Anomalous Increase in Carbon Capacitance at Pore Sizes Less Than 1 Nanometer

Carbon supercapacitors, which are energy storage devices that use ion adsorption on the surface of highly porous materials to store charge, have numerous advantages over other power-source technologies, but could realize further gains if their electrodes were properly optimized. Studying the effect of the pore size on capacitance could potentially improve performance by maximizing the electrode surface area accessible to electrolyte ions, but until recently, no studies had addressed the lower size limit of accessible pores. Using carbide-derived carbon, we generated pores with average sizes from 0.6 to 2.25 nanometer and studied double-layer capacitance in an organic electrolyte. The results challenge the long-held axiom that pores smaller than the size of solvated electrolyte ions are incapable of contributing to charge storage

Phonon Confinement Effects in the Raman Spectrum of Nanodiamond

Nanodiamonds (ND) exhibit unique properties due to their small size and high surface-to-volume ratio compared to bulk diamonds. A reduction in crystal size also affects ND Raman spectra. The confinement of optical phonons in nanocrystals (\u3c10 nm) results in asymmetrically broadened Raman lines, which are shifted toward lower wavenumbers. The phonon confinement model (PCM) relates the observed changes in the Raman spectra to the crystal size and can be used for size characterization at the nanoscale. While the PCM was successfully applied to a variety of materials including Si and BN, results remained unsatisfactory in the case of ND. In order to improve the agreement between the predictions of the model and experimental Raman spectra of ND, effects such as crystal size distribution, lattice defects, and the energy dispersion of the phonon modes were taken into consideration and incorporated into the PCM. This work has shown that phonon wave vectors from small vibrational domains lead to a broad shoulder peak at ~1250 cm-1, that is often observed in the Raman spectrum of ND

Carbide-derived carbons designed for efficient hydrogen storage

Carbide-derived carbons (CDCs) with specific surface area (SSA) ~ 2000 m2/g and open pore volume up to 80% are produced by chlorine etching of metal carbides. Tuning the pore size distribution by carbide precursor selection and etching temperature yields enhanced hydrogen storage capacity at both ambient and elevated pressure. Our goal is to establish the fundamental relation between capacity and SSA, pore size and pore volume

Formation of porous SiC ceramics by pyrolysis of wood impregnated with silica

International Journal of Applied Ceramic Technology, 3(6): pp. 485-490.Biomorphous β-SiC ceramics were produced at 1400°C from pine wood impregnated with silica. This one-step carbothermal reduction process decreases the cost of manufacturing of SiC ceramics compared to siliconization of carbonized wood in silicon vapor. The synthesized sample exhibits 14 m2/g surface area and has a hybrid pore structure with large 5- 20 μm tubular macropores and small (< 50 nm) slit shaped mesopores. SiC whiskers of 20- 400 nm in diameter and 5-20 μm in length formed within the tubular pores. These whiskers are expected to improve the filtration by removing dust particles that could otherwise penetrate through large pores. After ultrasonic milling, the powdered sample showed an average particle size of ~30 nm. The SiC nanopowder produced in this process may be used for manufacturing SiC ceramics for structural, tribological, and other applications

Fano Resonance Between Mie and Bragg Scattering in Photonic Crystals

We report the observation of a Fano resonance between continuum Mie scattering and a narrow Bragg band in synthetic opal photonic crystals. The resonance leads to a transmission spectrum exhibiting a Bragg dip with an asymmetric profile, which can be tunably reversed to a Bragg rise. The Fano asymmetry parameter is linked with the dielectric contrast between the permittivity of the filler and the specific value determined by the opal matrix. The existence of the Fano resonance is directly related to disorder due to non-uniformity of a-SiO2 opal spheres. Proposed theoretical "quasi-3D" model produces results in excellent agreement with the experimental data

Kroll-carbons based on silica and alumina templates as high-rate electrode materials in electrochemical double-layer capacitors

Hierarchical Kroll-carbons (KCs) with combined micro- and mesopore systems are prepared from silica and alumina templates by a reductive carbochlorination reaction of fumed silica and alumina nanoparticles inside a dense carbon matrix. The resulting KCs offer specific surface areas close to 2000 m2 g−1 and total pore volumes exceeding 3 cm3 g−1, resulting from their hierarchical pore structure. High micropore volumes of 0.39 cm3 g−1 are achieved in alumina-based KCs due to the enhanced carbon etching reaction being mainly responsible for the evolution of porosity. Mesopore sizes are uniform and precisely controllable over a wide range by the template particle dimensions. The possibility of directly recycling the process exhaust gases for the template synthesis and the use of renewable carbohydrates as the carbon source lead to a scalable and efficient alternative to classical hard- and soft templating approaches for the production of mesoporous and hierarchical carbon materials. Silica- and alumina-based Kroll-carbons are versatile electrode materials in electrochemical double-layer capacitors (EDLCs). Specific capacitances of up to 135 F g−1 in an aqueous electrolyte (1 M sulfuric acid) and 174 F g−1 in ionic liquid (1-ethyl-3-methylimidazolium tetrafluoroborate) are achieved when measured in a symmetric cell configuration up to voltages of 0.6 and 2.5 V, respectively. 90% of the capacitance can be utilized at high current densities (20 A g−1) and room temperature rendering Kroll-carbons as attractive materials for EDLC electrodes resulting in high capacities and high rate performance due to the combined presence of micro- and mesopores

Double-layer capacitance of carbide derived carbons in sulfuric acid

Electrochemical and Solid-State Letters, 8(7): pp. A357-A360. Retrieved September 19, 2006 from http://nano.materials.drexel.edu/Papers/EDLC_CDC.pdf. DOI: http://dx.doi.org/10.1149/1.1921134Nanoporous carbons obtained by selective leaching of Ti and Al from Ti2AlC, as well as B from B4C, were investigated as electrode materials in electric double-layer capacitors. Cyclic voltammetry tests were conducted in 1 M H2SO4 from 0-250 mV on carbons synthesized at 600, 800, 1000, and 1200°C. Results show that the structure and pore sizes can be tailored and that the optimal synthesis temperature is 1000°C. Specific capacitances for Ti2AlC CDCs and B4C CDCs were 175 and 147 F/g, respectively, compared to multiwall carbon nanotubes and two types of activated carbon, measured herein to be 15, 52, and 125 F/g, respectively

Mesoporous carbide-derived carbon with porosity tuned for efficient adsorption of cytokines

Biomaterials, 27(34): pp. 5755-5762.Porous carbons can be used for the purification of various bio-fluids, including the cleansing blood of inflammatory mediators in conditions such as sepsis or auto-immune diseases. Here we show that the control of pore size in carbons is a key factor to achieving efficient removal of cytokines. In particular, the surface area accessible by the protein governs the rate and effectiveness of the adsorption process. We demonstrate that novel mesoporous carbon materials synthesized from ternary MAX-phase carbides can be optimized for efficient adsorption of large inflammatory proteins. The synthesized carbons, having tunable pore size with a large volume of slit-shaped mesopores, outperformed all other materials or methods in terms of efficiency of TNF-α removal and the results are comparable only with highly specific antibody-antigen interactions

Oxygen-rich microporous carbons with exceptional hydrogen storage capacity

Porous carbons have been extensively investigated for hydrogen storage but, to date, appear to have an upper limit to their storage capacity. Here, in an effort to circumvent this upper limit, we explore the potential of oxygen-rich activated carbons. We describe cellulose acetatederived carbons that combine high surface area (3800 m2 g-1) and pore volume (1.8 cm3 g-1) that arise almost entirely (> 90%) from micropores, with an oxygen-rich nature. The carbons exhibit enhanced gravimetric hydrogen uptake (8.1 wt% total, and 7.0 wt% excess) at -196 ºC and 20 bar, rising to a total uptake of 8.9 wt% at 30 bar, and exceptional volumetric uptake of 44 g l-1 at 20 bar, and 48 g l-1 at 30 bar. At room temperature they store up to 0.8 wt% (excess) and 1.2 wt% (total) hydrogen at only 30 bar, and their isosteric heat of hydrogen adsorption is above 10 kJ mol-1

Interaction of Hydrogen with Graphitic Surfaces, Clean and Doped with Metal Clusters

Producción CientíficaHydrogen is viewed as a possible alternative to the fossil fuels in transportation. The technology of fuel-cell engines is fully developed, and the outstanding remaining problem is the storage of hydrogen in the vehicle. Porous materials, in which hydrogen is adsorbed on the pore walls, and in particular nanoporous carbons, have been investigated as potential onboard containers. Furthermore, metallic nanoparticles embedded in porous carbons catalyze the dissociation of hydrogen in the anode of the fuel cells. For these reasons the interaction of hydrogen with the surfaces of carbon materials is a topic of high technological interest. Computational modeling and the density functional formalism (DFT) are helping in the task of discovering the basic mechanisms of the interaction of hydrogen with clean and doped carbon surfaces. Planar and curved graphene provide good models for the walls of porous carbons. We first review work on the interaction of molecular and atomic hydrogen with graphene and graphene nanoribbons, and next we address the effects due to the presence of metal clusters on the surface because of the evidence of their role in enhancing hydrogen storage.Ministerio de Economía, Industria y Competitividad (Grant MAT2014-54378-R