Search

Physisorption of methane in porous solids has been actively studied to achieve high methane storage capacity, but it requires heavy vessels due to the high pressures involved. In addition, physisorption of methane is quite sensitive to temperature elevation, even near ambient conditions. We developed a method for high-density methane storage at ambient pressure by installing pore-entrance locks controlled by waste heat at 473 K. Under ambient conditions, the entrance locks are stable enough to store a large amount of highly pressurized methane in the carbon nanopores at 19.9 MPa and can be unlocked at 473 K for encapsulation and release of methane. This novel ambient pressure storage method for pressurized methane enables storage of more methane than any other adsorbent at 3.5 MPa and 298 K. The waste-heat open/close pore-entrance locking mechanism supports long-term storage of a renewable energy source and provides a stationary energy supply.

Separation of CO2 based on adsorption, absorption, and membrane techniques is a crucial technology necessary to address current global warming issues. Porous media are essential for all these approaches and understanding the nature of the porous structure is important for achieving highly efficient CO2 adsorption. Porous carbon is considered to be a suitable porous media for investigating the fundamental mechanisms of CO2 adsorption, because of its simple morphology and its availability in a wide range of well-defined pore sizes. In this study, we investigated the dependence of CO2 adsorption on pore structures such as pore size, volume, and specific surface area. We also studied slit-shaped and cylindrical pore morphologies based on activated carbon fibers of 0.6–1.7 nm and carbon nanotubes of 1–5 nm, respectively, with relatively uniform structures. Porous media with larger specific surface areas gave higher CO2 adsorption densities than those of media having larger pore volumes. Narrower pores gave higher adsorption densities because of deep adsorption potential wells. However, at a higher pressure CO2 adsorption densities increased again in nanopores including micropores and small mesopores. The optimal pore size ranges of CO2 adsorption in the slit-shaped and cylindrical carbon pores were 0.4–1.2 and 1.0–2.0 nm, respectively, although a high adsorption density was only expected for the narrow carbon nanopores from adsorption potentials. The wider nanopore ranges than expected nanopore ranges are reasonable when considering intermolecular interactions in addition to CO2–carbon pore interactions. Therefore, cooperative adsorption among CO2 in relatively narrow nanopores can allow for high density and high capacity adsorption.

Single-walled carbon nanotubes (SWCNTs) have been recognized as promising nanocarriers by many researchers from around the world through hundreds of articles published in the last decade pertaining to SWCNTs-based drug delivery applications. In line with this issue, systematic studies of non-covalent interaction between camptothecin (CPT) and the oxidized SWCNTs (Ox-SWCNTs) have been done in this work. Through the developed process of purification and acid oxidation, we obtained the Ox-SWCNTs that were essentially free of metals and well dispersed in aqueous solutions. A quenching phenomenon, which is indicative of the interactions between CPT and the Ox-SWCNTs, was observed and used as the basis of analysis for monitoring the adsorption of CPT. A comparison of the kinetic models and the overall adsorption capacity was best described by the pseudo second-order kinetic model and Weber–Morris kinetic model. Langmuir and Freundlich models were introduced to fit the adsorption isotherms data. The adsorption of CPT was found to be dependent on concentration and adsorption temperature. The thermodynamic analysis exhibited that the adsorption of CPT on the Ox-SWCNTs was exothermic and spontaneous.

In this study, CO2 occlusion of K2CO3 was examined at different temperatures under moist conditions. The CO2 occlusion rate increased with increasing temperatures, whereas the saturated occlusion amount decreased. The highest occlusion amount (i.e. 6.48 mmol·g–1) was obtained at 313 K. Results of X-ray powder diffraction analysis showed that the formation of bicarbonate as a result of the K2CO3 decomposition with CO2 and H2O involved two reactions with K4H2(CO3)3·1.5H2O as an intermediate. It was determined that the lower saturated occlusion amount at higher temperatures originated from the exothermic property of the second reaction. Because the equilibrium constant for the bicarbonate formation is smaller at higher temperatures, the reaction does not proceed as quickly or efficiently according to Le Châtelier’s principle. Therefore, the CO2 occlusion of K2CO3 is suitable for the saturated occlusion amount at lower temperatures.

The ability of an activated carbon (AC) to adsorb 18 different cytokines with molecular weights ranging from 8 kDa to 70 kDa and high mobility group box-1 (HMGB1) from inflammatory model plasma at 310 K and the mechanisms of adsorption were examined. Porosity analysis using N2 gas adsorption at 77K showed that the AC had micropores with diameters of 1-2 nm and mesopores with diameters of 5-20 nm. All 18 cytokines and HMGB1 were adsorbed on the AC; however, the shapes of the adsorption isotherms changed depending on the molecular weight. The adsorption isotherms for molecules of 8-10 kDa, 10-20 kDa, 20-30 kDa, and higher molecular weights were classified as H-2, L-3, S-3, and S-1 types, respectively. These results suggested that the adsorption mechanism for the cytokines and HMGB1 in the mesopores and on the surface of the AC differed as a function of the molecular weight. On the basis of these results, it can be concluded that AC should be efficient for cytokine adsorption.

To develop high-performance activated carbons (ACs) for adsorption heat pumps (AHPs), it is important to characterize the adsorption behaviors of the refrigerant molecules in the pores of ACs. Not only pore structures, such as pore size and shape, but also surface functionalities strongly influences the adsorption behaviors, especially for polar molecules, such as water and ethanol, which are typical refrigerants for AHP. In this study, we examined the influence of surface functional groups on the adsorption behaviors of ethanol molecules in carbon micropores using model ACs with different amounts of oxygen-containing surface functional groups but comparable porosities. For the AC with an increased amount of surface functional groups, ethanol adsorption/desorption isotherms showed significant decreases in the adsorption amounts and shortened adsorption equilibrium times compared to those with less surface functional groups throughout the entire relative pressure region. This suggests diffusional hindrance of ethanol molecules in micropores with abundant surface functional groups. To verify our hypothesis, we examined the influence of surface functional groups on the adsorption behavior of ethanol molecules using a solid-state NMR technique. The NMR results revealed that the hydroxyl group of ethanol molecules strongly interacts with the surface functional groups, giving rise to an oriented adsorption of ethanol molecules in the micropores with oxygen-containing surface functional groups. Furthermore, electrochemical analyses confirmed that diffusion resistance of electrolyte ions in the micropores increases after the introduction of oxygen-containing surface functional groups, which supports our hypothesis.

We fabricated nanoscale BaTiO3 and its asymmetric crystal structure was obtained using an asymmetric reaction field in carbon nanospaces. The nano-crystal phases changed from symmetric to asymmetric crystals with decreasing crystallite size. The fabrication of an asymmetric crystal in a nanospace can be adapted for various ceramic fabrications.

Electron density of single wall carbon nanotubes (SWCNT) is effectively modified by hexaiodobenzene (HIB) molecules using liquid-phase adsorption. UV-Vis-NIR absorption spectra of the HIB-adsorbed SWCNT, especially in the NIR region, showed a disappearance of S11 transitions between the V1 valance band and the C1 conduction band of van Hove singularities which can be attributed to the effective charge transfer between HIB and the SWCNT. The adsorption of HIB also caused significant peak-shifts (lower frequency shift around 170 cm−1 and higher shift around 186 cm‑1) and an intensity change (around 100–150 cm−1 and 270–290 cm−1) in the radial breathing mode of Raman spectra. The charge transfer from SWCNT to HIB was further confirmed by the change in the C1s peak of X-ray photoelectron spectrum, revealing the oxidation of carbon in SWCNT upon HIB adsorption.

High-pressure adsorption isotherms of hydrogen onto amorphous carbon mesotubes (ACMs) prepared from fluorine polymer and onto activated carbon fibres (ACFs) were measured at temperatures of 77, 196 and 303 K, respectively, at pressures up to 10 MPa. The adsorption isotherms for ACMs and ACFs at 77 K exhibited maxima at 1 MPa (8.0 wt%) and 4 MPa (3.7 wt%), respectively, although both isotherms at 303 K were of the Henry type and both amounts of hydrogen adsorbed at 8 MPa were less than 0.3 wt%. The maximum hydrogen adsorption amount for ACMs per unit micropore volume as determined by N 2 adsorption was 10-times larger than that for ACFs. ACMs are different from ACFs in that they are thought to have specific ultramicropores, although characterization using high-resolution transmission electron microscopy, X-ray photoelectron spectroscopy and Raman spectroscopy showed that they possessed a nanographitic structure similar to that of ACFs.

The adsorptivities of supercritical CH(4) and H(2) of the external and internal tube walls of single wall carbon nanotube (SWCNT) were determined. The internal tube wall of the negative curvature showed the higher adsorptivities for supercritical CH(4) and H(2) than the external tube wall of the positive curvature due to their interaction potential difference. Fine SWCNT bundles were prepared by the capillary force-aided drying treatment using toluene or methanol in order to produce the interstitial pore spaces having the strongest interaction potential for CH(4) or H(2); the bundled SWCNT showed the highest adsorptivity for supercritical CH(4) and H(2). It was clearly shown that these nanostructures of SWCNTs are crucial for supercritical gas adsorptivity., Article, ADSORPTION-JOURNAL OF THE INTERNATIONAL ADSORPTION SOCIETY. 17(3):643-651 (2011)

The adsorption of cyclohexene with two sp2and four sp3carbon atoms in graphitic slit pores was studied by performing grand canonical Monte Carlo simulation. The molecular arrangement of the cyclohexene on the graphitic carbon wall depends on the pore width. The distribution peak of the sp2carbon is closer to the pore wall than that of the sp3carbon except for the pore width of 0.7 nm, even though the Lennard-Jones size of the sp2carbon is larger than that of the sp3carbon. Thus, the difference in the interactions of the sp2and sp3carbon atoms of cyclohexene with the carbon pore walls is clearly observed in this study. The preferential interaction of sp2carbon gives rise to a slight tilting of the cyclohexene molecule against the graphitic wall. This is suggestive of a π-π interaction between the sp2carbon in the cyclohexene molecule and graphitic carbon.

Coordination polymers (CPs) or metal-organic frameworks (MOFs) have attracted considerable attention because of the tunable diversity of structures and functions. A 4,4'-bipyridine molecule, which is a simple, linear, exobidentate, and rigid ligand molecule, can construct two-dimensional (2D) square grid type CPs. Only the 2D-CPs with appropriate metal cations and counter anions exhibit flexibility and adsorb gas with a gate mechanism and these 2D-CPs are called elastic layer-structured metal-organic frameworks (ELMs). Such a unique property can make it possible to overcome the dilemma of strong adsorption and easy desorption, which is one of the ideal properties for practical adsorbents.

Activated carbon fibres with extremely high surface areas (ACFs) were prepared by CO2 re-activation using pitch-based ACFs having an original surface area of 1730 m2/g. The highest surface area of the re-activated ACFs was 2930 m2/g as determined from an αS-plot analysis of the nitrogen adsorption isotherm measured at 77 K. The ACF with the highest surface area showed excellent adsorptivity towards supercritical CH4 and H2. The amounts of CH4 and H2 adsorbed were enhanced by 52% and 30%, respectively, as a result of re-activation.

The importance of nanopore structures of carbons is shown in terms of interaction potential for various molecules including supercritical gases such as and . The key factors for adsorption of supercritical and are shown for single wall carbon nanohorn, single wall carbon nanotube, and double wall carbon nanotube. The cluster formation of molecules is a key process for water adsorption on hydrophobic carbon nanopores. The X-ray absorption spectroscopic examination elucidates an explicit dehydration structure of ions confined in carbon nanopores.

Elastic layer-structured metal organic frameworks (ELMs) having flexible two-dimensional structure show a gate phenomenon in sorption/desorption of simple gas molecules. The gate phenomenon is accompanied by expansion/shrinkage of the layers. The gas sorption/desorption is not based on a physical adsorption, but on a chemical reaction, which includes high cooperativity. The cooperative reaction could be analyzed thermodynamically. The gate phenomenon showed advantages in separation of CO2 from mixed gases and in storage of CH4 owing to easy release of absorbed molecules.

N2 adsorption isotherms of molecular sieve carbon were measured at 77 K and 303 K. The Ar adsorption isotherms of molecular sieve carbon samples were also measured at 303 K. The grand canonical Monte Carlo (GCMC) simulation technique was applied to calculate the N2 and Ar adsorption isotherms at 303 K using the ultramicropore volume determined by H2O adsorption. The comparative method of experimental and simulated isotherms of supercritical N2 and Ar at 303 K gave the width of the micropore mouth of the molecular sieve carbon, which can be applied to the ultramicropore width determination for other noncrystalline porous solids.

The nanoporosities and catalytic activities of Pd nanoparticles dispersed on single wall carbon nanohorns (Pd-SWCNHs) and oxidized single wall carbon nanohorns (Pd-ox-SWCNHs) were examined. A transmission electron microscopy (TEM) observation indicated that Pd nanoparticles of 2–3 nm size were highly dispersed on both the SWCNHs. X-ray photoelectron spectra and N2 adsorption isotherms at 77 K illustrated the differences in the deposition process mechanisms of the Pd-SWCNHs and Pd-ox-SWCNHs; the deposition process depended on the surface functional groups. The supercritical H2 adsorption isotherms at 77 K suggested the relationships between the interaction of Pd-SWCNHs and Pd-ox-SWCNHs with H2 and the catalytic activities for a water formation reaction in a gas phase at 273 or 298 K. The catalytic activity measurement and TEM observation of the catalysts after the reactions demonstrated that the Pd-SWCNHs and Pd-ox-SWCNHs are promising catalysts.

Titanium dioxide nanocrystalline particles were synthesized by peroxo titanium acid (PTA) approach from titanium alkoxide and inorganic salt precursors, and their structural and surface properties, porosities, and photocatalytic activities were comparatively examined by XRD, TG/DTA, DRIFT, UV-vis, low temperature N(2) adsorption, and methyl orange (MO) degradation. It was found that nanoparticles with single anatase phase can be obtained from alkoxide precursor even near room temperature if synthesis conditions are appropriately controlled. PTA-derived anatase nanoparticles from titanium alkoxide precursor have smaller crystalline sizes and better porosities, and contain less amount of peroxo group and no organic impurities as compared to those from TiCl(4) precursor. The advantages in structural property, porosity, and surface properties (few deficiencies) lead to a much better photocatalytic activity for TiO(2) nanoparticles from titanium alkoxide precursor in comparison with those from TiCl(4) precursor.

Single wall carbon nanotube (SWCNT), which has bundle structure and entangled structure, was untangled and cut by sonication in hydrogen peroxide (H2O2) solution. The untangled state of SWCNT was examined by SEM, TEM, Raman spectroscopy and N2 adsorption. It was confirmed that the surface area of sonicated nanotubes strongly depended on the sonication time. The BET specific surface area (SSA) of nanotubes sonicated for 3 h was maximum. The SSA decreased at 6 h or more of sonication time. These results indicated that the bundle structure was untangled and the cap of SWCNT was opened. Thus, N2 molecules can access the most efficiently inside of the SWCNT sonicated for 3 h. On the contrary, the sonication treatment for 6 h or more decomposed the nanotubes to produce amorphous carbon, evidenced by TEM and SEM observation; the amorphous carbon blocked the open pore sites such as the internal pore spaces and interstitial pores.

We showed water adsorption isotherms at 303 K on water-resistant three-dimensional (3-D) pillared-layer metal organic frameworks (MOFs) with 1-D semi-rectangular pores, of which size depends on the length of ligand. The shapes of all three adsorption isotherms are type I by IUPAC classification showing strong water-MOFs interaction. The adsorbed amount of water molecules on the hydrophilic site of carboxylic group in 2-D sheets coincided with the crystal water amount. The adsorption on the hydrophilic sites occurs at similar relative pressure even if the used ligand is different.

Naphthalene was adsorbed on single wall carbon nanotubes (SWNT) from trichloroethylene solution. The adsorbed state of naphthalene on dry SWNT samples was studied with X-ray photoelectron spectroscopy and Raman spectroscopy. Adsorption of naphthalene molecules on SWNTs in trichloroethylene provide a uniform coating of external surface of individual SWNTs. Also, a technique of the liquid phase adsorption of naphthalene succeeded to control the assembly structure of the SWNTs, leading to an explicit adsorption hysteresis in the nitrogen adsorption isotherm at 77 K.

The dispersion process of single-wall carbon nanotube (SWNT) by using sodium dodecylbenzene sulfonate (NaDDBS) was studied by means of surface tension measurements, ultraviolet-visible (UV-Vis) spectroscopy, scanning electron microscopy (SEM), and transmission electron spectroscopy (TEM). The critical micelle concentration (CMC) and the concentration where the surface tension begins to drop increase by the presence of SWNT. The isotherm of NaDDBS amount adsorbed on SWNT shows the plateau region at 0.2-6 mM and the saturated region above 40 mM. The external surface of SWNT bundle is fully covered with adsorbed NaDDBS at the plateau region, showing that SWNTs can be dispersed with the bundle form. On the other hand, SWNTs are dispersed in individual tubes at the saturated region, where the adsorption amount corresponds to coating of individual tube surfaces with NaDDBS. This dispersion state was confirmed by SEM and TEM observations. The effect of the dispersion state of SWNTs on radial breathing mode in Raman spectrum gave inherent peak shifts, being the in situ evidences on the step-wise dispersion mechanism of the SWNT bundle to the individual tubes.

SF6 and SF6-N2 mixed gases are used widely as insulators, but such gases have high greenhouse gas potential. The separation of SF6 from SF6-N2 mixed gases is an inevitable result of their use. Single-walled carbon nanohorns (CNHs) were used here for a fundamental study of the separation of SF6 and N2. The diameters of the interstitial and internal nanopores of the CNHs were 0.7 and 2.9 nm, respectively. The high selectivity of SF6 over N2 was observed only in the low-pressure regime in the interstitial 0.7 nm nanopores; the selectively was significantly decreased at higher pressures. In contrast, the high selectivity was maintained over the entire pressure range in the internal 2.9-nm nanopores. These results showed that the wide carbon nanopores were efficient for the separation of SF6 from the mixed gas.

ZSM-5 zeolites with SiO2/Al2O3 molar ratio of 24 were treated in 0.05 M aqueous sodium hydroxide solution at 325 K in different periods. The samples were characterized by means of nitrogen adsorption at 77 K, field emission scanning electron microscopy, X-ray diffractometry, and Fourier transform infrared spectroscopy. Analysis of the experimental results showed that the alkaline treatment periods have influence on the developments and structures of mesopores in the alkaline-treated ZSM-5 zeolites. Alkaline treatment initially develops mesopores mainly from the boundary portion of MFI zeolites to the bulk, while prolonged treatment destroys the mesopores, and an optimum mesoporosity is obtained by the treatment for 1.5 h. On the other hand, crystallinities and short-range order in alkaline treated zeolites have remained virtually unchanged according to the examination from X-ray diffractometry and Fourier transform infrared spectroscopy.

Phenanthrene was adsorbed from ethanol solution to the surface of single wall carbon nanotubes, which were previously physically and chemically characterized. Different anionic surfactants were added in the solutions to enhance the phenanthrene solubility and apparently have also improved the dispersion of two respective nanotube samples used. Adsorbed amount was determined through the concentration difference measured by UV-visible spectrophotometry. Results suggest that adsorption of phenanthrene is extremely improved in the case of nanotube purified with higher quality. These findings were confirmed by X-ray photoelectron spectroscopy. The influence of the surfactant on the adsorption kinetics of phenanthrene is suggested to be significant as well.

N2 adsorption on Cu–organic crystals [Cu(bpy)2(BF4)2] (bpy = bipyridine) at 77 K begins suddenly at P/P 0 = 0.1. This unique adsorption is named gate adsorption. Gate adsorption is associated with the change of crystal structure from GCMC and dynamic GCMC simulations. An expansion of 10% opens internal pore spaces in the crystal, giving rise to gate adsorption. The complete filling of the internal spaces with N2 molecules induces an expansion of 30%.

Single-wall carbon nanohorn (SWNH), which is a tubular particle with a cone cap, was oxidized in an oxygen flow at various temperatures. N(2) adsorption at 77 K, thermogravimetry (TG), differential thermal analysis (DTA), transmission electron microscopy, and Raman spectroscopy measurements were carried out on the oxidized SWNHs. The specific surface area of the oxidized SWNHs can be controlled by oxidation temperature, giving the maximum value of 1420 m(2)/g. The pore size distribution by the BJH method and the comparison plot of the N(2) adsorption isotherms of SWNH oxidized at different temperatures against that of as-grown SWNH revealed the minimum oxidation temperature for opening internal nanopores. TG-DTA analyses determined the components of as-grown SWNH: amorphous carbon 2.5 wt %, defective carbon at the cone part 15 wt %, tubular carbon 70 wt %, and graphitic carbon 12 wt %. These systematic analyses provided the exact internal nanopore volume of 0.49 mL/g for pure SWNH particles.

A novel nanoporous C/SiO2 composite was synthesized using graphite precursor by a soft chemical method and its adsorption properties were characterized by nonane, water, and nitrogen adsorption. It was found that only one part of micropores can strongly confine nonane molecules, indicating a wide micropore size distribution. Water adsorption leads to disappearance of one part of micropores, possibly due to closing of pores by dissociative adsorption of water on defective sites. Fractal analysis of the original and the differential nitrogen adsorption isotherms indicate that micropores have a rougher surface and mesopore a flatter surface, suggesting that micropores are surrounded by silica particles and mesopores involve the flat carbon layers.

The average interstitial nanopore structure of single-wall carbon nanohorn (SWNH) assemblies was determined using X-ray diffraction and grand canonical Monte Carlo (GCMC) simulation aided N(2) adsorption at 77 K. The interstitial nanopores of SWNH assemblies can be regarded as quasi one-dimensional pores due to the partial orientation of the SWNH particles; the average pore width of the interstitial pores is 0.6 nm. Good agreement between the GCMC simulation of a structural model with one-dimensional interstitial nanopores and an experimental adsorption isotherm below P/P(0) = 10(-4) is evidence of the quasi one-dimensionality of the interstitial nanopores. A snapshot from the GCMC simulation showed one-dimensional growth of adsorbed N(2) molecules.

Nanoporous metallic platinum with a high specific surface area of 91 m 2 /g was synthesized by a templating method using nonporous silica nanoparticles. The templating reaction is constituted of four steps: (1) a coating reaction of a Pt compound on the silica surface; (2) reduction of the Pt compound; (3) dissolution of the silica by alkaline treatment; (4) removal of residual carbon in the nanoporous platinum by heat treatment. Thus, nanoporous metallic platinum, stabilized by a small amount of carbon, can successfully be obtained by a relatively convenient synthetic process. This material can be a promising model material for development of new scientific fields concerned with electromagnetic properties and a functional material applicable to fuel cell or catalytic reactions.

Resorcinol-formaldehyde aerogels and carbon aerogels of different mesoporosities have been used as templates for preparing bimodal zeolites of mesopores. Samples were thoroughly characterized with X-ray diffraction, field emission scanning electron microscopy, thermogravimetric analysis, X-ray photoelectron spectroscopy, N(2) adsorption at 77 K, as well as FT-IR spectroscopy and (29)Si nuclear magnetic resonance spectroscopy. The mesoporous ZSM-5 zeolites have additional mesopores of 9-25 nm in widths and 0.07-0.2 cm(3)/g in volumes, besides their perfect inherent micropores. Experimental results show the mesoporous systems of the finally obtained zeolites can be influenced by proper preparation of resorcinol-formaldehyde aerogels and carbon aerogels through solution chemistry. Consequently, zeolites of tunable mesoporosities can be prepared with this unique methodology.