sample was proven to be stable in the aging adsorption-desorption tests (200 sorption-desorption cycles; circa 11 days of continuous process) exhibiting the CO2 uptake decrease of about 6%. The exchange with alkaline earth metals (Mg, Ca) led to a significant decrease of SSA and micropore volume which correlated with lower CO2 adsorption capacities. Interestingly, the divalent cations cause formation of mesopores, due to the relaxation of lattice strains.

ZnO/Carbon Spheres with Excellent Regenerability for Post-Combustion CO2 Capture.

This paper examines the synthesis of the ZnO/carbon spheres composites using resorcinol-formaldehyde resin as a carbon source and zinc nitrate as a zinc oxide source in a solvothermal reactor heated with microwaves. The influence of activation with potassium oxalate and modification with zinc nitrate on the physicochemical properties of the obtained materials and CO2 adsorption capacity was investigated. It was found that in the case of nonactivated material as well as activated materials, the presence of zinc oxide in the carbon matrix had no effect or slightly increased the values of CO2 adsorption capacity. Only for the material where the weight ratio of carbon:zinc was 2:1, the decrease of CO2 adsorption capacity was reported. Additionally, CO2 adsorption experiments on nonactivated carbon spheres and those activated with potassium oxalate with different amounts of zinc nitrate were carried out at 40 °C using thermobalance. The highest CO2 adsorption capacity at temperature 40 °C (2.08 mmol/g adsorbent) was achieved for the material after activation with potassium oxalate with the highest zinc nitrate content as ZnO precursor. Moreover, repeated adsorption/desorption cycle experiments revealed that the as-prepared carbon spheres were very good CO2 adsorbents, exhibiting excellent cyclic stability with a performance decay of less than 10% over up to 25 adsorption-desorption cycles.

Pressureless and Low-Pressure Synthesis of Microporous Carbon Spheres Applied to CO2 Adsorption.

In this work, low-pressure synthesis of carbon spheres from resorcinol and formaldehyde using an autoclave is presented. The influence of reaction time and process temperature as well as the effect of potassium oxalate, an activator, on the morphology and CO2 adsorption properties was studied. The properties of materials produced at pressureless (atmospheric) conditions were compared with those synthesized under higher pressures. The results of this work show that enhanced pressure treatment is not necessary to produce high-quality carbon spheres, and the morphology and porosity of the spheres produced without an activation step at pressureless conditions are not significantly different from those obtained at higher pressures. In addition, CO2 uptake was not affected by elevated pressure synthesis. It was also demonstrated that addition of the activator (potassium oxalate) had much more effect on key properties than the applied pressure treatment. The use of potassium oxalate as an activator caused non-uniform size distribution of spherical particles. Simultaneously higher values of surface area and total pore volumes were reached. A pressure treatment of the carbon materials in the autoclave significantly enhanced the CO2 uptake at 25 °C, but had no effect on it at 0 °C.

Nanocomposite Titania-Carbon Spheres as CO2 and CH4 Sorbents.

Photocatalysis can offer solutions for the transformation of greenhouse gases, such as methane and carbon dioxide. In the paper, a candidate for such a photocatalyst is presented, based on a composite of titania with carbon spheres. The material was obtained using microwave assisted solvothermal synthesis, enabling good dispersion of titania. The studies of carbon dioxide and methane adsorption were performed under ambient pressure and temperatures of 40, 60, and 80 °C. The effect of temperature increase was less favorable for carbon dioxide than for methane. Satisfying values of carbon dioxide and methane uptake were obtained-3.94 mmol CO2/g and 2.77 mmol CH4/g at 40 °C.

Equilibrium and kinetic studies on acid dye Acid Red 88 adsorption by magnetic ZnFe2O4 spinel ferrite nanoparticles.

A magnetic ZnFe2O4 (MNZnFe) was synthesized by microwave assisted hydrothermal method and was used as an adsorbent for the removal of acid dye Acid Red 88 (AR88) from aqueous solution. The effects of various parameters such as initial AR88 concentration (10-56 mg L(-1)), pH solution (3.2-10.7), and temperature (20-60°C) were investigated. Prepared magnetic ZnFe2O4 was characterized by XRD, SEM, HRTEM, ICP-AES, BET, FTIR, and measurements of the magnetic susceptibility. The experimental data were analyzed by the Langmuir and Freundlich models of adsorption. Equilibrium data fitted well with the Langmuir model. Pseudo-first-order and pseudo-second-order kinetic models and intraparticle diffusion model were used to examine the adsorption kinetic data. The adsorption kinetics was found to follow the pseudo-second-order kinetic model. Thermodynamics parameters, ΔG°, ΔH° and ΔS°, indicate that the adsorption of AR88 onto MNZnFe was spontaneous and exothermic in nature.

Cobalt-based Catalysts for Ammonia Decomposition.

An effect of promoters such as calcium, aluminium, and potassium oxides and also addition of chromium and manganese on the structure of cobalt catalysts was examined. Studies of the catalytic ammonia decomposition over the cobalt catalysts are presented. The studies of the ammonia decomposition were carried out for various ammonia-hydrogen mixtures in which ammonia concentration varied in the range from 10% to 100%. Co(0) catalyst, promoted by oxides of aluminium, calcium, and potassium, showed the highest activity in the ammonia decomposition reaction. Contrary to expectations, it was found that chromium and manganese addition into the catalysts decreased their activity.