Valorization of Olive Stone Biomass into Graphitic-Like Carbon for Cyclic and Selective CO 2 Adsorption Under Postcombustion Conditions

The effect of two atmospheric post-treatment conditions directly after the KOH activation of polyacrylonitrile-based nanofibres is studied in this work. As post-treatment different N2 : O2 flow conditions, namely high O2-flow and low O2-flow, are applied and their impact on occurring reactions and carbon nanofibres' properties is studied by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), Raman spectroscopy, elemental analysis and CO2 and Ar gas adsorption. At high O2-flow conditions a pyrophoric effect was observed on the KOH-activated carbon nanofibers. Based on the obtained results from the TGA and DSC the pyrophoric effect is attributed to the oxidation reactions of metallic potassium formed during the KOH activation process and a consequent carbon combustion reaction. Suppression of this pyrophoric effect is achieved using the low O2-flow conditions due to a lower heat formation of the potassium oxidation and the absence of carbon combustion. Compared to the high O2-flow samples no partial destruction of the carbon nanofibers is observed in the SEM images. The determination of the adsorption isotherms, the surface area, the pore size distribution and the isosteric enthalpies of adsorption show the superior properties under low O2-flow conditions. The present micropore volume is increased from 0.424 cm3 g-1 at high O2-flow to 0.806 cm3 g-1 for low O2-flow samples, resulting in an increase of CO2 adsorption capacity of 38% up to 6.6 mmol g-1 at 1 bar. This significant improvement clearly points out the importance of considering highly exothermic potassium oxidation reactions and possible post-treatment strategies when applying KOH activation to electrospun carbon nanofiber materials.

Comparisons of pore properties and adsorption performance of KOH-activated and steam-activated carbons

This study investigates the fabrication of granular activated carbon (AC) from biomass waste using three chemical activating agents: sodium carbonate (Na₂CO₃), potassium hydroxide (KOH), and zinc chloride (ZnCl₂), to evaluate their effects on structural, morphological, and electrical properties relevant to energy storage applications. An experimental laboratory-based method with a comparative activation approach was employed. The resulting activated carbon samples were characterized by X-ray diffraction (XRD), scanning electron microscopy coupled with energy-dispersive spectroscopy (SEM–EDS), and iodine adsorption and electrical measurements. XRD analysis revealed that all samples predominantly exhibit amorphous or turbostratic carbon structures with partial structural ordering, with ZnCl₂-activated samples showing higher short-range ordering than those activated with the other activators. SEM observations indicated qualitative differences in surface morphology and pore development, with more pronounced pores in the KOH-activated carbon. EDS analysis confirmed carbon-rich surfaces with minor residual inorganic elements originating from the activating agents and biomass precursor. Iodine adsorption results, used as a proxy indicator of microporosity, showed that the KOH-activated carbon exhibited the highest iodine number (630.70 mg/g). Electrical measurements, reported as apparent electrical conductivity under the applied packed-bed measurement conditions, also indicated the highest value for the KOH-activated sample (1724.10 S/m). Based on the parameters measured in this study, KOH activation produced the most favorable combined iodine adsorption and apparent electrical conductivity among the activation routes investigated. Therefore, KOH-activated biomass-derived carbon is identified as the most promising candidate for subsequent electrochemical validation toward supercapacitor electrode applications.

Comparisons of porous and adsorption properties of carbons activated by steam and KOH

Purpose – In this research, we have prepared activated carbon (AC) from the waste of banana peels (Musa acuminate L.) using potassium hydroxide (KOH) for carbon monoxide (CO) adsorption from motorcycle gas emission. Design/Methodology/Approach – The activation was conducted using a chemical activator (KOH) at various concentrations of 1, 2, and 3 N for 1, 2, and 3 h, respectively. Characteristics of banana peels AC (BPAC) produced were analyzed using the Fourier-transform infra-red spectroscopy and scanning electron microscopy. Findings – Results showed that KOH concentration and activation time strongly affected the CO adsorption and opening of the AC surface pore. There was an increase in the CO sorption when the KOH concentration was increased up to 3 N concentration. The highest CO adsorption from the emission occurred at 70.95% under KOH concentration of 3 N during the 3-h preparation. Research Limitations/Implications – BPAC has been used as an adsorbent for only CO from motorcycle gas emission but not as an adsorbent for HC, NO, NOx, or H2S. Practical Implications – BPAC can be used as the potential adsorbent for the removal of CO from motorcycle gas emission, and it is an environmental friendly, low cost, and easy to make adsorbent. Originality/Value – In this study, the AC is made from biomass and is used in wastewater treatment, but limited studies are found on the removal of CO from motorcycle gas emission.

Preparation of highly microporous carbons from fir wood by KOH activation for adsorption of dyes and phenols from water

Preparation of porous diatomite-templated carbons with large adsorption capacity and mesoporous zeolite K-H as a byproduct

Evaluating the performance of carbon-based adsorbents fabricated from renewable biomass precursors for post-combustion CO2 capture

Toward sustainable hydrogen storage and carbon dioxide capture in post-combustion conditions

The development of new materials with high adsorption capacity and selectivity is becoming attractive for the applications of clean energy and environment pollution control. Metal-organic frameworks (MOFs) are promising adsorbents for gas storage and separation, such as H2 and CH4 storage, and CO2 capture, due to their extraordinarily high porosity, adjustable pore sizes, controllable surface functionality and potential scalability for industrial applications. This thesis focuses on developing novel MOFs for selective gas adsorption with large adsorption capacities and high selectivity, as well as good thermal and chemical stability. The studies include optimizing the activation conditions for uniform and empty pores with MOFs Cu-BTC taken as a case study, designing novel MOFs structure with desired functional groups for high selectivity of CO2 over other gases, fabricating MOFs contained composites with desired electrostatic force with ZIF-8/CNTs as an example, and evaluating the selective gas adsorption performance of all the prepared materials. This thesis aims to establish the relationship between the structure features of MOFs (pore size, metal centres, surface functional groups and electrostatic force) and gas adsorption performance of MOFs (including adsorption capacity and selectivity). The first part of experimental chapters focuses on the preparation and activation of copper-based MOFs Cu-BTC. The materials were synthesized by solvothermal method and activated by six different solvents (chloroform, dichloromethane, acetone, ethanol, methanol and water) in the activation process. The effects of different activation solvents on the thermal stability, porous structure and CO2 adsorption of Cu-BTC were investigated. The more DMF molecules were evacuated from the pores of Cu-BTC, the better adsorption performance was reflected in the material. The high crystalline and nearly solvent-free frameworks with highest BET surface area (2042 m2/g), largest pore volume (0.823 cm3/g) as well as highest CO2 loading (11.60 mmol/g at 0 dC and 132 kPa) can be achieved while using methanol as activation solvent. Then the selective adsorption of CO2/N2 and CO2/CH4 on Cu-BTC were examined through the experimental measurement of equilibrium adsorption capacities from pure fluids (CO2, CH4 and N2) and mixtures of CO2/N2 and CO2/CH4. Grand Canonical Monte Carlo (GCMC) model was performed to predict the adsorption capacities from pure fluids and binary mixtures. The GCMC model gives reasonable predictions of the measured adsorption capacities for pure gases at low pressures (l5 bar), but significantly over predicts that at pressures greater than 5 bar. The GCMC model fails to provide a satisfactory fit of the binary adsorption measurements across the entire pressure range studied. The Ideal Adsorbed Solution Theory (IAST) model using best-fit parameters for Langmuir isotherms of each pure fluid provides more satisfactory predictions of CO2/N2 and CO2/CH4 than the GCMC model. This combined experimental and modelling approach can provide criteria to screen MOFs for the separation of gas mixtures at industrially relevant compositions, temperatures and pressures. The second part of experimental chapters mainly focuses on synthesising MOFs with enhanced affinity for CO2 and selectivity of CO2 over other gases. Three novel amino-functionalized MOFs with both open metal sites (OMSs) and Levis basic sites (LBSs) were synthesized by solvothermal reactions. Single crystal structure analysis showed that Mg-ABDC and Co-ABDC were isostructural comprising two-dimensional layer structures, while Sr-ABDC contained a three-dimensional motif. These amino-functionalized MOFs were further characterized by powder X-ray diffraction, thermal gravimetric analysis and N2 ads-desorption. Adsorption isotherms of CO2 and N2 were obtained at various temperatures (0, 25 and 35 dC) and then the adsorption capacity and CO2/N2 selectivity for these MOFs were compared. Based on results, both Mg-ABDC and Co-ABDC decorated by the -NH2 groups and the open metal sites exhibit high heat of CO2 adsorption (g 30 kJ/mol) and excellent adsorption selectivity of CO2 over N2 (g375). In contrast, Sr-ABDC displays poor adsorption properties due to small pore size, low surface area and small pore volume. Introducing desired electrostatic force into MOF structures by the incorporation of carbon nanotubes (CNTs) into MOFs can obtain better crystals and enhance the properties of composite. A series of ZIF-8/CNTs composites were successfully synthesized by solvothermal method. The contents of ZIF-8 and CNTs in the composites were calculated from Thermogravimetric Analysis data. CO2 and N2 adsorption at 273 K on the composites were also investigated and compared. Results show that there are interactions (synergetic effect) between ZIF-8 crystals and CNTs in the composites, reflected in the change of crystallinity, morphology, thermal stability, and adsorption properties. The surface area and adsorption capacities of ZIF-8/CNTs composites can be controlled by adjusting the CNTs content in the composites. In optimal CNTs loading ratio, the ZIF-8/CNTs composite showed improved adsorption capacities and selectivity of CO2/N2, illustrating that the incorporation of CNTs into MOFs synthesis is a promising approach to enhance the adsorption performance of MOFs.

Effects of oxygen-containing surface functionalities on the adsorption of mixtures including CO(2)/CH(4), CO(2)/N(2), and CO(2)/H(2)O have been investigated in the current work. Together with Bader charge analysis, electronic structure calculations have provided the initial framework comprising both the geometry and corresponding charge information required to carry out statistical-based molecular simulations. The adsorption isotherms and selectivity of CO(2) from CO(2)/N(2), CO(2)/CH(4), and CO(2)/H(2)O gas mixtures were determined by grand canonical Monte Carlo simulations at temperature/pressure conditions relevant to carbon capture and sequestration applications. The interactions between the surfaces with induced polarity and nonpolar/polar molecules have been investigated. It has been observed that, due to the induced polarity of the surface functionalization, the selectivity of CO(2) over CH(4) increases from approximately 2 to higher than 5, and the selectivity of CO(2) over N(2) increases from approximately 5 to 20, especially in the low-pressure regime. However, water vapor will always preferentially adsorb over CO(2) in carbon-based systems containing oxygen functionalized surfaces at conditions relevant to carbon capture application. Molecular simulation results indicate that the surface chemistry in micropores is tunable thereby influencing the selectivity for enhanced uptake of CO(2).

This paper demonstrates that nanospace engineering of KOH activated carbon is possible by controlling the degree of carbon consumption and metallic potassium intercalation into the carbon lattice during the activation process. High specific surface areas, porosities, sub-nanometer (<1 nm) and supra-nanometer (1–5 nm) pore volumes are quantitatively controlled by a combination of KOH concentration and activation temperature. The process typically leads to a bimodal pore size distribution, with a large, approximately constant number of sub-nanometer pores and a variable number of supra-nanometer pores. We show how to control the number of supra-nanometer pores in a manner not achieved previously by chemical activation. The chemical mechanism underlying this control is studied by following the evolution of elemental composition, specific surface area, porosity, and pore size distribution during KOH activation and preceding H3PO4 activation. The oxygen, nitrogen, and hydrogen contents decrease during successive activation steps, creating a nanoporous carbon network with a porosity and surface area controllable for various applications, including gas storage. The formation of tunable sub-nanometer and supra-nanometer pores is validated by sub-critical nitrogen adsorption. Surface functional groups of KOH activated carbon are studied by microscopic infrared spectroscopy.

Graphitic carbons with reasonable pore volume and appropriate graphitization degree can provide efficient Li + /electrolyte‐transfer channels and ameliorate the sluggish dynamic behavior of battery‐type carbon negative electrode in lithium‐ion capacitors (LICs). In this work, onion‐like graphitic carbon materials are obtained by using carbon quantum dots as precursors after sintering, and the effects of alkali metal salts on the structure, morphology and performance of the samples are focused. The results show that alkali metal salts as activator can etch graphitic carbons, and the specific surface area and pore size distribution are intimately related to the description of the alkali metal salt. Moreover, it also affects the graphitization degree of the materials. The porous graphitic carbons (S‐GCs) obtained by NaCl activation exhibit high specific surface area (77.14 m 2 ·g −1 ) and appropriate graphitization degree. It is expectable that the electrochemical performance for lithium‐ions storage can be largely promoted by the smart combination of catalytic graphitization and pores‐creating strategy. High‐performance LICs (S‐GCs//AC LICs) are achieved with high energy density of 92 Wh·kg −1 and superior rate capability (66.3 Wh·kg −1 at 10 A·g −1 ) together with the power density as high as 10020.2 W·kg −1 .

Adsorption of indole on KOH-activated mesoporous carbon

This work analyses the comparative effects of period-four transition metal (TM) dopants for CO molecular adsorption on the monolayer Graphene (Gr) supercell using the density functional theory (DFT) based ab initio method for the first time. Ten different TM dopant species (Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cr, Zn) have been incorporated and extensively studied in the context of Carbon Monoxide (CO) adsorption. The study elaborates on the effects of metallic doping in Gr on structural stability, electronic properties, adsorption strength, transduction efficacy, and CO recovery time. The study reveals that introducing each period-four TM dopant in the Gr lattice changes the semi-metallic nature, wherein distinct modulations in the energy band structure and the total density of state profiles can be observed after CO adsorption in each doped Gr matrix. The C atom of the polar CO molecule preferentially adsorbed on the doped TM, forming physical C-X (X: metal) bonds and resulting in slight vertical displacement of the dopant towards adsorbed CO. The results exhibit that depending on the strength of CO adsorption, the metallic dopants can be placed in the following order: Ti > V > Cr > Mn > Fe > Co > Ni > Cu > Zn > Sc, with a significant improvement in charge transfer during CO adsorption after Sc, Co, Ni, V, and Zn doping in Gr. Specifically, the Ni, Zn, and Sc-doped Gr ensures an efficient trade-off between adsorption stability and recovery time with high selectivity in CO2 and N2 environments.