CO2-pressure swing activation for efficient production of highly porous carbons

In this work, we describe a new type of activation method of carbon materials using pressure swing of CO2. The porosity development markedly depends on the pressure swinging frequency. The porous carbon obtained from pressure-swing activation shows an additional porosity development without pitting corrosion on the surface, which occurs on CO2 activation without pressure-swing. This phenomenon is ascribed to the enhancement of Knudsen diffusion and/or configurational diffusion of CO2 which is caused by an exterior stimulus from the pressure swing. (C) 2015 Elsevier Ltd. All rights reserved.ArticleCARBON. 85:245-248 (2015)journal articl

Comparative pore structure analysis of highly porous graphene monoliths treated at different temperatures with adsorption of N-2 at 77.4 K and of Ar at 87.3 K and 77.4 K

We prepared nanoporous graphene monolith of different porosity by high temperature treatment up to 2073 K in Ar. The porosity is comparatively evaluated with N-2 adsorption isotherms at 77.4 K and Ar adsorption isotherms at 87.3 K and 77.4 K. N-2 adsorption at 77.4 K shows an excess adsorption amount below 3 x 10(-3) of the relative pressure which is caused by the quadrupole moment of an N-2 molecule. This effect doesn't give significant influence on the determination of the total surface area from subtracting pore effect (SPE) method, the micropore volume from Dubinin-Radushkevich (DR) method and the total pore volumes from the Gurvitch rule. However, the peak of the micropore size distribution determined by Horvath-Kawazoe (HK) method from N-2 adsorption at 77.4 K shifts to a smaller size than that from Ar adsorption at 87.3 K by 0.05-0.09 nm. (C) 2015 Elsevier Inc. All rights reserved.ArticleMICROPOROUS AND MESOPOROUS MATERIALS. 209:72-78 (2015)journal articl

Robust graphene-based monoliths of homogeneous ultramicroporosity

Graphite oxide (GO) and graphene monoliths were prepared using the unidirectional freezing of GO water suspension. These materials were saturated with a poly(ammonium-4-styrene sulfonate) water soluble polymer and then carbonized at 1123 K. This process increases significantly the materials strength and density. A uniform deposition of the polymer-derived carbon on the external layers of the graphene sheets of the monolith was found. The carbon from polymer not only provided more contact between the graphene sheets but also apparently increased the overall graphitization level (based on Raman spectra). The modification decreased the electrical resistance by one order of magnitude compared to that of the graphene monolith. N-2 adsorption at 77 K showed that the thus-treated graphene monoliths have quite homogenous pores with the pore width of 0.7 nm. These pores, combined with large transport pores, and conductive properties make the monoliths tested the promising materials for separation, energy storage, and/or gas sensing. The tunability of the properties and pore structure of the robust graphene ultramicroporous monolith through the control of chemistry of the initial GO monolith was shown. (C) 2015 Elsevier Ltd. All rights reserved.ArticleCARBON. 87:87-97 (2015)journal articl

Air separation with graphene mediated by nanowindow-rim concerted motion

International audienceNanoscale windows in graphene (nanowindows) have the ability to switch between open and closed states, allowing them to become selective, fast, and energy-efficient membranes for molecular separations. These special pores, or nanowindows, are not electrically neutral due to passivation of the carbon edges under ambient conditions, becoming flexible atomic frameworks with functional groups along their rims. Through computer simulations of oxygen , nitrogen, and argon permeation, here we reveal the remarkable nanowindow behavior at the atomic scale: flexible nanowindows have a thousand times higher permeability than conventional membranes and at least twice their selectivity for oxygen/nitrogen separation. Also, weakly interacting functional groups open or close the nanowindow with their thermal vibrations to selectively control permeation. This selective fast permeation of oxygen, nitrogen, and argon in very restricted nanowindows suggests alternatives for future air separation membranes

Configurational evidence for antiferromagnetic interaction in disordered magnetic ionic liquids by X-ray scattering-aided hybrid reverse Monte Carlo simulation

Published online: 11 May 2020Magnetic ionic liquids (MIL) are a new type of ionic liquids that show paramagnetic response to magnetic fields. Here, we elucidate a plausible 3D liquid structure of the 1-ethyl-3-methyl-imidazolium tetrachloroferate (Emim[FeCl4]) and 1-butyl-3-methyl-imidazolium tetrachloroferate (Bmim[FeCl4]) MILs by X-ray scattering-aided hybrid reverse Monte Carlo simulations. Bmim[FeCl4] showed anomalously continuous structural changes over a wide temperature range (90–523 K) without crystallization, while Emim[FeCl4] displayed a melting point at 291 K with no glass transition.Conventional electron radial distribution function (ERDF) analysis provides misleading information about the structures of these MILs due to the mutual cancelation of the partial anion-anion and anion-cation ERDFs. Subsequent hybrid reverse Monte Carlo (HRMC) analysis revealed the precise coordination structures of both ionic liquids, and the alternating periodic arrangement of the anions and cations was visualized based on the HRMC simulation results. The results clearly revealed that the 1st coordination structure of the FeCl4 anion around the Bmim cation was widespread compared to that of the Emim cation, resulting in the absence of crystallization. In addition, we obtained new insights into the antiferromagnetic interaction between the FeCl4− ions of Bmim[FeCl4] even in the absence of the crystallization at low temperatures. Our results shed new light on the development of MILs not only for practical applications but also for the advancing the basic science of pure liquids with a high magnetic response.ArticleJournal of Molecular Liquids.311(1):113321(2020)journal articl

Noticeable Reverse Shift in the Melting Temperatures of Benzene and Carbon Tetrachloride Confined within the Micropores and Mesopores of Hydrophobic Carbons

Carbon aerogels contain both mesopores and micropores. In this study, benzene/CCl4 was adsorbed in the pores of carbon aerogels (both mesopores and micropores) and their phase behaviours were examined using differential scanning calorimetry. The bulk solid benzene melted at 278 K and the melting temperatures of benzene confined inside the mesopores and micropores of carbon aerogels were 258 and 293 K, respectively. Although the melting temperature depression of condensates in mesopores is well known, the observed elevation of the melting temperature for micropores is very limited in the strongly interacted system. Similar melting behaviours were observed for the confined CCl4; depression by 45 K in mesopores and elevation by 48 K in micropores showed about two times the change as compared with that of confined benzene.ArticleADSORPTION SCIENCE & TECHNOLOGY. 31(2-3):145-151 (2013)journal articl

Very high methane uptake on activated carbons prepared from mesophase pitch: A compromise between microporosity and bulk density

Two petroleum residues were pyrolyzed under two different conditions to obtain pitches with low or high mesophase content. The effect of the KOH: precursor ratio and the activation temperature on the packing density and porous texture of the carbons have been studied and optimized. Activated carbons combining high micropore volume (>1 cm3/g) and high packing density (0.7 g/cm3) have been successfully prepared. Regarding excess methane adsorption capacities, the best results (160 cm3 (STP)/cm3 at 25 °C and 3.5 MPa) were obtained using the pitch with the higher content of the more organized mesophase, activated at relatively low temperature (700 °C), with a medium KOH: precursor ratio (3:1). Some of the activated carbons exhibit enhanced adsorption capacity at high pressure, giving values as high as 175 cm3 (STP)/cm3 at 25 °C and 5 MPa and 200 cm3 (STP)/cm3 at 25 °C and 10 MPa (the same amount as in an empty cylinder but at half of the pressure), indicating a contribution of large micropores and narrow mesopores to adsorption at high pressure. The density of methane in pores between 1 and 2.5 nm at pressure up to 10 MPa was estimated to understand their contribution to the total adsorption capacity.Authors acknowledge financial support from MINECO: Project MAT2013-45008-p and CONCERT Project-NASEMS (PCIN-2013-057) and Generalitat Valenciana (PROMETEO/2009/002)

Selective probe of the morphology and local vibrations at carbon nanoasperities

We introduce a way to selectively probe local vibration modes at nanostructured asperities such as tips of carbon nanohorns. Our observations benefit from signal amplification in surface-enhanced Raman scattering (SERS) at sites near a silver surface. We observe nanohorn tip vibration modes in the range 200-500 cm(-1), which are obscured in regular Raman spectra. Ab initio density functional calculations assign modes in this frequency range to local vibrations at the nanohorn cap resembling the radial breathing mode of fullerenes. Careful interpretation of our SERS spectra indicates presence of caps with 5 or 6 pentagons, which are chemically the most active sites. Changes in the peak intensities and frequencies with time indicate that exposure to laser irradiation may cause structural rearrangements at the cap.ArticleJOURNAL OF CHEMICAL PHYSICS. 136(6):064505 (2012)journal articl

Electronically modified single wall carbon nanohorns with iodine adsorption

Tailoring electronic properties of single wall carbon nanohorn (SWCNH) is expected to develop the application potential in various fields. SWCNH is efficiently modified with iodine molecules by liquid phase adsorption. The adsorption isotherm of iodine on SWCNH was Langmuirian with the saturated adsorption amount of 185 +/- 10 mg g (1) (coverage 0.18), indicating a specific interaction between SWCNH and iodine. The DC electrical conductivity of SWCNH film prepared by dip-coating method increased with the iodine adsorption amount almost by a factor 10.ArticleCHEMICAL PHYSICS LETTERS. 501(4-6):485-490 (2011)journal articl