Experimental strategy for the preparation of adsorbent materials from torrefied palm kernel shell oriented to CO2 capture.

In this study, an experimental strategy to obtain biochar and activated carbon from torrefied palm kernel shell as an efficient material for CO2 removal was evaluated. Biochar was obtained by slow pyrolysis of palm kernel shell at different temperatures (350 °C, 550 °C, and 700 °C) and previously torrefied palm kernel shell at different temperatures (220 °C, 250 °C, and 280 °C). Subsequently, activated carbons were prepared by physical activation with CO2 from previously obtained biochar samples. The CO2 adsorption capacity was measured using TGA. The experimental results showed that there is a correlation between the change in the O/C and H/C ratios and the functional groups -OH and C=O observed via FTIR in the obtained char, indicating that both dehydration and deoxygenation reactions occur during torrefaction; this favors the deoxygenation reactions and makes them faster through CO2 liberation during the pyrolysis process. The microporous surface area shows a significant increase with higher pyrolysis temperatures, as a product of the continuous carbonization reactions, allowing more active sites for CO2 removal. Pyrolysis temperature is a key factor in CO2 adsorption capacity, leading to a CO2 adsorption capacity of up to 75 mg/gCO2 for biochar obtained at 700 °C from non-torrefied palm kernel shell (Char700). Activated carbon obtained from torrefied palm kernel shell at 280 °C (T280-CHAR700-AC) exhibited the highest CO2 adsorption capacity (101.9 mg/gCO2). Oxygen-containing functional groups have a direct impact on CO2 adsorption performance due to electron interactions between CO2 and these functional groups. These findings could provide a new experimental approach for obtaining optimal adsorbent materials exclusively derived from thermochemical conversion processes.

CO2 adsorption on carbonaceous materials obtained from forestry and urban waste materials: a comparative study.

The increasing emissions of gaseous pollutants of anthropogenic origin, such as carbon dioxide (CO2), which causes global warming, have raised great interest in developing and improving processes that allow their mitigation. Among them, adsorption on porous materials has been proposed as a sustainable alternative. This work presents a study of CO2 equilibrium adsorption at low temperatures (0, 10, and 20 °C) over a wide range of low pressures, on activated carbon derived from Eucalyptus (ES) and Patula pine (PP) forest waste, and carbonaceous material derived from waste tires (WT). The precursors of these materials were previously prepared, and their physicochemical properties were characterized. ES and PP were thermochemically treated with phosphoric acid, and WT was oxidized with nitric acid. Additionally, these materials were used to obtain monoliths using uniaxial compaction techniques and different binding agents, with better results obtained with montmorillonite. A total of six adsorbent solids had their textural and chemical properties characterized and were tested for CO2 adsorption. The highest specific surface area (1405 m2 g-1), and micropore properties were found for activated carbon derived from Eucalyptus whose highest adsorption capacity ranged from 2.27 mmol g-1 (at 0 °C and 100 kPa) to 1.60 mmol g-1 (at 20 °C and 100 kPa). The activated carbon monoliths presented the lowest CO2 adsorption capacities; however, the studied materials showed high potential for CO2 capture and storage applications at high pressures. The isosteric heats of adsorption were also estimated for all the materials and ranged from 16 to 45 kJ mol-1 at very low coverage explained by the energetic heterogeneity and weak repulsive interactions among adsorbed CO2 molecules.

Microwave-Assisted Synthesis of Zeolite A from Metakaolinite for CO2 Adsorption.

The global demand for energy and industrial growth has generated an exponential use of fossil fuels in recent years. It is well known that carbon dioxide (CO2) is mainly produced, but not only from fuels, which has a negative impact on the environment, such as the increasing emission of greenhouse gases. Thus, thinking about reducing this problem, this study analyzes microwave irradiation as an alternative to conventional heating to optimize zeolite A synthesis conditions for CO2 capture. Synthesis reaction parameters such as different temperatures (60-150 °C) and different time durations (1-6 h) were evaluated. The CO2 adsorption capacity was evaluated by CO2 adsorption-desorption isotherms at 25 °C and atmospheric pressure. The results showed that the synthesis of zeolite A by microwave irradiation was successfully obtained from natural kaolinite (via metakaolinization), reducing both temperature and time. Adsorption isotherms show that the most promising adsorbent for CO2 capture is a zeolite synthesized at 100 °C for 4 h, which reached an adsorption capacity of 2.2 mmol/g.

Modeling Adsorption of CO2 in Rutile Metallic Oxide Surfaces: Implications in CO2 Catalysis.

CO2 is the most abundant greenhouse gas, and for this reason, it is the main target for finding solutions to climatic change. A strategy of environmental remediation is the transformation of CO2 to an aggregated value product to generate a carbon-neutral cycle. CO2 reduction is a great challenge because of the large C=O dissociation energy, ~179 kcal/mol. Heterogeneous photocatalysis is a strategy to address this issue, where the adsorption process is the fundamental step. The focus of this work is the role of adsorption in CO2 reduction by means of modeling the CO2 adsorption in rutile metallic oxides (TiO2, GeO2, SnO2, IrO2 and PbO2) using Density Functional Theory (DFT) and periodic DFT methods. The comparison of adsorption on different metal oxides forming the same type of crystal structure allowed us to observe the influence of the metal in the adsorption process. In the same way, we performed a comparison of the adsorption capability between two different surface planes, (001) and (110). Two CO2 configurations were observed, linear and folded: the folded conformations were observed in TiO2, GeO2 and SnO2, while the linear conformations were present in IrO2 and PbO2. The largest adsorption efficiency was displayed by the (001) surface planes. The CO2 linear and folded configurations were related to the interaction of the oxygen on the metallic surface with the adsorbate carbon, and the linear conformations were associated with the physisorption and folded configurations with chemisorption. TiO2 was the material with the best performance for CO2 interactions during the adsorption.

Valorization of Different Fractions from Butiá Pomace by Pyrolysis: H2 Generation and Use of the Biochars for CO2 Capture.

This work valorizes butiá pomace (Butia capitata) using pyrolysis to prepare CO2 adsorbents. Different fractions of the pomace, like fibers, endocarps, almonds, and deoiled almonds, were characterized and later pyrolyzed at 700 °C. Gas, bio-oil, and biochar fractions were collected and characterized. The results revealed that biochar, bio-oil, and gas yields depended on the type of pomace fraction (fibers, endocarps, almonds, and deoiled almonds). The higher biochar yield was obtained by endocarps (31.9%wt.). Furthermore, the gas fraction generated at 700 °C presented an H2 content higher than 80%vol regardless of the butiá fraction used as raw material. The biochars presented specific surface areas reaching 220.4 m2 g-1. Additionally, the endocarp-derived biochar presented a CO2 adsorption capacity of 66.43 mg g-1 at 25 °C and 1 bar, showing that this material could be an effective adsorbent to capture this greenhouse gas. Moreover, this capacity was maintained for 5 cycles. Biochars produced from butiá precursors without activation resulted in a higher surface area and better performance than some activated carbons reported in the literature. The results highlighted that pyrolysis could provide a green solution for butiá agro-industrial wastes, generating H2 and an adsorbent for CO2.

CO2 Adsorption over 3d Transition-Metal Nanoclusters Supported on Pyridinic N3-Doped Graphene: A DFT Investigation.

CO2 adsorption on bare 3d transition-metal nanoclusters and 3d transition-metal nanoclusters supported on pyridinic N3-doped graphene (PNG) was investigated by employing the density functional theory. First, the interaction of Co13 and Cu13 with PNG was analyzed by spin densities, interaction energies, charge transfers, and HUMO-LUMO gaps. According to the interaction energies, the Co13 nanocluster was adsorbed more efficiently than Cu13 on the PNG. The charge transfer indicated that the Co13 nanocluster donated more charges to the PNG nanoflake than the Cu13 nanocluster. The HUMO-LUMO gap calculations showed that the PNG improved the chemical reactivity of both Co13 and Cu13 nanoclusters. When the CO2 was adsorbed on the bare 3d transition-metal nanoclusters and 3d transition-metal nanoclusters supported on the PNG, it experienced a bond elongation and angle bending in both systems. In addition, the charge transfer from the nanoclusters to the CO2 molecule was observed. This study proved that Co13/PNG and Cu13/PNG composites are adequate candidates for CO2 adsorption and activation.

Strategies for Improving the CO2 Adsorption Process of CPO-27-Mg through Thermal Treatment and Urea Functionalization.

In this work, the influence of degassing temperature and urea functionalization were investigated as ways to improve the CO2 adsorption performance of CPO-27-Mg. Through post-synthesis modification treatments, four samples with different degrees of urea functionalization were obtained, incorporating 10, 25, 50, and 100% of urea concerning the metal sites of the MOF. Alternatively, the influence of the degassing temperature of the non-functionalized MOF between 70 and 340 °C was also evaluated. The resulting compounds were characterized by N2 adsorption-desorption isotherms at -196 °C using TGA-MS, FTIR, and PXRD. Finally, the thermally treated and functionalized CPO-27-Mg was evaluated for CO2 capture.

CO2 Adsorption on PtCu Sub-Nanoclusters Deposited on Pyridinic N-Doped Graphene: A DFT Investigation.

To reduce the CO2 concentration in the atmosphere, its conversion to different value-added chemicals plays a very important role. Nevertheless, the stable nature of this molecule limits its conversion. Therefore, the design of highly efficient and selective catalysts for the conversion of CO2 to value-added chemicals is required. Hence, in this work, the CO2 adsorption on Pt4-xCux (x = 0-4) sub-nanoclusters deposited on pyridinic N-doped graphene (PNG) was studied using the density functional theory. First, the stability of Pt4-xCux (x = 0-4) sub-nanoclusters supported on PNG was analyzed. Subsequently, the CO2 adsorption on Pt4-xCux (x = 0-4) sub-nanoclusters deposited on PNG was computed. According to the binding energies of the Pt4-xCux (x = 0-4) sub-nanoclusters on PNG, it was observed that PNG is a good material to stabilize the Pt4-xCux (x = 0-4) sub-nanoclusters. In addition, charge transfer occurred from Pt4-xCux (x = 0-4) sub-nanoclusters to the PNG. When the CO2 molecule was adsorbed on the Pt4-xCux (x = 0-4) sub-nanoclusters supported on the PNG, the CO2 underwent a bond length elongation and variations in what bending angle is concerned. In addition, the charge transfer from Pt4-xCux (x = 0-4) sub-nanoclusters supported on PNG to the CO2 molecule was observed, which suggests the activation of the CO2 molecule. These results proved that Pt4-xCux (x = 0-4) sub-nanoclusters supported on PNG are adequate candidates for CO2 adsorption and activation.

Materiales carbonosos preparados a partir de cuesco de palma en la adsorción de CO2. Caracterización elemental, próxima y morfológica / Carbonaceous materials prepared from Palm shells for the adsorption of CO2. Elemental, proximal, and morphological characterization / Materiais carbonosos preparados a partir de Cuesco de Palma en a adsorção de CO2. Caracterização elementar, proximal e morfológica

Resumen En la presente investigación se prepararon sólidos porosos tipo carbón activado (CA) a partir de la activación química del cuesco de palma africana procedente de los cultivos de la región de la Guajira, Colombia, con soluciones de Fe(NO3)3 y Cu(NO3)2 con cambio en la concentración a dos diferentes temperaturas: 973 y 1073 K. Los sólidos adsorbentes preparados se caracterizaron para determinar sus propiedades fisicoquímicas y capacidades de adsorción de CO2. Los CA obtenidos presentan micro mesoporosidad con áreas superficiales entre 5 y 1300 m2g-1. Los valores con respecto al contenido de carbono fijo se encuentran entre 47,1 y 78,4%; los resultados evidencian que el proceso de activación tiene efectos sobre los parámetros texturales, composición elemental y proximal de los sólidos obtenidos. También se realizó la caracterización morfológica de la superficie de los materiales con SEM evidenciando la formación de mayor rugosidad en las muestras activadas a 1073 K, específicamente, los carbones activados con el nitrato cúprico; además, mediante EDX se cuantificó la presencia de algunos elementos. Los valores obtenidos de la adsorción de CO2 a bajas presiones se encuentran entre 80 y 250 mg•g-1, evidenciándose una mayor afinidad hacia los sólidos adsorbentes (MCu3 y MFe5).

Abstract In the present investigation, porous solids type activated carbon (CA) were prepared from the chemical activation of the African palm shells from the crops of the Guajira region, Colombia, with solutions of Fe(NO3)3 and Cu(NO3)2 with change in concentration at two different temperatures: 973 and 1073 K. The prepared adsorbent solids were characterized to determine their physicochemical properties and CO2 adsorption capacities. The CAs obtained present micro-mesoporosity with surface areas between 5 and 1300 m2g-1. The values with respect to the fixed carbon content are between 47.1% and 78.4%; the results show that the activation process has effects on the textural parameters, elemental and proximal composition of the solids obtained. The morphological characterization of the surface of the materials was also carried out with SEM, evidencing the formation of greater roughness in the samples activated at 1073 K, specifically, the activated carbons with cupric nitrate; furthermore, the presence of some elements was quantified by EDX. The values obtained from the adsorption of CO2 at low pressures are between 80 and 250 mg•g-1, showing a greater affinity towards adsorbent solids (MCu3 and MFe5).

Resumo Na presente investigação, sólidos porosos do tipo carvão ativado (CA) foram preparados a partir da ativação química do Cuesco de Palma Africana de lavouras da região de Guajira-Colômbia com soluções de Fe(NO3)3 e Cu(NO3)2 com alteração em concentração em duas temperaturas diferentes 973 e 1073 K. Os materiais preparados foram caracterizados para avaliar suas propriedades físico-químicas e capacidades de adsorção de CO2. Os (CAs) obtidos apresentam micro-mesoporosidade com áreas superficiais entre 5 e 1300 m g-1. Os valores com relação ao teor de carbono fixo estão entre 47,1 - 78,4%, os resultados mostram que o processo de ativação tem efeitos nos parâmetros texturais, composição elementar e proximal dos sólidos obtidos. A caracterização morfológica da superfície dos materiais também foi realizada com MEV, evidenciando a formação de maior rugosidade nas amostras ativadas a 1073 K, especificamente os carbonos ativados com nitrato cúprico, e a presença de alguns elementos foi quantificada por EDX. Os valores obtidos na adsorção de CO2 em baixas pressões estão entre 80-250 mg•g-1, mostrando uma maior afinidade para sólidos adsorventes (MCu3 e MFe5).

CO2 Capture by Hydroxylated Azine-Based Covalent Organic Frameworks.

Covalent organic frameworks (COFs) RIO-13, RIO-12, RIO-11, and RIO-11m were investigated towards their CO2 capture properties by thermogravimetric analysis at 1 atm and 40 °C. These microporous COFs bear in common the azine backbone composed of hydroxy-benzene moieties but differ in the relative number of hydroxyl groups present in each material. Thus, their sorption capacities were studied as a function of their textural and chemical properties. Their maximum CO2 uptake values showed a strong correlation with an increasing specific surface area, but that property alone could not fully explain the CO2 uptake data. Hence, the specific CO2 uptake, combined with DFT calculations, indicated that the relative number of hydroxyl groups in the COF backbone acts as an adsorption threshold, as the hydroxyl groups were indeed identified as relevant adsorption sites in all the studied COFs. Additionally, the best performing COF was thoroughly investigated, experimentally and theoretically, for its CO2 capture properties in a variety of CO2 concentrations and temperatures, and showed excellent isothermal recyclability up to 3 cycles.

Study of CO2 Adsorption on Chemically Modified Activated Carbon With Nitric Acid and Ammonium Aqueous.

The study of CO2 adsorption on adsorbent materials is a current topic of research interest. Although in real operating circumstances, the removal conditions of this gas is carried out at temperatures between 290 and 303 K and 1 Bar of pressure or high pressures, it is useful, as a preliminary approach, to determine CO2 adsorption capacity at 273K and 1 Bar and perform a thermodynamic study of the CO2 adsorption heats on carbonaceous materials prepared by chemical activation from African palm shell with CaCl2 and H3PO4 solutions, later modified with HNO3 and NH4OH, with the aim to establish the influence that these treatments have on the textural and chemical properties of the activated carbons and their relationship with the CO2 adsorption capacity. The carbonaceous materials were characterized by physical adsorption of N2 at 77K, CO2 at 273K, proximate analysis, Boehm titrations and immersion calorimetry in water and benzene. Activated carbons had a BET area between 634 and 865 m2g-1, with a micropore volume between 0.25 and 0.34 cm3g-1. The experimental results indicated that the modification of activated carbon with HNO3 and NH4OH generated a decrease in the surface area and pore volume of the material, as well as an increase in surface groups that favored the adsorption of CO2, which was evidenced by an increase in the adsorption capacity and the heat of adsorption.

Assessing CO2 Adsorption on Amino-Functionalized Mesocellular Foams Synthesized at Different Aging Temperatures.

A wide variety of solid sorbents has recently been synthesized for application in CO2 adsorption. Among them, mesoporous silicas deserve attention because of their ability to accommodate large concentrations of different chemicals as a consequence of their surface chemistry and tunable pore structure. Functionalized materials exhibit promising features for CO2 adsorption at high temperatures and low CO2 concentrations. This work aimed to assess the influence of the textural properties on the performance of CO2 adsorption on functionalized mesoporous silica. With this goal, several mesoporous silica foams were synthesized by varying the aging temperature, obtaining materials with larger pore diameter. Thus, the synthesized materials were functionalized by grafting or impregnation with 3-aminopropyltriethoxysilane, polyethylenimine, and tetraethylenepentamine as amine sources. Finally, the amino functionalized materials were assessed for CO2 capture by means of equilibrium adsorption isotherms at 25, 45, and 65°C. Among the most outstanding results, high aging temperatures favor the performance of impregnated materials by exposing greater pore diameters. Low or intermediate temperatures favor grafting by preserving an appropriate density of silanol groups.

Investigating greenhouse gas adsorption in MOFs SIFSIX-2-Cu, SIFSIX-2-Cu-i, and SIFSIX-3-Cu through computational studies.

The selective adsorption of CO2 in mixture with other greenhouse gases by porous materials is challenging and it has several consequences from the environmental and economic point of view. We carried out DFT calculations with periodic boundary conditions and plane waves basis set to better understand the adsorption of CO2, CO, CH4, N2, O2, and H2 within the pore of the metal-organic frameworks (MOFs) SIFSIX-2-Cu, SIFSIX-2-Cu-i, and SIFSIX-3-Cu. These porous materials have a copper ion coordinated to an organic linker and the inorganic SiF62- pillar, and they show a remarkable CO2 uptake. Our results show that the adsorption occurs preferentially close to the inorganic pillar SiF6, which polarizes the gas molecule, increasing the electrostatic contribution to the interaction. The adsorption strength correlates with the size of the pore, and it is stronger in the smaller porous of SIFSIX-3-Cu for all gases. The successive loading of CO2 in a T-shape form inside the porous indicates a synergic polarization effect, increasing the adsorption energy in SIFSIX-2-Cu and SIFSIX-2-Cu-i, but not in SIFSIX-3-Cu. For all materials, we observe the following order in the adsorption energy: CO2 > CH4 > CO > N2 > O2 > H2, suggesting that a thermodynamic separation could be possible; however, kinetic effects are also important in SIFSIX-3-Cu. Graphical abstract.

Tailoring activated carbons from Pinus canariensis cones for post-combustion CO2 capture.

Activated carbons (ACs) from Pinus canariensis cones were developed by KOH chemical activation. The effect of the impregnation KOH/carbonized cones ratio (IR = 1, 2, or 3) and temperature (873, 973, 1073 K) on main chemical, textural, and morphological characteristics of the resulting ACs was systematically examined. CO2 adsorption capacity from gaseous streams was evaluated by gravimetric adsorption tests, and the analysis of breakthrough curves was determined in a packed-bed column at 303 K and atmospheric pressure. Comparison of CO2 adsorption capacities of the ACs at 273 K and 303 K at equilibrium showed that those samples developed at 973 K with IR = 3 (BET surface area ~ 1900 m2 g-1) attained the highest values (6.4 mmol g-1 and 1.9 mmol g-1, respectively), even though the ACs obtained at 1073 K with the same IR exhibited the largest surface area (2200 m2 g-1). Thermodynamic parameters evaluated from CO2 adsorption isotherms determined in the range 273-333 K for the former sample pointed to a physisorption, spontaneous, and exothermic process; isosteric heat of adsorption was also estimated for the range of surface coverage of the equilibrium isotherms. The kinetics of CO2 adsorption onto all the ACs was successfully described by the linear driving force model. The breakthrough curves were properly represented by the Thomas' model, the longest breakthrough time and highest adsorption capacity being also attained for the bed packed with the ACs developed at 973 K with IR = 3. Higher CO2 adsorption capacities of the ACs were directly related to the presence of narrow micropores (< 0.9 nm) induced by the stronger activation conditions. However, an excessively severe combination of the IR and activation temperature exerted a negative influence on CO2 adsorption onto the ACs, likely due to micropores widening.

CO2 Capture with Mesoporous Silicas Modified with Amines by Double Functionalization: Assessment of Adsorption/Desorption Cycles.

CO2 adsorption on mesoporous silica modified with amine by double functionalization was studied. Adsorption microcalorimetry was used in order to investigate the influence of increasing the nitrogen surface density on double functionalized materials with respect to the only grafted materials. The distribution of sites and the rate-controlling mechanism of adsorption were evaluated. A Tian Calvet microcalorimeter coupled to a manometric setup was used to evaluate the energy distribution of adsorption sites and to calculate the thermokinetic parameters from the differential enthalpy curves. CO2 and N2 adsorption equilibrium isotherms at 50 and 75 °C were measured with a magnetic suspension balance, allowing for the computation of working capacity and selectivity at two temperatures. With these data, an Adsorbent Performance Indicator (API) was calculated and contrasted with other studied materials under the same conditions. The high values of API and selectivity confirmed that double functionalized mesoporous silica is a promising adsorbent for the post combustion process. The adsorption microcalorimetric study suggests a change in active sites distribution as the amine density increases. Maximum thermokinetic parameter suggests that physisorption on pores is the rate-controlling binding mechanism for the double-functionalized material.

Toward a Delaminated Organotalc: The Use of Polyamidoamine Dendrons.

A sequence of generations of the polyamideamine dendron, PAMAM-talc-Gn (n = 1-7), was constructed on the surfaces of ethylenediaminepropyl-functionalized magnesium phyllosilicate lamellas by using a modified microwave-assisted synthesis. The successful functionalization of the inorganic layers by the organic dendrimer was confirmed by FTIR and (13)C NMR spectroscopies, elemental analyses, and thermogravimetric analysis (TGA). The solid materials presented an increase in their interlamellar space and disorganization of lamella packing with the growth of the dendrons. Thermal-programmed desorption analysis showed that the lower dendron generation, PAMAM-talc-G1, adsorbed 1.30 mmol of CO2/g of sorbent at 30 °C. PAMAM-talc-G5 adsorbed the double of PAMAM-talc-G3, probably due to the higher amount of the primary amine group; however, PAMAM-talc-G5 adsorbed more CO2 than PAMAM-talc-G7 probably because in the delaminated seventh generation intradendron N-H interactions were more prevalent than in the fifth generation and blocked CO2 interaction sites.

CO2adsorption on activated carbon honeycomb-monoliths: a comparison of Langmuir and Tóth Models.

Activated carbon honeycomb-monoliths with different textural properties were prepared by chemical activation of African palm shells with H(3)PO(4), ZnCl(2) and CaCl(2) aqueous solutions of various concentrations. The adsorbents obtained were characterized by N(2) adsorption at 77 K, and their carbon dioxide adsorption capacities were measured at 273 K and 1 Bar in volumetric adsorption equipment. The experimental adsorption isotherms were fitted to Langmuir and Tóth models, and a better fit was observed to Tóth equation with a correlation coefficient of 0.999. The maximum experimental values for adsorption capacity at the highest pressure (2.627-5.756 mmol·g(-1)) are between the calculated data in the two models.