Carbon Dioxide Adsorption over Activated Biocarbons Derived from Lemon Peel.

The rising concentration of CO2 in the atmosphere is approaching critical levels, posing a significant threat to life on Earth. Porous carbons derived from biobased materials, particularly waste byproducts, offer a viable solution for selective CO2 adsorption from large-scale industrial sources, potentially mitigating atmospheric CO2 emissions. In this study, we developed highly porous carbons from lemon peel waste through a two-step process, consisting of temperature pretreatment (500 °C) followed by chemical activation by KOH at 850 °C. The largest specific surface area (2821 m2/g), total pore volume (1.39 cm3/g), and micropore volume (0.70 cm3/g) were obtained at the highest KOH-to-carbon ratio of 4. In contrast, the sample activated with a KOH-to-carbon ratio of 2 demonstrated the greatest micropore distribution. This activated biocarbon exhibited superior CO2 adsorption capacity, reaching 5.69 mmol/g at 0 °C and 100 kPa. The remarkable adsorption performance can be attributed to the significant volume of micropores with diameters smaller than 0.859 nm. The Radke-Prausnitz equation, traditionally employed to model the adsorption equilibrium of organic compounds from liquid solutions, has been shown to be equally applicable for describing the gas-solid adsorption equilibrium. Furthermore, equations describing the temperature dependence of the Radke-Prausnitz equation's parameters have been developed.

Activated Carbon for CO2 Adsorption from Avocado Seeds Activated with NaOH: The Significance of the Production Method.

The rise in atmospheric greenhouse gases like CO2 is a primary driver of global warming. Human actions are the primary factor behind the surge in CO2 levels, contributing to two-thirds of the greenhouse effect over the past decade. This study focuses on the chemical activation of avocado seeds with sodium hydroxide (NaOH). The influence of various preparation methods was studied under the same parameters: carbon precursor to NaOH mass ratio, carbonization temperature, and nitrogen flow. For two samples, preliminary thermal treatment was applied (500 °C). NaOH was used in the form of a saturated solution as well as dry NaOH. The same temperature of 850 °C of carbonization combined with chemical activation was applied for all samples. The applied modifications resulted in the following textural parameters: specific surface area from 696 to 1217 m2/g, total pore volume from 0.440 to 0.761 cm3/g, micropore volume from 0.159 to 0.418 cm3/g. The textural parameters were estimated based on nitrogen sorption at -196 °C. The XRD measurements and SEM pictures were also performed. CO2 adsorption was performed at temperatures of 0, 10, 20, and 30 °C and pressure up to 1 bar. In order to calculate the CO2 selectivity over N2 nitrogen adsorption at 20 °C was investigated. The highest CO2 adsorption (4.90 mmol/g) at 1 bar and 0 °C was achieved.

Chemical Activation of Banana Peel Waste-Derived Biochar Using KOH and Urea for CO2 Capture.

This article describes the synthesis and characterization of porous carbon derived from waste banana peels by chemical activation with KOH or by activation KOH and urea modification. The as-synthesized samples were carefully characterized by various techniques. The prepared carbonaceous materials possess highly developed micropore and mesopore structures and high specific surface area (up to 2795 cm2/g for materials synthetized with KOH and 2718 cm2/g for activated carbons prepared with KOH and urea). A series of KOH-activated samples showed CO2 adsorption at 1 bar to 5.75 mmol/g at 0 °C and 3.74 mmol/g at 25 °C. The incorporation of nitrogen into the carbon sorbent structure increased the carbon uptake capacity of the resulting materials at 1 bar to 6.28 mmol/g and to 3.86 mmol/g at 0 °C and 25 °C, respectively. It was demonstrated that treatment with urea leads to a significant increase in nitrogen content and, consequently, CO2 adsorption, except for the material carbonized at 900 °C. At such a high temperature, almost complete decomposition of urea occurs. The results presented in this work could be used in the future for utilization of biomass such as banana peels as a low-cost adsorbent for CO2 capture, which could have a positive impact on the environment and human health protection.

Enzymatically catalyzed furan-based copolyesters containing dilinoleic diol as a building block.

A more environmentally friendly method for creating sustainable alternatives to traditional aromatic-aliphatic polyesters is a valuable step towards resource-efficiency optimization. A library of furan-based block copolymers was synthesized via temperature-varied two-step polycondensation reaction in diphenyl ether using Candida antarctica lipase B (CAL-B) as a biocatalyst where dimethyl 2,5-furandicarboxylate (DMFDCA), α,ω-aliphatic linear diols (α,ω-ALD), and bio-based dilinoleic diol (DLD) were used as the starting materials. Nuclear magnetic spectroscopy (1H and 13C NMR), Fourier transform spectroscopy (FTIR) and size exclusion chromatography (SEC) were used to analyze the resulting copolymers. Additionally, crystallization behavior and thermal properties were studied using X-ray diffraction (XRD), digital holographic microscopy (DHM), and differential scanning microscopy (DSC). Finally, oxygen transmission rates (OTR) and dynamic mechanical analysis (DMTA) of furan-based copolyesters indicated their potential for medical packaging.

Enhancement of CO2 adsorption on activated carbons produced from avocado seeds by combined solvothermal carbonization and thermal KOH activation.

A new strategy for ultramicroporous activated carbons production from avocado seeds was developed. Combined solvothermal carbonization and thermal KOH activation were conducted. Solvothermal carbonizations were performed in a stainless-steel autoclave lined with Teflon at the temperature of 180 °C for 12 h in three different liquids (water, methanol, isopropyl alcohol). Chars were activated by KOH. The carbonization combined with activation took place in the oven at 850 °C for 1 h. All the samples were very good CO2 sorbents. The highest CO2 adsorption at a pressure of 1 bar was achieved for activated carbon produced using isopropanol. The best carbon dioxide adsorption was equal to 6.47 mmol/g at 0 °C and 4.35 mmol/g at 20 °C.

Influence of Surface Roughness on the Properties of Nitrided Layer on 42CrMo4 Steel.

A crucial factor of a nitriding process of treated parts is surface roughness. Eight samples of 42CrMo4 steel were used to investigate the parameter represented by Ra. In the study, the innovative combined microhardness profiles were used to present results within the compound zone and diffusion layer. Therefore, two loads were applied in the compound zone, 5 gf, and diffusion layer, 500 gf. Observation with SEM and chemical analysis of the investigated samples showed a correlation between microstructure, nitrogen concentration and microhardness of the compound zone. XRD diffraction was used to identify the phase composition. Moreover, the X-ray photoelectron spectroscopy technique was also applied in the study. No distinct correlations between compound zone morphology and the Ra parameter were observed. The thickness value of the structure was constant and fluctuated around 20 µm in the vast majority of the examined cases. However, analysis of the results revealed a dependence between the Ra parameter and diffusion layer thickness. The values of this parameter varied in the range of 356-394 µm depending on the Ra parameter. A distinct nitrided layer was observed on the polished sample.

Investigation of CO2 Adsorption on Avocado Stone-Derived Activated Carbon Obtained through NaOH Treatment.

Activated carbons were prepared from avocado stone through NaOH activation and subsequent carbonization. The following textural parameters were achieved: specific surface area: 817-1172 m2/g, total pore volume: 0.538-0.691 cm3/g, micropore volume 0.259-0.375 cm3/g. The well-developed microporosity resulted in a good CO2 adsorption value of 5.9 mmol/g at a temperature of 0 °C and 1 bar and selectivity over nitrogen for flue gas simulation. The activated carbons were investigated using nitrogen sorption at -196 °C, CO2 sorption, X-ray diffraction, and SEM. It was found that the adsorption data were more in line with the Sips model. The isosteric heat of adsorption for the best sorbent was calculated. It was found that the isosteric heat of adsorption changed in the range of 25 to 40 kJ/mol depending on the surface coverage. The novelty of the work is the production of highly microporous activated carbons from avocado stones with high CO2 adsorption. Before now, the activation of avocado stones using NaOH had never been described.

W-SBA-15 as an Effective Catalyst for the Epoxidation of 1,5,9-Cyclododecatriene.

The results of a study on the epoxidation of 1,5,9-cyclododecatriene (CDT) on a W-SBA-15 catalyst using the batch and half-periodic methods are presented. During this study, the activity of the W-SBA-15 catalyst was compared to that of the Ti-SBA-15 catalyst, and the W-SBA-15 catalyst was found to be about 20 times more active than the Ti-SBA-15 catalyst. The highest CDT conversion so far, amounting to 86 mol%, was obtained after carrying out the 4 h epoxidation process. Conducting the studied process using the semi-batch method did not result in the significant improvement in value functions describing this process (CDT conversion and selectivity of CDT transformation to ECDD), but the fastest H2O2 dosing rate (246 µL/h) allowed us to obtain 9 mol% higher CDT conversion in comparison to the batch method.

Carbon Dioxide Adsorption over Activated Carbons Produced from Molasses Using H2SO4, H3PO4, HCl, NaOH, and KOH as Activating Agents.

Cost-effective activated carbons for CO2 adsorption were developed from molasses using H2SO4, H3PO4, HCl, NaOH, and KOH as activating agents. At the temperature of 0 °C and a pressure of 1 bar, CO2 adsorption equal to 5.18 mmol/g was achieved over activated carbon obtained by KOH activation. The excellent CO2 adsorption of M-KOH can be attributed to its high microporosity. However, activated carbon prepared using HCl showed quite high CO2 adsorption while having very low microporosity. The absence of acid species on the surface promotes CO2 adsorption over M-HCl. The pore size ranges that are important for CO2 adsorption at different temperatures were estimated. The higher the adsorption temperature, the more crucial smaller pores were. For 1 bar pressure and temperatures of 0, 10, 20, and 30 °C, the most important were pores equal and below: 0.733, 0.733, 0.679, and 0.536 nm, respectively.

Waste-based nanoarchitectonics with face masks as valuable starting material for high-performance supercapacitors.

Surgical face masks waste is a source of microplastics (polymer fibres) and inorganic and organic compounds potentially hazardous for aquatic organisms during degradation in water. The monthly use of face masks in the world is about 129 billion for 7.8 billion people. Therefore, in this contribution the utilization of hazardous surgical face masks waste for fabrication of carbon-based electrode materials via KOH-activation and carbonization was investigated. The micro-mesoporous materials were obtained with specific surface areas in the range of 460 - 969 m2/g and a total pore volume of 0.311 - 0.635 cm3/g. The optimal sample showed superior electrochemical performance as an electrode material in supercapacitor in the three-electrode system, attaining 651.1F/g at 0.1 Ag-1 and outstanding capacitance retention of 98 % after a test cycle involving 50'000 cycles. It should be emphasized that capacitance retention is one of the most crucial requirements for materials used as the electrodes in the supercapacitor devices. In this strategy, potentially contaminated face masks, common pandemic waste, is recycled into highly valuable carbon material which can serve in practical applications overcoming the global energy crisis. What is more, all microorganisms, including coronaviruses that may be on/in the masks, are completely inactivated during KOH-activation and carbonization.

Management of surgical mask waste to activated carbons for CO2 capture.

The worldwide COVID-19 pandemic has resulted in a huge amount of face masks being used up and thrown away, resulting in increased environmental pollution and infection risks. In our work, we have developed a highly efficient process of neutralizing face mask waste into a useful carbon material. Then, the prepared activated carbon was used for CO2 adsorption studies. A series of activated carbons from face masks used as a precursor were synthesized using KOH and the activation temperature was in the range of 600-800 °C. All materials were characterized by well-developed porosity. The influence of activation temperature on the textural properties of prepared activated carbons and their adsorption abilities were investigated. The highest CO2 adsorption was received for the M_800 carbon and it was 3.91 mmol/g at the temperature of 0 °C and the pressure of 1 bar. M_800 carbon exhibited also high selectivity of CO2 over N2. Seven equilibrium isotherms were applied to the experimental data to find out the best fit (Langmuir, Freundlich, Sips, Toth, Unilan, Fritz-Schlunder and Radke-Prausnitz isotherms). The presented research provides an environmentally friendly and cost-effective method of recycling waste masks into a valuable product in the form of carbon and its potential use in the absorption of harmful CO2 influencing the greenhouse effect.

Fabrication of Antibacterial Metal Surfaces Using Magnetron-Sputtering Method.

One-hundred-nanometer films consisting of silver, copper, and gold nanocrystallites were prepared, and their antibacterial properties were quantitatively measured. The magnetron-sputtering method was used for the preparation of the metallic films over the glass plate. Single- and double-layer films were manufactured. The films were thoroughly characterized with the XRD, SEM, EDS, and XPS methods. The antibacterial activity of the samples was investigated. Gram-negative Escherichia coli, strain K12 ATCC 25922 (E. coli), and Gram-positive Staphylococcus epidermidis, ATCC 49461 (S. epidermidis), were used in the microbial tests. The crystallite size was about 30 nm in the cases of silver and gold and a few nanometers in the case of copper. Significant oxidation of the copper films was proven. The antibacterial efficacy of the tested samples followed the order: Ag/Cu > Au/Cu > Cu. It was concluded that such metallic surfaces may be applied as contact-killing materials for a more effective fight against bacteria and viruses.

CO2 Adsorption on Activated Carbons Prepared from Molasses: A Comparison of Two and Three Parametric Models.

Activated carbons with different textural characteristic were derived by the chemical activation of raw beet molasses with solid KOH, while the activation temperature was changed in the range 650 °C to 800 °C. The adsorption of CO2 on activated carbons was investigated. Langmuir, Freundlich, Sips, Toth, Unilan, Fritz-Schlunder, Radke-Prausnitz, Temkin-Pyzhev, Dubinin-Radushkevich, and Jovanovich equations were selected to fit the experimental data of CO2 adsorption. An error analysis (the sum of the squares of errors, the hybrid fractional error function, the average relative error, the Marquardt's percent standard deviation, and the sum of the absolute errors) was conducted to examine the effect of using various error standards for the isotherm model parameter calculation. The best fit was observed to the Radke-Prausnitz model.

The Studies on α-Pinene Oxidation over the TS-1. The Influence of the Temperature, Reaction Time, Titanium and Catalyst Content.

The work presents the results of studies on α-pinene oxidation over the TS-1 catalysts with different Ti content (in wt%): TS-1_1 (9.92), TS-1_2 (5.42), TS-1_3 (3.39) and TS-1_4 (3.08). No solvent was used in the oxidation studies, and molecular oxygen was used as the oxidizing agent. The effect of titanium content in the TS-1 catalyst, temperature, reaction time and amount of the catalyst in the reaction mixture on the conversion of α-pinene and the selectivities of appropriate products was investigated. It was found that it is most advantageous to carry out the process of α-pinene oxidation in the presence of the TS-1 catalyst with the titanium content of 5.42 wt% (TS-1_2), at the temperature of 85 °C, for 6 h and with the catalyst TS-1 content in the reaction mixture of 1 wt%. Under these conditions the conversion of α-pinene amounted to 34 mol%, and the selectivities of main products of α-pinene oxidation process were: α-pinene oxide (29 mol%), verbenol (15 mol%) and verbenone (12 mol%). In smaller quantities also campholenic aldehyde, trans-pinocarveol, myrtenal, myrtenol, L-carveol, carvone and 1,2-pinanediol were also formed. These products are of great practical importance in food, cosmetics, perfumery and medicine industries. Kinetic studies were also performed for the studied process.

Activated Carbon Modification towards Efficient Catalyst for High Value-Added Products Synthesis from Alpha-Pinene.

DT0-activated carbons modified with HCl and HNO3 acids, which were used for the first time in the catalytic process of alpha-pinene isomerization, are presented in this study. The carbon materials DT0, DT0_HCl, DT0_HNO3, and DT0_HCl_HNO3 were examined with the following methods: XRF, SEM, EDX, XPS, FT-IR, XRD, and N2 adsorption at -196 °C. It was shown that DT0_HCl_HNO3-activated carbon was the most active material in the alpha-pinene isomerization process. Detailed studies of alpha-pinene isomerization were carried out over this carbon by changing the reaction parameters such as time (5-180 min) and temperature (60-175 °C). The 100% conversion of alpha-pinene was achieved at the temperature of 160 °C and catalyst content of 5 wt% after 3 h over the DT0_HCl_HNO3 catalyst. Camphene and limonene were the main products of the alpha-pinene isomerization reaction.

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.

Computer Analysis of the Effect of Activation Temperature on the Microporous Structure Development of Activated Carbon Derived from Common Polypody.

This paper presents the results of a computer analysis of the effect of activation process temperature on the development of the microporous structure of activated carbon derived from the leaves of common polypody (Polypodium vulgare) via chemical activation with phosphoric acid (H3PO4) at activation temperatures of 700, 800, and 900 °C. An unconventional approach to porous structure analysis, using the new numerical clustering-based adsorption analysis (LBET) method together with the implemented unique gas state equation, was used in this study. The LBET method is based on unique mathematical models that take into account, in addition to surface heterogeneity, the possibility of molecule clusters branching and the geometric and energy limitations of adsorbate cluster formation. It enabled us to determine a set of parameters comprehensively and reliably describing the porous structure of carbon material on the basis of the determined adsorption isotherm. Porous structure analyses using the LBET method were based on nitrogen (N2), carbon dioxide (CO2), and methane (CH4) adsorption isotherms determined for individual activated carbon. The analyses carried out showed the highest CO2 adsorption capacity for activated carbon obtained was at an activation temperature of 900 °C, a value only slightly higher than that obtained for activated carbon prepared at 700 °C, but the values of geometrical parameters determined for these activated carbons showed significant differences. The results of the analyses obtained with the LBET method were also compared with the results of iodine number analysis and the results obtained with the Brunauer-Emmett-Teller (BET), Dubinin-Radushkevich (DR), and quenched solid density functional theory (QSDFT) methods, demonstrating their complementarity.

Correction: MOF-5 derived carbon as material for CO2 adsorption.

[This corrects the article DOI: 10.1039/C9RA01786K.].

MOF-5 derived carbon as material for CO2 absorption.

In our study we prepared MOF-5 derived carbon to reveal the thermodynamics of CO2 absorption processes in great detail. Porous carbon material was prepared from a metal-organic framework (MOF-5) via carbonization at 1000 °C. The obtained structure consists only of carbon and exhibits a BET specific surface area, total pore volume and micropore volume of 1884 m2 g-1, 1.84 cm3 g-1 and 0.59 cm3 g-1, respectively. Structural analysis allowed the assumption that this material is an ideal candidate for efficient CO2 absorption. The CO2 uptake was 2.43 mmol g-1 at 25 °C and 1 bar. Additionally, the absorption over a wide range of temperatures (25, 40, 60, 80 and 100 °C) and pressures (in range of 0-40 bar) was investigated. It is shown that the CO2 absorption isotherm fits a multitemperature Sips model. The calculated Sips equation parameters allows the isosteric heat of adsorption to be obtained. The isosteric heat of adsorption for CO2 decreased substantially with an increase in surface coverage by gas molecules. This indicates a negligible intermolecular interaction between CO2 molecules. A decrease in the isosteric heat of adsorption with surface coverage is a result of the disappearance of favourable adsorption sites.

A Comparison of Hydrogen Storage in Pt, Pd and Pt/Pd Alloys Loaded Disordered Mesoporous Hollow Carbon Spheres.

Comprehensive study to evaluate the ability of hydrogen uptake by disordered mesoporous hollow carbon spheres doped witch metal such as Pt, Pd or Pt/Pd was conducted. They were synthesized facilely using sonication and then calcination process under vacuum at the temperature of 550 °C. The effect on hydrogen sorption at neat-ambient conditions (40 °C, up to 45 bar) was thoroughly analyzed. The results clearly revealed that metal functionalization has a significant impact on the hydrogen storage capacity as the mechanism of gas uptake depends on two factors: metal type and certain size of particles. Thus, functionalized spheres adsorb hydrogen by physisorption forming metal hydrides or metal hydrides combined with hydrogen spillover effect. As a result, a sample with narrower distribution of nanoparticles and smaller specific size exhibited enhanced hydrogen uptake.