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Polygranular nuclear graphite, manufactured at 2800–3000 °C from a carbonized filler and binder mix, has high graphitization degree, crystalline structure close to perfect graphite, and about 20% porosity. The pore surfaces expose large regions of rough, defective prismatic edges of graphite crystallites which are the locus of graphite materials surface sites active for oxidation, chemisorption, and electron transfer. However, we show that high-resolution N2 and Kr first monolayer adsorption on polygranular graphite (P/P0

Microstructural changes induced by neutron irradiation of superfine grain graphite G347A (Tokai Carbon, Japan) were examined by nitrogen adsorption at 77 K and by three microscopy techniques (SEM, TEM and FIB-SEM tomography). The specimens were irradiated at doses of up to 30 dpa, covering stages before and after the turnaround fluence at three temperatures (300, 450, 750 °C) of their irradiation envelope. The initial graphite densification at low fluences did not produce any detectable effect in the pore size range ( 50 nm) at high irradiation fluences and more structural changes on multiple scales, from nanometers to microns. This work demonstrates the unique ability of gas adsorption techniques to analyze open pores with sizes between sub-nanometer and sub-micron in bulk nuclear graphite, with supporting microscopy results.

We report results of vibrational neutron spectroscopy investigation aimed to identify the state of hydrogen adsorbed in ultramicroporous carbon. The mobility of hydrogen confined in carbon pores was probed as a function of temperature and pressure using inelastic neutron scattering, and the molecular translational and rotational motions were studied. At low loading rotation of H 2 molecules adsorbed in the smallest carbon pores (∼4–5 A) is severely hindered, suggesting that the interaction between H 2 and the host matrix is anisotropic. At higher loading, H 2 molecules behave as a nearly free rotor, implying lower anisotropic interactions with adsorption sites. At 77 K where bulk H 2 is a gas, deconvolution of elastic/quasielastic signal provide evidence of pressure-dependent fractions of immobile (solid-like) and partially mobile (liquid-like) hydrogen, which correlate with the excess adsorption isotherm at 77 K. Effective H 2 density in pores changes from solid-like to liquid-like with increasing pressure at 77 K. Surprisingly, immobile and partially mobile H 2 is present even at temperatures as high as ∼110 K where bulk hydrogen exists only in gas form.

Even when not functionalized intentionally, most carbon materials are not hydrophobic and readily adsorb water molecules from atmospheric water vapor. We have equilibrated an ultramicroporous carbon at several levels of relative humidity, thereby attaining various hydration levels. The water molecules were adsorbed on the pore walls (but did not fill completely the pore volume) and thus could be better described as hydration, or surface, rather than confined, water. We used quasielastic neutron scattering to perform a detailed investigation of the dependence of microscopic dynamics of these adsorbed water species on the hydration level and temperature. The behavior of hydration water in ultramicroporous carbon clearly demonstrates the same universal traits that characterize surface (hydration) water in other materials that are surface-hydrated. Thus, unless special treatment is intentionally applied to ultramicroporous carbon, the species filling its pores in various applications, ranging from hydrogen molecules to electrolytes, likely find themselves in contact with non-freezing water molecules characterized by rich microscopic dynamics.

Graphite serves as the neutron moderator of British Gas-Cooled Reactors and is a candidate material for the Generation IV of nuclear power stations. The neutron irradiation affects the crystalline structure of graphite; this damage results in volumetric changes of the bulk material and generation of porosity. Dimensional changes induced by irradiation in graphite bricks can make difficult the refueling operations and reduce the stability of the graphite core. Some of the neutron irradiation damage mechanisms in the crystal lattice of graphite are not well understood. Results of TEM, SEM, FIB-SEM tomography, gas adsorption and optical microscopy will be combined to help understand how the irradiation affects graphite at multiple length scales. Furthermore, some new evidence of porosity and microstructural changes generated by irradiation will be presented.

The high pressure adsorption behavior of CO2 at T = 296 K in microporous carbon was investigated by small-angle neutron scattering (SANS) technique. A strong densification of CO2 in micropores accompanied by non-monotonic adsorption-induced pore deformation was observed. The density of confined CO2 increases rapidly with pressure and reaches the liquid –like density at 20 bar, which corresponds to the relative pressure of P/Psat∼0.3. At P > 20 bar density of confined CO2 increases slowly approaching a plateau at higher pressure. The size of micropores first increases with pressure, reaches a maximum at 20 bar, and then decreases with pressure. A complementary SANS experiment conducted on the same microporous carbon saturated with neutron-transparent and non-adsorbing inert gas argon shows no deformation of micropores at pressures up to ∼200 bars. This result demonstrates that the observed deformation of micropores in CO2 is an adsorption-induced phenomenon, caused by the solvation pressure - induced strain and strong densification of confined CO2.

Small angle neutron scattering (SANS), scanning transmission electron microscopy (STEM) and gas adsorption, were applied to study the morphology and hydrogen adsorption properties of a wood-based ultramicroporous carbon (UMC) and a poly(furfuryl alcohol) derived carbon (PFAC). The polydispersed spherical model and the Guinier analysis of the scattering profiles were applied to obtain morphological parameters such as average pore size and pore size distribution of the two carbons; the results agreed reasonably well with independent gas sorption measurements and structural analysis by electron microscopy. The density of hydrogen physisorbed in these two carbons at room temperature and at moderate pressures was investigated by in situ SANS measurements. The experimental data, analyzed using a modified Kalliat model for decoupling scattering contributions from pores of different sizes, indicate that the molecular hydrogen acquires high densities preferentially in pores of subnanometer size at all measured pressures. These results support existing quantum mechanical and thermodynamical models that have predicted that the narrowest pores enhance the adsorption due to the overlapping of the potential fields from both wall sides in the slit-like pores. The structural information at a nanometer level gained via this work could guide the new development of porous-carbon based materials for hydrogen storage.

A series of gasification experiments, using two right cylinder specimens (� 12.7 � 25.4 mm and 25.4 � 25.4 mm) of PCEA nuclear graphite in ambient airflow, measured the total gasification flux at weight losses up to 41.5% and temperatures (893–1015 K) characteristics of those for in-pores gasification Mode (a) and in-pores diffusion-limited Mode (b). The chemical kinetics parameters for the gasification of PCEA graphite are determined using a multi-parameters optimization algorithm from the measurements of the total gasification rate and transient weight loss in experiments. These parameters are: (i) the pre-exponential rate coefficients and the Gaussian distributions and values of specific activation energies for adsorption of oxygen and desorption of CO gas; (ii) the specific activation energy and pre-exponential rate coefficient for the breakup of stable un-dissociated C(O2) oxygen radicals to form stable (CO) complexes; (iii) the specific activation energy and pre-exponential coefficient for desorption of CO2 gas and; (iv) the initial surface area of reactive free sites per unit mass. This area is consistently 13.5% higher than that for nuclear graphite grades of NBG-25 and IG-110 and decreases inversely proportional with the square root of the initial mass of the graphite specimens in the experiments. Experimental measurements successfully validate the chemical-reactions kinetics model that calculates continuous Arrhenius curves of the total gasification flux and the production rates of CO and CO2 gases. The model results at different total weight losses agree well with measurements and expand beyond the temperatures in the experiments to the diffusion-limited mode of gasification. Also calculated are the production rates of CO and CO2 gases and their relative contributions to the total gasification rate in the experiments as functions of temperature, for total weight losses of 5% and 10%. Published by Elsevier B.V.

The advantages of activated carbon fibers (ACF) over granular activated carbon (GAC) are reviewed and their relationship to ACF structure and texture are discussed. These advantages make ACF very attractive for gas storage applications. Both adsorbed natural gas (ANG) and hydrogen gas adsorption performance are discussed. The predicted and actual structure and performance of lignin-derived ACF are reviewed. The manufacture and performance of ACF derived monolith for potential automotive natural gas (NG) storage applications are reported. Future trends for ACF for gas storage are considered to be positive. The recent improvements in NG extraction coupled with the widespread availability of NG wells means a relatively inexpensive and abundant NG supply in the foreseeable future. This has rekindled interest in NG-powered vehicles. The advantages and benefit of ANG compared to compressed NG offer the promise of accelerated use of ANG as a commuter vehicle fuel. It is to be hoped the current cost hurdle of ACF can be overcome opening ANG applications that take advantage of the favorable properties of ACF versus GAC. Lastly, suggestions are made regarding the direction of future work.

The object of this CRADA project between Oak Ridge National Laboratory (ORNL) and United Technologies Research Center (UTRC) is the characterization of lignin-derived activated carbon fibers (LACF) and determination of their adsorption properties for volatile organic compounds (VOC). Carbon fibers from lignin raw materials were manufactured at Oak Ridge National Laboratory (ORNL) using the technology previously developed at ORNL. These fibers were physically activated at ORNL using various activation conditions, and their surface area and pore-size distribution were characterized by gas adsorption. Based on these properties, ORNL did down-select five differently activated LACF materials that were delivered to UTRC for measurement of VOC adsorption properties. UTRC used standard techniques based on breakthrough curves to measure and determine the adsorption properties of indoor air pollutants (IAP) - namely formaldehyde and carbon dioxide - and to verify the extent of saturated fiber regenerability by thermal treatments. The results are summarized as follows: (1) ORNL demonstrated that physical activation of lignin-derived carbon fibers can be tailored to obtain LACF with surface areas and pore size distributions matching the properties of activated carbon fibers obtained from more expensive, fossil-fuel precursors; (2) UTRC investigated the LACF potential for use in air cleaning applications currently pursuedmore » by UTRC, such as building ventilation, and demonstrated their regenerability for CO2 and formaldehyde, (3) Both partners agree that LACF have potential for possible use in air cleaning applications.« less

Potassium-doped activated carbon was prepared by mixing potassium salt with polyfurfuryl alcohol precursor followed by carbonization and activation. Several experimental techniques, such as thermogravimetric analysis, gas adsorption, X-ray diffraction and Raman scattering spectroscopy were employed to understand the effects of potassium on the texture and pore structures of the activated carbon, which ultimately affects the hydrogen adsorption properties. After doping with potassium, the activated carbon exhibits higher surface area, higher micropore volume, and enhanced hydrogen adsorption capacity. Understanding of how alkali metals affect surface area and micropore development in activated carbon may help to clarify the hydrogen adsorption mechanism and improve the design of suitable carbon-based hydrogen storage materials.

A scanning transmission electron microscopy investigation of two nanoporous carbon materials, wood-based ultramicroporous carbon and poly(furfuryl alcohol)-derived carbon, is reported. Atomic-resolution images demonstrate they comprise isotropic, three-dimensional networks of wrinkled one-atom-thick graphene sheets. In each graphene plane, nonhexagonal defects are frequently observed as connected five- and seven-atom rings. Atomic-level modeling shows that these topological defects induce localized rippling of graphene sheets, which interferes with their graphitic stacking and induces nanopores that lead to enhanced adsorption of H(2) molecules. The poly(furfuryl alcohol)-derived carbon contains larger regions of stacked layers, and shows significantly smaller surface area and pore volume than the ultramicroporous carbon.

We investigated the structure of two disordered carbons: activated carbon fibers (ACF) and ultramicroporous carbon (UMC). These carbons have highly porous structure with large surface areas and consequently low macroscopic density that should enhance adsorption of hydrogen. We used the atomic pair distribution function to probe the local atomic arrangements. The results show that the carbons maintain an in-plane local atomic structure similar to regular graphite, but the stacking of graphitic layers is strongly disordered. Although the local atomic density of these carbons is lower than graphite, it is only {approx}20% lower and is much higher than the macroscopic density due to the porosity of the structure. For this reason, the density of graphene sheets that have optimum separation for hydrogen adsorption is lower than anticipated.

Palladium-modified activated carbon fibers (Pd-ACF) were synthesized by melt-spinning, carbonization and activation of an isotropic pitch carbon precursor premixed with an organometallic Pd compound. The hydrogen uptake at 25 °C and 20 bar on Pd-ACF exceeded the expected capacity based solely on Pd hydride formation and hydrogen physisorption on the microporous carbon support. Aberration-corrected scanning transmission electron microscopy (STEM) with sub-Angstrom spatial resolution provided unambiguous identification of isolated Pd atoms occurring in the carbon matrix that coexist with larger Pd particles. First principles calculations revealed that each single Pd atom can form Kubas-type complexes by binding up to three H 2 molecules in the pressure range of adsorption measurements. Based on Pd atom concentration determined from STEM images, the contribution of various mechanisms to the excess hydrogen uptake measured experimentally was evaluated. With consideration of Kubas binding as a viable mechanism (along with hydride formation and physisorption to carbon support) the role of hydrogen spillover in this system may be smaller than previously thought.

The effect of mixing chemically-activated ultramicroporous carbon (UMC) with Pd nanopowder is investigated. Results show that Pd addition doubles the rate of hydrogen uptake, but does not enhance the hydrogen capacity or improve desorption kinetics. The effect of Pd on the rate of hydrogen adsorption supports the existence of the hydrogen spillover mechanism in the Pd – UMC system.

Hydrogen adsorption on ultramicroporous carbon was investigated at near-ambient temperatures using volumetric and gravimetric methods. The results showed that the main process, physisorption, is accompanied by a slow process of different nature, that causes slow uptake at high pressures and hysteresis on desorption. The combined result is unusually high levels of hydrogen uptake at near-ambient temperatures and pressures (e.g. up to 0.8 wt.% at 25 °C and 2 MPa). The heat of adsorption corresponding to the slow process leading to high uptake (17–20 kJ/mol) is higher than usually reported for carbon materials; the adsorption kinetics is slow, and the isotherms exhibit pronounced hysteresis. These unusual properties were attributed to contributions from polarization-enhanced physisorption induced by traces of alkali metals residual from chemical activation. The results support the hypothesis that polarization-induced physisorption in high surface area carbons modified with traces of alkali metal ions is an alternate route for increasing the hydrogen storage capacity of carbon adsorbents.

Palladium-modified activated carbon fibers (Pd-ACF) are being evaluated for adsorptive hydrogen storage at near-ambient conditions because of their enhanced hydrogen uptake in comparison to Pd-free ACF. The net uptake enhancement (at room temperature and 2 MPa) is in excess of the amount corresponding to formation of β-Pd hydride and is usually attributed to hydrogen spillover. In this paper, inelastic neutron scattering was used to investigate the state of hydrogen in Pd-containing activated carbon fibers loaded at 77 K with 2.5 wt % H2. It was found that new C−H bonds were formed, at the expense of physisorbed H2, during prolonged in situ exposure to 1.6 MPa hydrogen at 20 °C. This finding is a postfactum proof of the atomic nature of H species formed in presence of a Pd catalyst and of their subsequent spillover and binding to the carbon support. Chemisorption of hydrogen may explain the reduction in hydrogen uptake from first to second adsorption cycle.

We present a framework for rapidly predicting gas adsorption properties based on van der Waals density functional calculations and thermodynamic modeling. Utilizing this model and experimentally determined pore size distributions, we are able to accurately predict uptakes in five activated carbon materials without empirical potentials or lengthy simulations. Our results demonstrate that materials with smaller pores and higher heats of adsorption can still have poor adsorption characteristics due to relatively low densities of highly adsorbent pores.

Quasielastic neutron scattering of H(2) and D(2) in the same nanoporous carbon at 10-40 K demonstrates extreme quantum sieving, with D(2) diffusing up to 76 times faster. D(2) also shows liquidlike diffusion while H(2) exhibits Chudley-Elliott jump diffusion, evidence of their different relationships with the local lattice of adsorption sites due to quantum effects on intermolecular interactions. The onset of diffusion occurs at 22-25 K for H(2) and 10-13 K for D(2). At these temperatures, H(2) and D(2) have identical thermal de Broglie wavelengths that correlate with the dominant pore size.

We have doped poly(furfuryl alcohol)-derived activated carbon (PFAC) with two alkali metals, potassium (K) and lithium (Li), by previously reacting the metals with naphthalene in the presence of tetrahydrofuran (THF), followed by introducing them to pristine PFAC. The THF molecule causes a minor alteration of the microstructure of PFAC as confirmed by Raman spectra, X-ray diffraction, and pore textural analysis. Raman spectra and X-ray diffraction indicated a slight localized ordering toward the stacking defects of disordered carbon, as in PFAC, which can be attributed to the movement of THF molecules within the internal planes of graphene sheets. Pore textural analysis confirmed the lowering of the specific surface area and pore volume of both K- and Li-doped PFACs (BET SSA, 1378 m(2)/g (PFAC); 1252 m(2)/g (K-PFAC), 1081 m(2)/g (Li-PFAC)). Volumetric hydrogen adsorption measurements at temperatures of 298, 288, 273, and 77 K and pressures of up to 1 bar indicated the enhanced adsorption potential imposed by the presence of alkali metals, which can be reconfirmed by the elevated heats of adsorption of metal-doped PFACs (Li-PFAC, -(10-11) kJ/mol; K-PFAC, -(16-19) kJ/mol) compared to that of pristine PFAC (-9.6 kJ/mol).

We report on the use of in-situ small angle neutron scattering (SANS) technique to study the phase behavior of hydrogen confined in narrow pores of ultramicroporous carbon (UMC) with a very large surface area (2630 m2/g) and pore volume (1.3 cm3/g). The effect of pore size and pressure on hydrogen adsorbed on UMC at room temperature and pressures up to ∼200 bar were investigated. In a previous experiment, we have measured the density of adsorbed H2 gas in the nanopores and mesopores of polyfurfuryl alcohol-derived activated carbon (PFAC) by SANS technique. Here, a comparative SANS study between the UMC and PFAC was conducted in order to further investigate the densification of H2 as a function of pore size and pressure. Initial results suggest that the density of confined H2 in both UMC and PFAC is considerably higher than that of the bulk hydrogen gas. The density is systematically higher in the narrow pores and decreases with increasing pore size. These results clearly demonstrate the advantage of adsorptive storage over compressed gas storage and emphasize the greater efficiency of micropores over mesopores in the adsorption process, which can be used to guide the development of new carbon adsorbents tailored for maximum H2 storage capacities at near-ambient temperatures.

In this work, we present a model for analyzing activated carbon micropore structures based on graphene sheet walls of finite thickness and extent. This is a two-dimensional modification of the widely used infinite slit pore model that assumes graphite-like infinitely extended pore walls. The proposed model has two versions: (1) a strip pore constructed with graphene strip walls that have a finite length L in the x-direction and are infinite in the y-direction. Strip pores are open on both sides in the x-direction; (2) a channel pore, i.e. a strip pore partially closed along one edge by a perpendicularly orientated graphene wall. This more realistic model allows pore termination via both physical pore entrances and pore blockage. The model consequently introduces heterogeneity of the adsorption potential that is reduced near pore entrances and enhanced near the corners of pore walls. These energetically heterogeneous structures fill with adsorbate more gradually than homogeneous pores of the same width. As a result, the calculated adsorption isotherms are smoother and less steep for the finite versus the infinite pore model. In the application of this model for carbon characterization, it is necessary to make an assumption about the pore length. In this work, we made this assumption based on high-resolution scanning transmission electron microscopy (STEM) results. We find the agreement between the experiment and the model significantly better for the finite than for the infinite pore model.

Entrapping hydrogen molecules within the nanopores of solid adsorbents serves as a unique alternative for on-board storing of hydrogen for transportation purposes. The key advantage of the physisorption process for hydrogen storage is the higher density values achieved with the adsorbed gas, compared to that of the compressed phase, translating into higher storage capacities at lower pressures. The necessary condition for effective adsorption is the presence of narrow micropores of < 2 nm in width which provide the most suitable environment of hydrogen adsorption. Despite numerous theoretical calculations or indirect experimental estimations, there has not been a direct experimental measurement of the density of adsorbed hydrogen as a function of pressure and/or pore size. In the present study, we report on the use of in-situ small angle neutron scattering (SANS) to study the phase behavior of hydrogen confined in narrow micropores. We provide for the first time direct experimental measurements of the effect of pore size and pressure on hydrogen adsorbed on a polyfurfuryl alcohol-derived activated carbon (PFAC), at room temperature and pressures up to 207 bar. SANS studies were carried out at the General-Purpose Small-Angle Neutron Scattering spectrometer of the High Flux Isotope Reactor at Oak Ridge National Laboratory. The measurements covered the Q-range from 0.01 to 0.8 Å-1, covering the pores in the range of 9 to 34 Å of the PFAC material. Initial results suggest that the density of adsorbed hydrogen is higher than the density of bulk hydrogen gas and increases with decreasing pore size.

Proton adsorption isotherms were used to calculate the affinity distribution of proton binding sites for [gamma] alumina and F-modified alumina samples. The isotherms were obtained by potentiometric titration over as broad a pH interval as allowed by the samples being studied. The affinity distribution were calculated using the local solution of the adsorption integral equation. A smoothing spline procedure was employed, and a criterion for optimal smoothing was proposed. The method was tested by model calculations and verified on simple chemical compounds with known proton affinity characteristics. The apparent distribution spectra for oxides, with electrostatic effects neglected, showed well-defined peaks that were assigned to protonation/deprotonation processes of distinct -O(H) or -OH(H) groups in various surface configurations. A correlation was obtained between the evaluated log K values for proton association equilibria and values predicted by structural models. These results confirm that proton adsorption isotherms are sensitive to the heterogeneity existing at oxide surfaces. We find that ionic strength effects on apparent distribution were minor when compared with the effect of surface structure and chemical composition. 56 refs., 18 figs., 1 tab.

Potentiometric titration data for γ-Al2O3 have been converted to proton-binding curves and deconvoluted, which gave the pH-dependent number and strength of surface groups with different proton acceptor/donor properties. The deconvoluted isotherm was reconstructed based on the assumption of a 1-pK multisites description of the amphoteric γ-Al2O3 surface.We find that our picture of the oxide surface as consisting of structurally non-equivalent oxo and hydroxo groups allows for assignment of proton-binding processes to hydroxy groups with different acidic/basic properties, as determined independently from infrared spectra. Furthermore, we find that, based on models of the γ-Al2O3 surface consisting of individual low-index planes, the development of surface charge as a function of pH has completely different characteristics on different surface planes.Adsorption of [Pd(NH3)4]2+ cations was measured at fixed ionic strength and varying pH and initial concentration. Although the pH dependence of adsorbed amounts could be predicted on the basis of the 1-pK multisites description, the effects of concentration could not be described exactly. In conjunction with results from temperature-programmed reduction and UV–VIS spectroscopy, we propose the concept of geometrical constraints during adsorption–impregnation of precursor ions on the manifold of charged sites revealed by proton-transfer reactions.

A method for characterization of carbon surfaces' acidity using a continuous distribution of acidity constants is proposed. The method is based on potentiometric titration measurements. Titration curves are transformed into proton adsorption isotherms, and are analyzed to yield the distribution of acidity constants. Calculation of the distribution function is sensitive to experimental errors, and therefore a careful smoothing treatment must be applied to the experimental data. The method is tested by application to organic compounds and the calculated pK values are in excellent agreement with literature data. The method is then applied to study the evolution of acidic groups, in terms of their pK values, subsequent to modification processes such as oxidation and reduction of activated carbons. It is demonstrated that the method is sensitive to the changes in the number and character of surface acidic groups.

Efficient storage of hydrogen for use in fuel cell-powered vehicles is a challenge that is being addressed in different ways, including adsorptive, compressive, and liquid storage approaches. In this paper we report on adsorptive storage in nanoporous carbon fibers in which palladium is incorporated prior to spinning and carbonization/activation of the fibers. Nanoparticles of Pd, when dispersed in activated carbon fibers (ACF), enhance the hydrogen storage capacity of ACF. The adsorption capacity of Pd-ACF increases with increasing temperature below 0.4 bar, and the trend reverses when the pressure increases. To understand the cause for such behavior, hydrogen uptake properties of Pd with different degrees of Pd-carbon contact (Pd deposited on carbon surface and Pd embedded in carbon matrix) are compared with Pd-sponge using in situ XRD under various hydrogen partial pressures (Rietveld refinement and profile analysis of diffraction patterns does not show any significant changes in carbon structure even under 10 bar H2. Pd forms β PdH0.67 under 10 bar H2, which transforms to α PdH0.02 as the hydrogen partial pressure is decreased. However, the equilibrium pressure of transition (corresponding to a 1:1 ratio of α and β phases) increases with increasing the extent of Pd-carbon contact. This pressure is higher for Pd embedded in carbon than for Pd deposited on carbon surface. Both these Pd-carbon materials have higher H2 desorption pressure than pure Pd, indicating that carbon “pumps out” hydrogen from PdHx and the pumping power depends on the extent of Pd-carbon contact. These results support the spillover mechanism (dissociative adsorption of H2 followed by surface diffusion of atomic H).

Preparation, characterization, and transport properties of nanoparticles and porous solids: synthesis of a polysilazane coating on a silica gel via chemical surface coating comparing liquid and gas phase chlorosilylations - a composition and porosity study preparation of molecular sieves by pillaring of synthetic clays engineering of nanosize superparamagnetic particles for use in magnetic carrier technology acid-base behaviour of surfaces of porous materials electro-optical spectroscopy of colloidal systems NMR studies of colloidal oxides polymer surface dynamics using surface-modified glasses via dynamic contact angle measurements microporous structure of collagen fibres adsorption a onto oxides - the role of diffusion electrokinetic phenomena in porous media and around aggregates transport processes in microemulsions structural effects on diffusivity within aggregates of colloidal zirconia. Adsorption from vapour/gas phase onto nanoparticle and porous solids: characterization of energetically heterogeneous surfaces from experimental adsorption isotherms computer simulations of the structural and thermodynamic properties of adsorbed phases surface heterogeneity effects on adsorption equilibria and kinetics -rationalizations of the Elovich equation single and multicomponent adsorption equilibria of hydrocarbons on activated carbon - the role of microspore size distribution surface and structural properties of modified porous silicas surface chemistry of activated carbon materials - state of the art and implications of adsorption nanodimensional magnetic assembly of confined O2 heat of adsorption of pure gas and multicomponent gas mixtures on microporous adsorbents. Adsorption from the liquid phase onto nanoparticles and porous solids: charge regulation at the surface of a porous solid surface ionization and complexation the surface charge of alkali halides in their saturated solutions ionic adsorbates on hydrophobic surfaces adsorption of metal ions to humic acid hydrous metal oxides as adsorbents for aqueous heavy metals adsorption of ions on alumina protein adsorption onto latex particles adsorption of pharmaceutical organics on porous materials

Conventional approaches to understanding the gas adsorption capacity of nanoporous carbons have emphasized the relationship with the effective surface area, but more recent work has demonstrated the importance of local structures and pore-size-dependent adsorption. These developments provide new insights into local structures in nanoporous carbon and their effect on gas adsorption and uptake characteristics. Experiments and theory show that appropriately tuned pores can strongly enhance local adsorption, and that pore sizes can be used to tune adsorption characteristics. In the case of H2 adsorbed on nanostructured carbon, quasielastic and inelastic neutron scattering probes demonstrate novel quantum effects in the motion of adsorbed molecules.

The results of a combined study using diffuse reflectance spectra, temperature-programmed reduction, and extended X-ray absorption-edge fine structure of chlorine-containing precursors formed during preparation of Pd/Al 2 O 3 catalysts are reported. The catalyst dried (385 K) after impregnation contains both PdCl 4 2- species adsorbed electrostatically (about 60-70%) and strongly interacted PdCl x O y species. Calcination at 775 and 925 K results in decomposition of the initial impregnated species, formation of highly distorted PdCl x O y structures, and nucleation of disordered PdO clusters. Growth of large PdO particles occurs during calcination at 1075 K. The reduction of the oxide phase is more facile than that of chlorinated species in intimate interaction with alumina. The concept of geometrical constraints during adsorption of square planar PdCl 4 2- species on various configurations of positively charged hydroxyl groups on different crystal planes of alumina is discussed. It is proposed that electrostatic adsorption is favored on (100) and (110) planes, where the adsorbate matches the configuration of oppositely charged surface sites. The misfit between adsorbed species and surface hydroxyls on the (111) planes leads to ligand-substituted species.