- Nano Express
- Open Access
The CO2 Storage Capacity of the Intercalated Diaminoalkane Graphene Oxides: A Combination of Experimental and Simulation Studies
© Xu et al. 2015
- Received: 18 June 2015
- Accepted: 28 July 2015
- Published: 8 August 2015
To study the effect of interlayer spacing of pillared graphene oxides (GOs) on CO2 uptake, we have obtained CO2 isotherms with respect to the interlayer distance of pillared graphene oxide by both experimental and simulation methods. Interlayer distances of GO were modulated by intercalation of three kinds of diaminoalkanes with a different number of carbon atoms (NH2(CH2) n NH2, n = 4, 8, and 12) as pillars. The intercalated GOs (IGOs) and their reduced products (RIGOs) are characterized using a variety of approaches such as X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), and N2 adsorption. Gas adsorption performance shows that the CO2 uptake of IGOs and RIGOs decrease with the increase of the interlayer distance at low pressure, while at high pressure, the adsorption capacity of IGO-12 has a larger growth than those of both IGO-4 and IGO-8 and surpasses them at 30 bar. The contribution of the electrostatics to CO2 adsorption is larger than that of van der Waals force at low pressures, whereas for the high pressures, the adsorption is dominated by van der Waals force.
- Intercalated graphite oxides
- CO2 adsorption
- Grand canonical Monte Carlo simulation
With the economic growth and industrial development, the excess fossil fuel combustion leads to a rapid increase of global warming and climate change. The rising atmospheric levels of CO2 are considered to be responsible for the warming effect on the climate, because CO2 emissions account for ca. 70 % of the gaseous irradiative force causing the greenhouse effect [1, 2]. Therefore, reducing the anthropogenic emission of CO2 has recently become a political and technological priority . Efficient CO2 capture from existing emission sources plays a crucial role in reducing greenhouse gases in large quantities. However, CO2 has a very low density under ambient conditions and thus is very difficult to be stored. Among various methods, adsorptive storage and capture of CO2 by physical adsorption in porous media is considered as an energetically efficient and technically feasible approach, where the gas sorption and storage capacity is mainly governed by a large accessible surface area and pore structure . A wide variety of tailor-made porous materials, such as various carbon-based adsorbents (e.g., activated carbons [5, 6], carbon nanotubes [7, 8], and graphene ), zeolites [10, 11], and metal−organic frameworks (MOFs) [12, 13] have been proposed and studied for CO2 storage application. Among them, graphene and graphene-based materials are considered as very promising candidates for the adsorption and storage of CO2  due to their unique properties such as large theoretical specific surface area and structural and chemical tenability. For example, Lee et al. reported an adsorption of 6.4 mmol g−1 of CO2 at 30 bar and 298 K on exfoliated graphene oxide (GO) with a specific surface area (SSA) of 547 m2 g−1 and a total pore volume of 2.47 cm3 g−1 . Mishra and Ramaprabhu found that a hydrogen-exfoliated graphene with a SSA of 443 m2 g−1 shows an enhanced CO2 adsorption of 21.6 mmol g−1 at 11 bar and 298 K . Meng and Park developed a kind of vacuum exfoliated graphene nanoplates with a high capture capacity, up to 56 mmol g−1, at 30 bar and 298 K . They also found that the improved CO2 capture capacity of the graphene nanoplates is attributed to the larger interlayer spacing and higher interior void volume .
However, most of the pure graphene materials prepared seem very difficult to reach the theoretical specific surface area (2600 m2 g−1 ) and realize expanded graphene layers without any supports inserted between them. Therefore, pillaring of graphene or graphene oxide with organic ligands has been considered . Recently, Zhou et al. designed and fabricated a porous graphene material by linking non-planar terpyridine complexes through an azide–alkyne click reaction . This complex possesses high specific surface area of 440 m2 g−1, and its carbon dioxide capacity could reach up to 2.6 mmol g−1 at 273 K and 1 atm. Burress et al.  developed a novel pillared graphene oxide framework (GOF) material by cross-linking the benzenediboronic acids between GO layers. The GOF material shows the maximum interlayer distance of 1.05 nm and SSA of 470 m2 g−1 and presents a good CO2 adsorption of ~2.7 mmol g−1 at 4 bar and room temperature . All these demonstrate that interlayer spacing of graphene-based materials could be tuned using pillaring molecules and thus remarkably influences their gas adsorption capacity. However, to the best of our knowledge, the investigations are rather scarce for dealing with the evolution of CO2 adsorption properties with interlayer spacing of graphene-intercalated materials.
In this work, we investigated CO2 uptake for a wide range of interlayer distances using the three-dimensional structure of GO obtained from intercalation of diaminoalkanes (H2N(CH2) n NH2). The interlayer spacing of intercalated composites was controlled precisely by adjusting the number of methylene units in H2N(CH2) n NH2 (n = 4, 8, and 12). The effect of structural parameters of intercalated composites on their CO2 adsorption properties was studied by a combination of experiment and grand canonical Monte Carlo (GCMC) simulation.
Graphite powder (~1.5 μm) was purchased from Qingdao Ruisheng Graphite Co., Ltd. The diaminoalkanes were purchased from Aladdin Chemical Reagents Company. All others reagents were purchased from Shanghai Chemical Reagents Company and used as received. Graphite oxide was prepared according to a modified Hummers method . GO suspension (6 mg ml−1) was prepared by dispersing graphite oxide in deionized water under ultrasonication for 1 h. The diaminoalkane-intercalated graphene oxides (IGOs) were synthesized according to Margarita’s method . In a typical synthesis, 4.16 mmol of 1,n-diaminooctane (where n represents the number of methylene units in diaminoalkanes) was dissolved into 35 mL of ethanol under stirring. The resulting solution was added into 33 ml of the as-prepared GO suspension under vigorous stirring at ambient temperature. The reaction continued for 48 h at room temperature with continuous stirring. Afterwards, the resulting solution was isolated by centrifugation, washed sequentially with deionized water/ethanol mixture (1:1 volume ratio) four times, then filtered, and dried in a vacuum oven at 80 °C for 24 h. The as-synthesized IGOs were then reduced by hydrazine hydrate at room temperature and dried at 50 °C under vacuum. The resultant was designated as reduced IGO (RIGOs).
The interlayer distances of IGOs and RIGOs were examined by X-ray powder diffraction (XRD; PANalytical B.V., Netherlands) using a Cu Kα1 radiation (0.15405 nm). The surface properties of the samples were characterized using Fourier transform infrared spectroscopy (FT-IR; Nicolet 6700, USA) and X-ray photoelectron spectroscopy (XPS; PHI 5000 VersaProbe, ULVAC-PHI, Japan). Nitrogen adsorption–desorption isotherms were measured at liquid nitrogen temperature (77 K) and CO2 adsorption was performed at 273 K and 298 K using a surface area and porosity analyzer (ASAP2020M, Micromeritics, USA). The carbon samples were degassed under turbomolecular vacuum before sorption measurements. N2 and CO2 gases with super high purity (99.999 %) were used for the physisorption measurements. The Brunauer, Emmett, and Teller (BET) equation was used to calculate the apparent surface area from N2 adsorption data obtained at P/P 0 between 0.05 and 0.2. For advanced porosity analysis, pore size distributions and cumulative pore volumes were determined by using non-local density functional theory (NLDFT) method considering sorption of CO2 at 273 K in carbon as a model adsorbent and slit-like pores as a pore model. The implemented NLDFT model was supplied by the Quantachrome Autosorb ASiQwin 2.0 software. Note that microscopic methods based on statistical mechanics, such as NLDFT, which allow describing the configuration of the adsorbed phase on a molecular level, are currently considered as the more accurate method.
The Model Structure of IGOs
The periodic models of [C36O2(OH)7(HN(CH2)4NH)]4, [C32O(OH)5(HN(CH2)8NH)]4, and [C28O(OH)3(HN(CH2)12NH)]4 are representative of IGO-n (n = 4, 8, and 12) structures, respectively (Additional file 1: Figure S1). The chemical composition of the models was similar to that indicated by the experimental measurement of diaminoalkane, epoxy, and hydroxyl. The models were generated by using the periodic density functional theory (DFT) calculation, which were performed using the PW91 GGA functional with the double numerical basis set containing polarization functions (DNP) available in the DMol3 code packed in the Materials Studio (MS) 5.0 package [23, 24].
In this study, CO2 molecule was represented by the conventional rigid linear triatomic model with three charged LJ interaction sites (C–O bond length of 0.1149 nm) centered on each atom as developed by Harris and Yung (see Additional file 1: Table S1) . The interactions between the adsorbates and IGOs were described by a combination of site–site LJ and Coulombic potentials. In this work, the universal force fields (UFF)  (see Additional file 1: Table S1), which have been widely used to predict the thermodynamic and dynamic properties of various guests in graphene materials, were employed to model the atoms of IGOs. All the LJ cross-interaction parameters between the adsorbate/adsorbate and adsorbate/IGOs were determined by the Lorentz–Berthelot mixing rule, i.e., ε ij = (ε ii ε jj )1/2, σ ij = (σ ii + σ jj )/2.
Atomic Partial Charge for IGOs
The Mulliken charges were used to simulate the adsorption isotherms of CO2 in the IGOs. These charges were obtained from the periodic DFT calculation, which were performed on the optimized unit cells of IGO using the PW91 GGA functional and the DNP basis set with the DMol3 code packed in the MS 5.0 package [23, 24].
Grand canonical Monte Carlo (GCMC) simulations were conducted to explore the adsorption behaviors of CO2 in the graphene using the MuSic code that was developed by the Snurr group from the Western University (USA) . For the simulations of CO2, four types of attempts are considered: (i) insert, (ii) delete, (iii) transport, and (iv) rotate. The simulation box consisted of 8 (2 × 2 × 2) unit cells for the IGO-4, 24 (2 × 6 × 2) unit cells for the IGO-8, and 12 (3 × 2 × 2) unit cells for the IGO-12 materials. A cutoff radius of 1.2 nm was applied to the LJ interactions, while the long-range electrostatic interactions were handled by the Ewald summation method. Periodic boundary conditions (PBC) were considered in all the three dimensions. The Peng–Robinson equation of state was used to convert the pressure to the corresponding fugacity that was used in the GCMC simulations. For each state point, GCMC simulations consisted of 1 × 107 steps to ensure the equilibration, followed by 1 × 107 steps to sample the desired thermodynamic properties.
Physicochemical properties of GO, RGO, IGOs, and RIGOs
XRD d-spacing (nm)
S BET a (m2 g−1)
S mic b (m2 g−1)
Cumulative pore volume of CO2 (cm3 g−1)
To further modulate the interlayer distance, the reduction by hydrazine hydrate was performed at room temperature. As shown in Fig. 1, RIGOs show two new reflection peaks at 23° (002) and 42.4° (100), suggesting partial reduction of GO. The main reflection peaks of the RIGO-4, RIGO-8, and RIGO-12 appear at 11.3°, 9.5°, and 7.2°, with corresponding interplanar distances of 0.79, 0.94, and 1.24 nm (Table 1), respectively. The interplanar distances of RIGOs are slightly shorter than that of IGOs due to the removal of oxygen-containing groups that weaken the steric effect. However, the pillared structures of RIGOs are maintained after hydrazine reduction at room temperature.
The C 1s XPS spectra of IGOs
The N 1s XPS spectra of IGOs
CO2 Capture Performances
After hydrazine reduction, the micropore surface area determined by CO2 adsorption is found to be 334.7, 148.1, and 118.5 m2 g−1 for RIGOA-n (n = 4, 8, and 12), respectively, and the corresponding CO2 uptake capacity reaches as high as 1.97, 0.80, 0.60 mmol g−1 at 1 atm and 273 K. For RIGOA-n (n = 4, 8, and 12), all their CO2 uptake capacities are larger than that of RGO (~0.28 mmol g−1 at 1 atm and 273 K). When the temperature increases to 298 k, the CO2 adsorption capacity decreases for both IGO-n (0.58, 0.44, and 0.07 mmol g−1 at 1 atm for n = 4, 8, and 12, respectively) and RIGO-n (1.37, 0.66, and 0.29 mmol g−1).
We investigated the effect of interlayer spacing on CO2 uptake for pillared graphene oxides by both experimental and simulation methods. Interlayer distances of GO were tuned by intercalation of three diaminoalkanes (NH2(CH2) n NH2, n = 4, 8, and 12) with different lengths of alkyl chain. At low pressures, the CO2 adsorption capacity of IGOs decreases with the increase of the interlayer distance, where the electrostatic interaction of adsorbent has a larger contribution to the adsorption than van der Waals force. As the pressure increases, CO2 uptake of IGO-12 increases sharply and surpasses those of both IGO-4 and IGO-8 at 30 bar, where the van der Waals force plays a dominant role. This new finding demonstrates that the modulation of interlayer spacing of pillared graphene oxides could enhance their CO2 adsorbability, which provides useful information to design graphene-based materials with superior CO2 adsorption capacity.
This work was supported by the National Natural Science Foundation of China (51107076), Distinguished Young Scientist Foundation of Shandong Province (JQ201215), Natural Science Foundation of Shandong Province (ZR2015BQ009), Taishan Scholar Foundation (ts20130929), Promotive Research Fund for Excellent Young and Middle-aged Scientists of Shandong Province (BS2012NJ015), and Fundamental Research Funds for the Central Universities (12CX02014A and 15CX08010A).
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