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Article

Optimized Porous Carbon Particles from Sucrose and Their Polyethyleneimine Modifications for Enhanced CO2 Capture

by
Betul Ari
1,
Erk Inger
2,
Aydin K. Sunol
3 and
Nurettin Sahiner
1,3,4,*
1
Department of Chemistry, Faculty of Science, Canakkale Onsekiz Mart University, Terzioglu Campus, Canakkale 17100, Turkey
2
Department of Airframe and Powerplant Maintenance, Atilim University, Incek, Ankara 06830, Turkey
3
Department of Chemical and Biomolecular Engineering, College of Engineering, University of South Florida, Tampa, FL 33620, USA
4
Department of Ophthalmology, Morsani College of Medicine, University of South Florida, 12901 Bruce B. Downs Blvd, MDC21, Tampa, FL 33612, USA
*
Author to whom correspondence should be addressed.
J. Compos. Sci. 2024, 8(9), 338; https://doi.org/10.3390/jcs8090338
Submission received: 14 July 2024 / Revised: 4 August 2024 / Accepted: 26 August 2024 / Published: 27 August 2024
(This article belongs to the Special Issue Progress in Polymer Composites, Volume III)
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Abstract

:
Carbon dioxide (CO2), one of the primary greenhouse gases, plays a key role in global warming and is one of the culprits in the climate change crisis. Therefore, the use of appropriate CO2 capture and storage technologies is of significant importance for the future of planet Earth due to atmospheric, climate, and environmental concerns. A cleaner and more sustainable approach to CO2 capture and storage using porous materials, membranes, and amine-based sorbents could offer excellent possibilities. Here, sucrose-derived porous carbon particles (PCPs) were synthesized as adsorbents for CO2 capture. Next, these PCPs were modified with branched- and linear-polyethyleneimine (B-PEI and L-PEI) as B-PEI-PCP and L-PEI-PCP, respectively. These PCPs and their PEI-modified forms were then used to prepare metal nanoparticles such as Co, Cu, and Ni in situ as M@PCP and M@L/B-PEI-PCP (M: Ni, Co, and Cu). The presence of PEI on the PCP surface enables new amine functional groups, known for high CO2 capture ability. The presence of metal nanoparticles in the structure may be used as a catalyst to convert the captured CO2 into useful products, e.g., fuels or other chemical compounds, at high temperatures. It was found that B-PEI-PCP has a larger surface area and higher CO2 capture capacity with a surface area of 32.84 m2/g and a CO2 capture capacity of 1.05 mmol CO2/g adsorbent compared to L-PEI-PCP. Amongst metal-nanoparticle-embedded PEI-PCPs (M@PEI-PCPs, M: Ni, Co, Cu), Ni@L-PEI-PCP was found to have higher CO2 capture capacity, 0.81 mmol CO2/g adsorbent, and a surface area of 225 m2/g. These data are significant as they will steer future studies for the conversion of captured CO2 into useful fuels/chemicals.

1. Introduction

Technological progress and growth depend on energy, and energy demand is steadily rising with time. As the population is rapidly growing, there is a great need to meet the energy demand with sustainable and green energy sources. Unfortunately, a noteworthy part of the increasing energy demand is met by fossil fuels that produce greenhouse emissions [1,2]. Reducing fossil fuel consumption and simultaneously reducing greenhouse gas has a significant impact and is a step forward for a green future [3]. Carbon dioxide (CO2) is a greenhouse gas with a steady increase in concentration at an recognizable level, causing global concern [4,5]. Prior to the 1850s, the amount of CO2 in the atmosphere remained constant at around 235 ± 50 ppm for about 400,000 years [5,6]. However, after the Industrial Revolution, the amount of CO2 in the atmosphere also began to increase. The latest data reveal that the amount of CO2 in the atmosphere has reached its peak, 420 ppm, which is about an 80% increase from the 1850s levels to recent years [4,6]. Without taking necessary precautions, it is anticipated that the amount of CO2 in the atmosphere will reach 600–1500 ppm in 2030, threating human and environmental health [7]. It was suggested that there are two effective measures that can be taken to reduce CO2 emissions in the atmosphere and at the same time increase the efficient use of alternative and clean energy sources [8,9]. In order to reduce CO2 emissions, numerous approaches have been suggested to reduce energy consumption, involving increasing energy conversion efficiency, converting to low-carbon fuels with high productivity, and using sustainable and renewable energy sources [10,11]. In the last few decades, there has been increasing interest in CO2 capture, storage, and conversion technologies to decrease CO2 levels in the atmosphere [12]. A simultaneous CO2 capture and its use by converting into methane, methanol, ethanol [13], acetone, acetaldehyde, and other useful chemicals that serve as fuels in various industrial processes are assumed very attractive [10,14,15]. Accordingly, the demand for clean energy is increasing constantly in the world. As the vast majority of energy is provided by fossil fuels such as coal, oil, and natural gas, which cause CO2 emissions, a momentous request has led to the development of new technologies that prevent emissions or eliminate the release of CO2 and toxic gas into the atmosphere. Many materials with interesting characteristics such as porous materials including zeolitic imidazolate frameworks (ZIFs) [16,17], metal organic frameworks (MOFs) [18,19,20,21], covalent organic frameworks (COFs) [22,23,24], and carbon-based materials [25,26] are the most promising materials for CO2 capture and storage technologies. Among these materials, carbon-based materials especially have great potential in industrial utilization due to their cost effectiveness, chemical modification, impregnation, regeneration, higher adsorption ability (e.g., substantial amount of CO2 adsorption capability [27]), and sustainable utilization. Therefore, carbon-based materials are of significant importance as adsorbents, especially for the CO2 and toxic gas removal, and then for further catalytic use regarding environmental and energy concerns. However, capturing and storing CO2 alone is not enough. The most effective results can be achieved when the captured CO2 can be converted into fuel or another useful chemical [28].
This research aimed to prepare sucrose-derived porous carbon particles (PCPs) and then modify them with amine group-containing compounds, B-PEI and L-PEI, as B-PEI-PCP and L-PEI-PCP, as these polymers are known for their selective CO2 capture ability. Additionally, the determination of the CO2 capture ability of B-PEI-PCP and L-PEI-PCP and their metal-nanoparticle-containing forms such as M@PEI-PCPs (M: Ni, Co, Cu) was conducted with the intention to attain preliminary information for their potential direct use in fuel and/or other useful chemical production via the catalytic conversion of the captured CO2, employing these in situ prepared metal nanocatalysts (M: Ni, CO, Cu). Then, the CO2 capture capacity of all the prepared carbon-based absorbents at 25 °C was investigated.

2. Materials and Methods

2.1. Materials

D(+) Sucrose (Carlo Erba, Val-de-Reuil, France) was used as precursor in the preparation of sucrose-derived carbon particles. Silica (SiO2) particles were used to generate pores within carbon particles (CPs) to obtain porous carbon (PCPs) particles. To synthesize SiO2 particles, tetraethyl orthosilicate (TEOS, 98%, Sigma Aldrich, Milwaukee, WI, USA) was used; ammonium hydroxide (NH4OH, 25%, Sigma Aldrich, Milwaukee, WI, USA) and ethanol (ethanol absolute anhydrous, ≥99.9%, Carlo Erba, Cornaredo, Italy) were used to prepare SiO2 particles. Sodium hydroxide pellets (NaOH, AFG, Cologne, Germany) were used to remove SiO2 particles from carbon particles–silica (SiO2@CP). In the chemical modification of CPs, nitric acid (HNO3, ≥65%, Sigma-Aldrich, Milwaukee, WI, USA) and sulfuric acid (H2SO4, 95%–97%, Merck, Darmstadt, Germany) were used for first oxidation of CPs. Then, epichlorohydrin (ECH, 99%, Sigma-Aldrich, Milwaukee, WI, USA) was used as a coupling agent, with branched polyethyleneimine (B-PEI, Mw: 25,000, Sigma Aldrich, Milwaukee, WI, USA) and linear PEI (L-PEI, Mw: ~23,000) used as modification agents. Cobalt chloride hexahydrate (CoCl2.6H2O, 98%, Acros, Geel, Belgium), copper chloride (CuCl2 anhydrous, 98%, Acros), and nickel chloride hexahydrate (NiCl2.6H2O, 98%, Acros, Geel, Belgium) were used as received and employed in the preparation of metal nanoparticles. Sodium borohydride (NaBH4, 98%, Merck, Darmstadt, Germany) was used as reduction agent and for metal ions. Ethanol (technical grade, Birkim, Istanbul, Turkey) and distilled water (DI water) were used for washing all obtained particles.

2.2. Synthesis of SiO2 Particles

The SiO2 particles were prepared using the modified Stober method [29,30]. Accordingly, 15 mL of ethanol and 2.25 mL of NH4OH solution were transferred to a plastic bottle and stirred under 800 rpm at room temperature until a homogeneous solution was obtained. Then, 2.25 mL TEOS was added into this solution and reacted for 2 h to obtain SiO2 particles via hydrolysis and condensation reactions in the ethanol-NH4OH solution. Finally, the obtained SiO2 particles were precipitated at 10,000 rpm for 20 min and washed with DI water twice, and then with an ethanol/DI water mixture (1:1, v:v) twice, and finally with ethanol once by centrifugation at 10,000 rpm. Finally, SiO2 particles were dried first with the help of a heat gun and then in an oven at 50 °C, and then kept in airtight tubes for later use.

2.3. Synthesis of Sucrose-Derived Porous Carbon Particles (PCPs)

Sucrose-derived porous carbon particles (PCPs) were synthesized following the hydrothermal carbonization method as reported previously by our group [31]. For a typical hydrothermal process, 50 mL of 1 M sucrose solution was prepared in a Teflon-lined reaction chamber. Then, 10% SiO2 particles (1.7 g) by weight of sucrose were added to this solution and stirred at 500 rpm for 12 h at room temperature. After 12 h, this solution was placed in a stainless steel autoclave reactor and then it was heated from 20 °C to 200 °C at a heating rate of 6 °C/min for 30 min in an oven. Then, the reactor was held at 200 °C for 4 h. After this first process was completed, the autoclave reactor was unloaded from the oven and the SiO2@CP mixture was left to cool at room temperature. Subsequently, this mixture was centrifuged at 10,000 rpm for 20 min to collect the SiO2@CPs. The collected solid particles were washed several times through centrifugation with an ethanol/DI water mixture (1:1, v:v) and the final product was freeze-dried. For the carbonization process, a certain amount of cleaned product was transferred into porcelain crucibles, placed in the oven, and purged with N2 gas for 15 min to stabilize the ambient atmosphere. Then, the oven was heated to 500 °C at a heating rate of 2.5 °C/min under N2 atmosphere and kept for 40 min at this temperature. Then, the porcelain crucibles containing the SiO2@CP composite were removed from the furnace and left to cool to ambient temperature. Solvents in the order of DI water and ethanol/DI water mixture 50:0 (v:v) were used to wash the SiO2@CP composite twice before freeze-drying. Finally, the SiO2@CP composite was treated with 50 mL of 1 M NaOH solution for 24 h to remove SiO2 particles to attain porous carbon particles. Next, the porous carbon particles (PCPs) were collected via centrifugation at 10,000 rpm for 20 min. The collected solid product was washed thrice with DI water, thrice with an ethanol/DI water mixture (50:50, v:v), and twice with ethanol to remove dissolved SiO2 particles. Lastly, clean PCPs were freeze-dried and stored in an airtight tube for further use as adsorbents and for modification reactions.

2.4. Modification of Porous Carbon-Based Particles

The modification of carbon-based particles was performed as reported in the literature with some modifications [32,33]. Firstly, the prepared PCPs weighing 4.5 g were treated with 450 mL of a concentrated H2SO4:HNO3 mixture (3:1 volume) for 4 h to generate -OH and -COOH functional groups on PCPs. After functionalization, e.g., generation of -OH and -COOH groups on PCPs, the PCPs were washed with DI water by centrifuging at 10,000 rpm, and then treated with a 50 mL 1 M NaOH solution for 2 h at room temperature (200 rpm mixing rate). Then, NaOH-treated PCP particles were again centrifuged and washed with DI water once at 10,000 rpm and dried in a freeze-dryer. Afterward, for each modification agent, a medium of 25 mL of DI water at pH 12 adjusted with 1 M NaOH was used. These DI waters were transferred into 50 mL round-bottomed flasks and 0.5 g of activated PCP was added into each flask. Each flask was stirred for 15 min at 750 rpm at ambient temperature. These flasks were placed in an oil bath at 90 °C under 750 rpm mixing for 15 min to equilibrate the temperature. Next, a 1.5 mL EPC was added to each flask mixing under the same conditions for 1 h. Separately, a 2 g B-PEI was dissolved in 5 mL of DI water at pH adjusted to 12. Also, 2 g of L-PEI was dissolved in the same volume of DI water at 90 °C. Then, these modification agents were slowly added to the reaction medium with the help of an injector, and the reactions proceeded for 1 h. Finally, the amine-modified porous carbon particles (M-PCPs) were washed with DI water and ethanol once each and centrifuged at 10,000 rpm, and then finally freeze-dried for further use.

2.5. Preparation of Co, Cu, and Ni Metal Nanoparticles inside PCPs and PEI-PCPs

The freeze-dried PCPs and PEI-modified PCPs weighed about 100 mg and were transferred in a 1000 ppm 50 mL ethanol solution of Co, Cu, and Ni metal salts. These solutions were stirred at room temperature for about 24 h under a 500 rpm mixing rate. The metal ion-loaded PCPs (M@PCPs) and PEI-modified PCPs (M@B-PEI-PCPs or M@L-PEI-PCPs) were washed twice with ethanol by centrifugation at 10,000 rpm and then freeze-dried. Then, these metal-ions-loaded samples were transferred in 50 mL 0.2 M NaBH4 aqueous solution and mixed under 500 rpm at room temperature to attain corresponding metal nanoparticles within modified carbon porous particles. Finally, the Co, Cu, and Ni metal-nanoparticle-containing composites were washed twice with ethanol and freeze-dried for further use.

2.6. Determination of Metal Nanoparticle Content of Metal-Loaded PCPs and PEI-Modified PCPs

A total of 50 mg of metal-loaded samples was placed in 30 mL of a 5 M HCl aqueous solution and stirred at a 500 rpm mixing rate until the metal nanoparticles were dissolved. Then, the acid solutions were diluted 1:100 with DI water and the metal ion content of the solution for the obtained samples was determined through atomic absorption spectroscopy (AAS, Thermo, Bedford, MA, USA, ICA 3500 AA SPECTRO).

2.7. Characterization of Carbon-Based Particles

The sucrose-derived carbon-based particles functional group analysis was determined by using Fourier transform infrared spectroscopy (FT-IR, Thermo Fisher Scientific, Bedford, MA, USA) in the 4000–650 cm−1 wavenumber range. Thermogravimetric analysis of all the prepared carbon-based particles was conducted using a thermal gravimetric analyzer (TGA, SII TG/DTA 6300, Kyoto, Japan). In TGA measurements, samples weighing about 3 mg were placed in a TGA alumina crucible and heated from 35 °C up to 100 °C under the N2 atmosphere with a flow rate of 10 mL/min at 10 °C/min heating rate and held for 10 min to eliminate moisture. Then, the temperature was progressively increased from 100 °C to 750 °C, and the changes in the weight loss as a function of temperature of the samples were recorded. The morphological structures of PCP and PEI-PCPs were assessed using a field emission scanning electron microscope (FESEM, QUANTA 400 F). The samples were coated with Au–Pt in a few nm thickness. The images were recorded under a high vacuum at 30 kV at different magnifications. A high-resolution transmission electron microscope (HRTEM, JEOL 2100 F 200 kV, Kyoto, Japan) was used to determine the size of porous-based carbon particles. High-contrast transmission electron microscopy (CTEM, FEI 120 kV, Hillsboro, OR, USA) was used to determine the shape and size of metal nanoparticles within M@B-PEI-PCPs. In all TEM analyses, carbon-based particles were dispersed in ethanol and mixed in an ultrasonic cleaner for 1.45 min, then a drop of this suspension was placed onto the grid and left to dry overnight. Then, the images were recorded the next day. The X-ray diffraction (XRD) patterns of the samples were obtained using an XRD device (PANALYTICAL Brand X’PERT PRO MPD Diffractometer). The XRD analysis was performed using the Cu Kα X-ray generator. Scans were taken between 2 theta 3–70° using 0.02 step size, ¼ divergence slit, and ½ antiscatter slit. Samples were manually pressed onto a glass slide sample holder. The surface area and pore characteristics of sucrose-derived carbon-based particles were analyzed using the N2 adsorption–desorption isotherms (Micromeritics, Tristar II Surface Area and Porosity Analyzer) via the surface area analyzer. Before analysis, porous carbon particles were outgassed at 200 °C for 16 h using a degasser (Micromeritics, Flow Prep 060) under N2 gas, whereas the PEI-modified and metal-nanoparticle-embedded PCPS were outgassed at 100 °C for 16 h. The surface area of all samples was calculated using the Brunauer–Emmett–Teller (BET) equation and their pore volumes and pore sizes were calculated using the Barret–Joyner–Halenda (BJH) method.

2.8. CO2 Capture and CO2 Adsorption/Desorption Studies

The CO2 adsorption–desorption isotherms of each sample were calculated at 25 °C by volumetric gas adsorption–desorption studies employing a surface area analyzer (Micromeritics, Tristar II Surface Area and Porosity Analyzer). Before CO2 adsorption–desorption analysis, as mentioned earlier, PCPs were outgassed with N2 gas for 16 h at 200 °C while the degassing temperatures of PEI-PCPs and M@PEI-PCPs were 100 °C for the same duration of time. After the outgas period was completed, the tubes were placed in the ports and were filled with a fixed amount of CO2 until the equilibrium pressure was reached. The analysis was carried out by volumetric gas CO2 adsorption–desorption studies at 25 °C.

3. Results and Discussion

3.1. Structure of Carbon-Based Particles

A schematic presentation of the synthesis of PCP via hydrothermal carbonization method is shown in Figure 1a. It involved hydrothermal processing of a sucrose–silica mixture to obtain carbon composite particles, then the carbonization process, and then the removal of silica particles from SiO2@CP to attain PCPs. Silica particles are widely used as templates to synthesize porous carbonaceous materials [34]. As reported in some studies in the literature, template silica materials can be easily removed by treating with hydrofluoric acid (HF) [35,36] or sodium hydroxide (NaOH) [31,33,37]. As reported in the XRD analysis of PCPs used in this and our previous study [31,33], no SiO2 peak was observed in the XRD patterns of PCPs. On the other hand, we also reported XPS analysis results of sucrose-derived porous carbon particles, and according to the XPS analysis results, trace amounts of SiO2 residue (0.5%) were detected in the structure of PCPs after they were treated with 1 M NaOH for 24 h. Therefore, it was presumed that PCPs were attained by the removal of SiO2 moieties from the carbonous network [31,33].
The morphologies of PCPs are shown in SEM images in Figure 1b. PCPs have a smooth surface morphology with spherical shapes. The PCPs have a particle size range of about 1–10 µm.
The schematic diagram of the oxidation reaction of PCPs and subsequent modification reaction with PEI is presented in Figure 2a. As shown, PCPs were oxidized by strong oxidizing acid treatments to generate –COOH and –OH functional groups on their surfaces. Therefore, the oxidized PCPs were then further treated with 1 M NaOH for activation. Next, these NaOH-activated PCPs reacted with epoxy groups of ECH, used as a coupling agent. Then, ECH-modified PCPs were reacted with B-PEI and L-PEI to form the corresponding amine functionality on PCP surfaces.
The surface morphology and particle size of B-PEI-PCP and L-PEI-PCP were determined through FE-SEM, and the corresponding FE-SEM images are shown in Figure 2b,c, respectively. As the surface of the particles is coated with B-PEI and L-PEI after the modification of PCP with PEIs, both PEI-modified PCPs have a rough surface morphology. The particle sizes of both B-PEI-PCPs and L-PEI-PCPs range from 2.5 µm to 10 µm.
To confirm the modification of PCPs with B-PEI and L-PEI, the FT-IR spectra of PCPs before and after PEI modification were compared and are shown in Figure 3a. The treatment of PCPs with H2SO4:HNO3 (3:1 volume) generates new functional groups, such as the formation of C=O and –OH functional groups on PCPs, which was corroborated by the occurrence of a peak at 1713 cm−1 for C=O and an –OH peak at 1073 cm−1, respectively. Also, the observed new peaks at 1532 cm−1 and 1228 cm−1 were attributed to N –H bending vibrations and C –N stretching vibrations, respectively, upon PEI modifications.
Thermal degradations of PCPs and PEI-modified PCPs were analyzed using TGA, and the corresponding thermograms are shown in Figure 3b. As seen, PCPs started to degrade at 250 °C with a weight loss of 2%, and the degradation ended with a total weight loss of 54% until heating up to 750 °C. On the other hand, B-PEI-PCPs began to degrade at 250 °C with a weight loss of 5%; at 550 °C, the weight loss reached approximately 42%; and up to 750 °C, the total weight loss of B-PEI-PCPs was 88%. Interestingly, B-PEI-PCPs and L-PEI-PCPs exhibited similar degradation profiles. For L-PEI-PCPs, the degradation started at 270 °C with a 2% weight loss and continued to degrade at 500 °C with a 29% weight loss, and as the temperature reached 750 °C, the total weight loss was 77%. Overall, it can be said that the thermal stability of PEI-modified PCPs was decreased slightly due to the presence of polymeric PEI chains, as confirmed by new peaks’ formation, as corroborated in the FT-IR spectrum of PEI-modified PCPs. And these groups affect the thermal stability of PCPs, depending on the nature of the PEI chains; for example, B-PEIs are more thermally degradable than L-PEIs on their PCP-modified forms.
As the PEI-modified PCPs are used in the loading of and in situ reduction of Co, Cu, and Ni salts, the metal nanoparticle content of carbon-based particles, M@PEI-PCPs (M: Ni, Co, and Cu), is significantly important in some catalytic applications. Additionally, PCPs can also act both as a template for metal nanoparticle preparation and for CO2 capture. Therefore, M@PEI-PCPs and M@PCPs can convert captured CO2 into useful products such as methanol, formic acid, carbon monoxide, and so on at different high temperatures due to the presence of metal nanoparticles embedded within carbonous structures. Thereby, the metal nanoparticles act as a catalyst. Therefore, both PCPs and PEI-PCPs were loaded with metal nanoparticles, and their CO2 capture performances were evaluated. The metal nanoparticle amounts were determined with atomic absorption spectroscopy (AAS) measurements after dissolving the corresponding metal nanoparticles from M@PCP and M@PEI-PCPs in concentrated acid solutions, as mentioned above, and the associated results are summarized in Table 1.
As seen in the table, PEI-modified PCPs loaded the highest amount of Cu metal nanoparticles, 74.6 ± 5 mg/g, in comparison to B-PEI-PCPs and L-PEI-PCPs, which had 44.5 ± 5 and 29.9 ± 2 mg/g, respectively. Surface area, pore size, pore structure, pore distribution, and functional groups on the surfaces are important parameters affecting the adsorption behavior of adsorbents [38]. In physical adsorption, the adsorbed amount of materials is generally directly proportional to the surface area of the adsorbent, and adsorption amounts of adsorbates increase with the increasing surface area of the adsorbent [39,40]. As the surface area of PCPs is larger than the surface area of PEI-PCPs, they have a higher number of metal ions loading, hence the metal nanoparticles are attained.
To better understand the structure of B-PEI-modified PCPs and their metal-nanoparticle-embedded forms, their XRD analysis was conducted and the XRD patterns of PCPs, B-PEI-PCPs, Co@B-PEI-PCPs, Cu@B-PEI-PCPs, and Ni@B-PEI-PCPs are shown in Figure 4a. The XRD patterns shown in Figure 4a show that all carbon-based particles have an amorphous structure, which is clearly seen by observing the wide peak at 2θ = 23–24°. XRD patterns of Cu@B-PEI-PCP show four peaks at 2θ = 23.3°, 31.6°, 36.4°, and 43.2°. The peak at 2θ = 43.2° is attributed to the presence of Cu metal nanoparticles [41]. In the XRD pattern of Ni@B-PEI-PCP, three peaks are observed at 2θ = 24.4°, 31.6°, and 45.3°. Here, the peak at 2θ = 45.3 is assigned to the existence of Ni metal nanoparticles [42].
The surface morphology and particle size of PCPs and B-PEI-PCPs were determined through FE-SEM, and the corresponding FE-SEM images are shown in Figure 4b,c, respectively. As can be seen from Figure 4b, PCPs have a smooth surface morphology with a spherical particle shape. The PCPs have a particle size of about a few μms. On the other hand, as the particle surface was coated with B-PEI after the modification of PCPs with B-PEI, B-PEI-PCPs possessed a rough surface morphology with the particle sizes of B-PEI-PCPs ranging from 2.5 µm to 10 µm. TEM images of the same samples are shown in Figure 4d. As can be seen from the HRTEM images, PCP exhibits a graphite sheet-like structure. The CTEM image of M@B-PEI-PCPs revealed a dark dot for metal nanoparticles, Co, Cu, and Ni, and a dark grey region in the middle for B-PEI-PCPs, confirming the successful preparation of metal nanoparticles on B-PEI-PCPs and M@B-PEI-PCPs. The CTEM images of B-PEI-PCPs and M@B-PEI-PCPs show that the metal nanoparticles are spherical and distributed almost evenly throughout the structures. The sizes of Co and Ni metal nanoparticles are approximately 5–10 nm, while the sizes of Cu metal nanoparticles are in the range of 10–20 nm.
The surface area of the carbon-based particles was assessed via Brunauer–Emmett–Teller (BET) method using the N2 adsorption–desorption isotherm, and the surface area, pore size, and pore volume were determined by the BJH method. The N2 adsorption–desorption isotherms of PEI-modified PCPs and metal-nanoparticle-embedded PCPs are shown in Figure 5a,b, respectively. The isotherms are typical isotherms of mesoporous materials, with pore size ranges of 2–50 nm.
The surface area of the PCPs, PEI-PCPs, and M@PEI-PCPs was assessed through BET method, employing the N2 adsorption–desorption isotherm, and the surface area, pore size, and pore volume were calculated by the BJH method; the corresponding results are summarized in Table 2. The surface areas of PCPs, B-PEI-PCPs, and L-PEI-PCPs were calculated as 325.58, 32.84, and 2.18 m2/g, respectively. Their pore sizes were calculated as 2.94, 19.31, and 13.96 nm, and their pore volumes were determined as 0.07, 0.31, and 0.63 cm3/g, respectively. The surface area of PEI-modified PCPs decreased significantly compared to PCPs. For example, the surface area value of B-PEI-PCPs decreased nearly 10-fold, changing from 325.58 m2/g to 32.84 m2/g. On the other hand, the pore size of 2.94 nm increased to 19.31 nm and the pore volume of 0.065 cm3/g changed to 0.31 cm3/g. The surface area of L-PEI-PCPs was also decreased by about 150-fold, from 325.58 m2/g to 2.18 m2/g. Moreover, the pore size of 2.94 nm increased to 10.24 nm and the pore volume of 0.07 cm3/g changed to 0.63 cm3/g. On the other hand, the surface areas and pore volumes of metal-nanoparticle-embedded PCPs are close to or smaller than those of PCPs.
Consequently, the surface area of PEI-modified PCPs is smaller than that of PCPs. This is reasonable as the surfaces and pores of the PEI-modified PCPs are coated by PEI.
Figure 5c,d show the pore size distribution graphs of PCPs, PEI-modified PCPs, and metal-nanoparticle-embedded PCPs. It was determined that PCPs, PEI-modified PCPs, and metal-nanoparticle-embedded PCPs samples are mesoporous materials. Upon modification and metal nanoparticle loading, the specific surface area was decreased. The surface area, pore size, and pore volume of PCPs vary slightly depending on the chain structure of the PEI modifying agents. According to the BET analysis results, due to the flexible chain structures, B-PEI and L-PEI can typically cover mostly the outer surface of PCPs. Therefore, the surfaces of PCPs become covered, resulting in a much lower surface area. The surface area of both B-PEI- and L-PEI-modified PCPs decreases due to coating of the particle surface with PEI, as expected. On the other hand, as the modification is not selective, the surface area may decrease significantly, whereas it may cause a slight increase in pore size and pore volume values.

3.2. CO2 Capture Studies of Carbon-Based Particles

High surface area and pore volume make activated carbon attractive for many uses as an adsorbent material in industry. Activated carbon is a suitable adsorbent material for CO2 capture and storage, especially because of its high porosity. In addition to the specific physical or chemical binding ability, the CO2 capture performance of the adsorbents is affected by various factors, e.g., the size, surface area, porosity, pore distribution, and pore volume of the adsorbent [7,43,44].
Figure 6 shows the CO2 adsorption–desorption isotherm of PCPs, PEI-modified-PCPs, metal-nanoparticles-loaded porous carbon particles (M@PCPs), and metal-nanoparticles-loaded PEI-modified porous carbon particles (M@PEI-PCPs). As seen in Figure 6a, PCP has a higher CO2 capture capacity than its PEI-modified forms. Table 3 summarizes the CO2 adsorption capacities of all the porous carbon-based materials, as illustrated in Figure 6. The data in Table 3 were calculated in mmol at standard conditions (25 °C) based on the maximum CO2 adsorption values at 1.18 atm (899 mmHg) of the samples presented in Figure 6. In Table 3, B-PEI-PCPs have a higher CO2 capture capacity compared to L-PEI-PCPs. However, this is not better than the unmodified or metal-nanoparticle-embedded forms of PCP. A CO2 capture value of 2.36 mmol per gram of PCP particle decreased to 1.05 mmol and 0.96 mmol CO2/g absorbent after modification of this particle with B-PEI and L-PEI, respectively. This decrease can be attributed to the decrease in surface area values, as the PEI chains can block the pores, resulting in coating the particle surface with B- or L-PEI chains after modification [45]. The adsorption curve of PCPs and M@PCPs showed a continuous increase in CO2 adsorption capacity, while the CO2 adsorption curves of M@PEI-PCPs exhibited a rapid increase in the relatively low pressure range (0–0.4 atm). According to the IUPAC classification, the CO2 adsorption isotherms in all carbon-based particles follow the Type I physical adsorption isotherm, which represents the monolayer formation of molecules (mesoporous) [46]. The CO2 adsorption–desorption isotherms of all carbon-based particles show that their concavities are variable. The concavities confirm the affinity of CO2 adsorption to carbon-based particles. The CO2 adsorption–desorption isotherms of PCPs and M@PCPs show the highest concavities and that the concavity curves’ shapes are close to each other. However, the adsorption–desorption isotherms of M@PEI-PCPs have a curve that describes the slow affinity to CO2. Generally, adsorption isotherm curves are below desorption isotherm curves [47]. Therefore, the amount of CO2 captured in the gas phase adsorption isotherm is lower than the desorption isotherm [48]. The CO2 adsorption isotherms show that adsorption and desorption curves coincide in the cases of PCPs and M@PCPs. Figure 6 shows that no significant hysteresis loop was observed in the CO2 adsorption–desorption isotherms of carbon-based materials. As can be seen from Figure 6, the CO2 adsorption–desorption isotherms show that adsorption and desorption curves coincide with PCPs and all M@PCPs. However, there was no overlap in the hysteresis loop of the CO2 adsorption–desorption isotherms of all M@PEI-PCPs. The slow affinity of M@PEI-PCPs to CO2 aids in explaining the lack of overlap in the hysteresis loop of the CO2 adsorption–desorption isotherm. Positive hysteresis loops were observed in the CO2 adsorption–desorption isotherms of all carbon-based particles.
As seen from Figure 6b–d, the CO2 adsorption–desorption isotherms of Co, Cu, and Ni metal-nanoparticle-embedded M@PCPs (Co@PCP, Cu@PCP, or Ni@PCP) show almost the same CO2 capture capacities. On the other hand, a decrease in the CO2 capture capacity of each M@PEI-PC was observed.
Table 4 summarizes the comparison of various biomass-derived carbon-based materials’ CO2 capture performance with the prepared PCP in this study. As summarized in Table 4, the CO2 capture performance of the PCP catalyst is as good the as CO2 capture abilities of some of the biomass-derived carbon-based materials, such as KMHC [49] and GS_KOH_1 [50], reported in the literature. On the other hand, PCP exhibits much better CO2 capture performance than HC [49], MHC [49], and leaves [51] adsorbents.
However, there are also studies that reported higher CO2 capture performances than that of PCP. Among these reported studies, PDS_KOH_1 [50], AS-2-600 [52], and OC700 [53] adsorbents exhibited much better CO2 capture capacity than PCP adsorbents under the same conditions as given in Table 4.

4. Conclusions

In this study, porous carbon particles, PCPs, which are very versatile adsorbents, were used for CO2 capture technologies. They were prepared from a nature molecule, sucrose. Employing hydrothermal and carbonization methods and using SiO2 particles as porogen, PCPs were readily prepared. The prepared PCPs were further chemically modified with branched and linear PEIs to increase the functionality. A decrease in the surface area of the PEI-modified PCPs was observed after modification due to pore blockage of the PEI chain on the PCP surfaces. According to BET results, the surface area value of PCPs was 325.58 m2/g before modification, then decreased to 32.84 and 2.18 m2/g after modification with B-PEI and L-PEI, respectively. In addition, pore blocking due to the surface coating of these amine groups coming from PEIs caused a significant decrease in surface area [54,55,56]. The use of PCPs, B-PEI-PCPs, and PEI-PCPs as adsorbents in CO2 capture at 25 °C under 1.18 atm (899 mmHg) pressure revealed that PCPs adsorbed 2.36 mmol CO2/g absorbent, whereas the B-PEI-PCPs and L-PEI-PCPs adsorbed 1.05 and 0.96 mmol CO2/g absorbent, respectively. Again, the reason for the decrease in CO2 capture capacity can be explained due to the decrease in surface area of B/L-PEI-PCPs as a result of the modification. On the other hand, the presence of PEI on the surface of PCPs is useful, enabling the generation of new functional groups such as amines that are also known for CO2 binding tendency as well as metal ion binding ability, so that the adsorbed CO2 can be converted into useful fuels/chemicals. For this purpose, Co, Cu, and Ni metal nanoparticles were prepared within both PCPs and PEI-PCPs, and their CO2 capture performances were compared. It was found that the CO2 capture performances of M@PCPs are very close to each other, e.g., Cu@PCP, Co@PCP, and Ni@PCP captured 1.66, 1.73, and 1.72 mmol CO2/g absorbent, respectively. On the other hand, a decrease in CO2 adsorption capacity was observed in the CO2 for M@PEI-PCPs compared to PEI-PCPs or M@PCPs. Although the CO2 capture capacity of M@PCPs or M@PEI-PCPs are not as high as PCPs, these materials contain metal nanoparticles that enable further use of the captured CO2 for different fuel or chemical compound generation such as methanol, ethanol, acetone, formic acid, etc., for future studies. In fact, our future studies will focus on the use of M@PCP and M@PEI-PCP composites as catalysts to convert the captured CO2 into fuel and/or different compounds, and this may be possible at high temperatures. Therefore, M@PCPs will have the advantage of being resistant to high temperatures in comparison to PEI-containing forms, M@PEI-PCPs, which are composites to be used as catalysts for the catalytic conversion of the captured CO2.

Author Contributions

Conceptualization, N.S.; methodology, B.A. and N.S.; validation, B.A. and N.S.; formal analysis, E.I. and A.K.S.; investigation, B.A.; resources, N.S. and A.K.S.; writing—original draft preparation, B.A. and N.S.; writing—review and editing, N.S., E.I. and A.K.S.; visualization, N.S. and E.I.; supervision, N.S. and A.K.S.; project administration, N.S.; funding acquisition, N.S. and A.K.S. All authors have read and agreed to the published version of the manuscript.

Funding

This research received no external funding.

Data Availability Statement

Data are contained within the article.

Acknowledgments

The support from the Scientific and Technological Council of Turkey (TUBITAK-2219) is greatly appreciated.

Conflicts of Interest

The authors declare no conflicts of interest.

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Jcs 08 00338 g001
Figure 1. (a) Synthesis diagram and (b) FE-SEM image of the synthesis of sucrose-derived porous carbon particles (PCPs).
Figure 1. (a) Synthesis diagram and (b) FE-SEM image of the synthesis of sucrose-derived porous carbon particles (PCPs).
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Figure 2. The schematic illustration of the modification of (a) porous carbon particles and their amination with (b) B-PEI and (c) L-PEI and their corresponding SEM images.
Figure 2. The schematic illustration of the modification of (a) porous carbon particles and their amination with (b) B-PEI and (c) L-PEI and their corresponding SEM images.
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Figure 3. (a) FT-IR spectra and (b) thermal degradation profiles of PCPs and their PEI-modified forms.
Figure 3. (a) FT-IR spectra and (b) thermal degradation profiles of PCPs and their PEI-modified forms.
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Figure 4. (a) XRD patterns of PCP and B-PEI-PCPs and the metal-nanoparticle-loaded forms of B-PEI-PCPs, SEM images of (b) PCPs and (c) B-PEI-PCPs, and (d) TEM images of PCPs, B-PEI-PCPs, and M@B-PEI-PCPs (M: Co, Cu, and Ni).
Figure 4. (a) XRD patterns of PCP and B-PEI-PCPs and the metal-nanoparticle-loaded forms of B-PEI-PCPs, SEM images of (b) PCPs and (c) B-PEI-PCPs, and (d) TEM images of PCPs, B-PEI-PCPs, and M@B-PEI-PCPs (M: Co, Cu, and Ni).
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Figure 5. N2 adsorption–desorption isotherms of (a) PCPs and PEI-modified PCPs (B-PEI-PCP and L-PEI-PCP); (b) metal-nanoparticle-embedded PCPs (M@PCPs). Pore size distribution of (c) PCPs and PEI-modified PCPs (B-PEI-PCP and L-PEI-PCP); (d) metal-nanoparticle-embedded PCPs (M@PCPs).
Figure 5. N2 adsorption–desorption isotherms of (a) PCPs and PEI-modified PCPs (B-PEI-PCP and L-PEI-PCP); (b) metal-nanoparticle-embedded PCPs (M@PCPs). Pore size distribution of (c) PCPs and PEI-modified PCPs (B-PEI-PCP and L-PEI-PCP); (d) metal-nanoparticle-embedded PCPs (M@PCPs).
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Figure 6. CO2 adsorption–desorption isotherms of (a) porous carbon-based particles, (b) Co metal-nanoparticle-embedded porous carbon-based particles, (c) Cu metal-nanoparticle-embedded porous carbon-based particles, and (d) Ni metal-nanoparticle-embedded porous carbon-based particles.
Figure 6. CO2 adsorption–desorption isotherms of (a) porous carbon-based particles, (b) Co metal-nanoparticle-embedded porous carbon-based particles, (c) Cu metal-nanoparticle-embedded porous carbon-based particles, and (d) Ni metal-nanoparticle-embedded porous carbon-based particles.
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Table 1. Metal nanoparticle contents of M@PCPs and M@PEI-PCPs (M: Ni, Co, and Cu).
Table 1. Metal nanoparticle contents of M@PCPs and M@PEI-PCPs (M: Ni, Co, and Cu).
PCPs TypesCo (mg/g)Cu (mg/g)Ni (mg/g)
PCP74.6 ± 572.1 ± 721.4 ± 3
B-PEI-PCPs36.6 ± 244.5 ± 510.2 ± 0.2
L-PEI-PCPs26.9 ± 129.9 ± 23.1 ± 0.9
Table 2. Surface area, pore volume, and pore size of carbon-based particles.
Table 2. Surface area, pore volume, and pore size of carbon-based particles.
Carbon Particle TypesSurface Area (m2/g) aPore Size (nm) bPore Volume (cm3/g) b
PCP325.582.940.07
B-PEI-PCPs32.8419.31 0.31
L-PEI-PCPs2.1813.960.63
Co@PCP125.2010.800.27
Cu@PCP255.5712.420.33
Ni@PCP226.7310.520.12
a Measured using N2 adsorption with the Brunauer–Emmett–Teller (BET) method. b Pore volume and pore size in diameter calculated by the desorption data using the Barrett–Joyner–Halenda (BJH) method.
Table 3. CO2 capture capacities of the carbon-based materials at 25 °C under 1.18 atm (899 mmHg) pressure.
Table 3. CO2 capture capacities of the carbon-based materials at 25 °C under 1.18 atm (899 mmHg) pressure.
PCPs TypesCO2 Capture (mmol/g)
PCP2.36
B-PEI-PCP1.05
L-PEI-PCP0.96
Co@PCP1.66
Co@B-PEI-PCP0.63
Co@L-PEI-PCP0.59
Cu@PCP1.73
Cu@B-PEI-PCP0.51
Cu@L-PEI-PCP0.41
Ni@PCP1.72
Ni@B-PEI-PCP0.81
Ni@L-PEI-PCP0.87
Although the presence of B-PEI or L-PEI on PCPs and their metal-nanoparticle-containing form, M@B/L-PEI-PCP, reduced the CO2 adsorption capacity, it also provided some amine functionality which would be very useful in the catalytic conversion of the capture of CO2 to some useful product such as methanol, ethanol, formic acid, etc. [7,10,11,12].
Table 4. Comparison of CO2 capture performance of PCP with other biomass-derived carbon-based materials.
Table 4. Comparison of CO2 capture performance of PCP with other biomass-derived carbon-based materials.
Biomass-DerivedAdsorbentsTemperature (°C)CO2 Capture (mmol/g)Reference
Coffee groundsHC350.14[49]
MHC0.85
KMHC2.67
Palm date seedsPDS_KOH_1254.36[50]
Guava seedsGS_KOH_1253.02[50]
LeaveA. procera leaves252.11[51]
SawdustAS-2-600254.80[52]
Tobacco stemOC700254.84[53]
SucrosePCP252.36This study
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Ari, B.; Inger, E.; Sunol, A.K.; Sahiner, N. Optimized Porous Carbon Particles from Sucrose and Their Polyethyleneimine Modifications for Enhanced CO2 Capture. J. Compos. Sci. 2024, 8, 338. https://doi.org/10.3390/jcs8090338

AMA Style

Ari B, Inger E, Sunol AK, Sahiner N. Optimized Porous Carbon Particles from Sucrose and Their Polyethyleneimine Modifications for Enhanced CO2 Capture. Journal of Composites Science. 2024; 8(9):338. https://doi.org/10.3390/jcs8090338

Chicago/Turabian Style

Ari, Betul, Erk Inger, Aydin K. Sunol, and Nurettin Sahiner. 2024. "Optimized Porous Carbon Particles from Sucrose and Their Polyethyleneimine Modifications for Enhanced CO2 Capture" Journal of Composites Science 8, no. 9: 338. https://doi.org/10.3390/jcs8090338

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