High-Resolution N2 Adsorption Isotherms at 77.4 K: Critical Effect of the He Used During Calibration

Accurate characterization of the microporous structure in porous solids is of paramount importance for several applications such as energy and gas storage, nanoconfinement reactions, and so on. Among the different techniques for precise textural characterization, high-precision gas adsorption measurement of probe molecules at cryogenic temperatures (e.g., N2 at 77.4 K and Ar at 87.3 K) is the most widely used, after appropriate calibration of the sample holder with a probe gas, which does not experience physisorption processes. Although traditionally helium has been considered not to be adsorbed in porous solids at cryogenic temperatures, here we show that even at 77.4 K (high above its boiling temperature, 4 K) the use of He in the calibration step can give rise to erroneous interpretations when narrow micropores/constrictions are present.

Textural Characterization of Micro- and Mesoporous Carbons Using Combined Gas Adsorption and n-Nonane Preadsorption

Porous carbon and carbide materials with different structures were characterized using adsorption of nitrogen at 77.4 K before and after preadsorption of n-nonane. The selective blocking of the microporosity with n-nonane shows that ordered mesoporous silicon carbide material (OM-SiC) is almost exclusively mesoporous whereas the ordered mesoporous carbon CMK-3 contains a significant amount of micropores (25%). The insertion of micropores into OM-SiC using selective extraction of silicon by hot chlorine gas leads to the formation of ordered mesoporous carbide-derived carbon (OM-CDC) with a hierarchical pore structure and significantly higher micropore volume as compared to CMK-3, whereas a CDC material from a nonporous precursor is exclusively microporous. Volumes of narrow micropores, calculated by adsorption of carbon dioxide at 273 K, are in linear correlation with the volumes blocked by n-nonane. Argon adsorption measurements at 87.3 K allow for precise and reliable calculation of the pore size distribution of the materials using density functional theory (DFT) methods.

Evaluation of hectorites, synthesized in different conditions, as soot combustion catalysts after impregnation with copper

Two microporous hectorites were prepared by conventional and microwave heating, and a delaminated mesoporous hectorite by an ultrasound-assisted synthesis. These three hectorites were impregnated with copper. The characterization techniques used were XRD, N2 adsorption, TEM and H2 reduction after selective surface copper oxidation by N2O (to determine copper dispersion). The catalytic activity for soot combustion of the copper-free and the copper-containing hectorites was tested under a gas mixture of 500 ppm NOx/5% O2/N2 (and 5% O2/N2 in some cases), evaluating their stability through three consecutive soot combustion experiments. The delaminated hectorite showed the highest surface area (353 m2/g) allowing the highest dispersion of copper. This copper-containing catalyst was the most active for soot combustion among those prepared and tested in this study. We have also concluded that the Cu/hectorite-catalyzed soot combustion mechanism is based on the activation of the O2 molecule and not on the NO2-assisted soot combustion.

Isotopic study of ceria-catalyzed soot oxidation in the presence of NOx

The ceria-catalyzed soot oxidation mechanism has been studied by a pulse technique with labeled O2 in the absence and presence of NO, using ceria–soot mixtures prepared in the loose contact mode. In the absence of soot, the ceria-catalyzed oxidation of NO to NO2 takes place with ceria oxygen and not with gas-phase O2. However, the oxygen exchange process between gas-phase O2 and ceria oxygen (to yield back O2, but with oxygen atoms coming from ceria) prevailed with regard to the ceria-catalyzed oxidation of NO to NO2. Gas-phase O2 did not react directly with soot when pulsed to a soot–ceria loose contact mixture. Instead, ceria oxygen is transferred to soot (this step does not require gas-phase molecular oxygen to be present), and gas-phase O2 fills up the vacancies created on the oxide in a further step. The transfer of oxygen between ceria and soot occurred directly in the absence of NO. However, in the presence of NO, NO2 is expected to be additionally generated by ceria oxygen oxidation, which also reacts with soot. The main reaction products of the ceria-catalyzed soot oxidation reaction with NO/O2 were CO2 and NO. Additionally, evidence of the reduction of NOx to N2 was found.

Low metal content Co and Ni alumina supported catalysts for the CO2 reforming of methane

Low metal content Co and Ni alumina supported catalysts (4.0, 2.5 and 1.0 wt% nominal metal content) have been prepared, characterized (by ICP-OES, TEM, TPR-H2 and TPO) and tested for the CO2 reforming of methane. The objective is to optimize the metal loading in order to have a more efficient system. The selected reaction temperature is 973 K, although some tests at higher reaction temperature have been also performed. The results show that the amount of deposited carbon is noticeably lower than that obtained with the Co and Ni reference catalysts (9 wt%), but the CH4 and CO2 conversions are also lower. Among the catalysts tested, the Co(1) catalyst (the value in brackets corresponds to the nominal wt% loading) is deactivated during the first minutes of reaction because CoAl2O4 is formed, while Ni(1) and Co(2.5) catalysts show a high specific activity for methane conversion, a high stability and a very low carbon deposition.

Biodiesel production by acid catalysis with heteropolyacids supported on activated carbon fibers

Different catalysts, based on heteropolyacids supported on activated carbon fibers, have been prepared for palmitic acid esterification reaction. The influence of the catalyst (heteropolyacid) and the support on the catalytic activity have been analyzed. The results prove that an adequate combination of both is required to achieve the most suitable catalysts. Regarding to the heteropolyacid, phosphomolybdic acid seems to be the most suitable appropriate taking into account its lowest leaching. About the support, it must show an optimum microporosity, which must be wide enough to allow the entrance and exit of the reagents and products but not too wide in order to avoid the leaching of the catalyst. In addition, both decreasing of the catalytic activity and its recovery over several cycles have been analyzed.

Photocatalytic oxidation of propene in gas phase at low concentration by optimized TiO2 nanoparticles

In the present study, nanocrystalline titanium dioxide (TiO2) was prepared by sol–gel method at low temperature from titanium tetraisopropoxide (TTIP) and characterized by different techniques (gas adsorption, XRD, TEM and FTIR). Variables of the synthesis, such as the hydrolyzing agent (acetic acid or isopropanol) and calcination temperatures (300–800 °C), were analyzed to get uniform size TiO2 nanoparticles. The effect that these two variables have on the structure of the resultant TiO2 nanoparticles and on their photocatalytic activity is investigated. The photocatalytic activities of TiO2 nanoparticles were evaluated for propene oxidation at low concentration (100 ppmv) under two different kinds of UV light (UV-A ∼ 365 nm and UV-C ∼ 257.7 nm) and compared with Degussa TiO2 P-25, used as reference sample. The results show that both hydrolyzing agents allow to prepare TiO2 nanoparticles and that the hydrolyzing agent influences the crystalline structure and its change with the thermal treatments. Interestingly, the prepared TiO2 nanoparticles possess anatase phase with small crystalline size, high surface area and higher photocatalytic activity for propene oxidation than commercial TiO2 (Degussa P-25) under UV-light. Curiously, these prepared TiO2 nanoparticles are more active with the 365 nm source than with the 257.7 nm UV-light, which is a remarkable advantage from an application point of view. Additionally, the obtained results are particularly good when acetic acid is the hydrolyzing agent at both wavelengths used, possibly due to the high crystallinity, low anatase phase size and high surface oxygen groups’ content in the nanoparticles prepared with it, in comparison to those prepared using isopropanol.

Total oxidation of naphthalene using palladium nanoparticles supported on BETA, ZSM-5, SAPO-5 and alumina powders

A range of catalysts based on Pd nanoparticles supported on inorganic supports such as BETA and ZSM-5 zeolites, a silicoaluminophosphate molecular sieve (SAPO-5) and γ-alumina as a standard support have been tested for the total oxidation of naphthalene (100 ppm, total flow 50 ml/min) showing a conversion to carbon dioxide of 100% between 165 and 180 °C for all the analysed catalysts. From the combined use of zeolites with PVP polymer protected Pd based nanoparticles, enhanced properties have been found for the total abatement of naphthalene in contrast with other kinds of catalysts. A Pd/BETA catalyst has been demonstrated to have excellent activity, with a high degree of stability, as shown by time on line experiments maintaining 100% conversion to CO2 during the 48 h tested.

Spherical activated carbon as an enhanced support for TiO2/AC photocatalysts

Titanium dioxide nanoparticles prepared in situ by sol–gel method were supported on a spherical activated carbon to prepare TiO2/AC hybrid photocatalysts for the oxidation of gaseous organic compounds. Additionally, a granular activated carbon was studied for comparison purposes. In both types of TiO2/AC composites the effect of different variables (i.e., the thermal treatment conditions used during the preparation of these materials) and the UV-light wavelength used during photocatalytic oxidation were analyzed. The prepared materials were deeply characterized (by gas adsorption, TGA, XRD, SEM and photocatalytic propene oxidation). The obtained results show that the carbon support has an important effect on the properties of the deposited TiO2 and, therefore, on the photocatalytic activity of the resulting TiO2/AC composites. Thus, the hybrid materials prepared over the spherical activated carbon show better results than those prepared over the granular one; a good TiO2 coverage with a high crystallinity of the deposited titanium dioxide, which just needs an air oxidation treatment at low-moderate temperature (350–375 °C) to present high photoactivity, without the need of additional inert atmosphere treatments. Additionally, these materials are more active at 365 nm than at 257.7 nm UV radiation, opening the possibility of using solar light for this application.

Spherical carbons: Synthesis, characterization and activation processes

Spherical carbons have been prepared through hydrothermal treatment of three carbohydrates (glucose, saccharose and cellulose). Preparation variables such as treatment time, treatment temperature and concentration of carbohydrate have been analyzed to obtain spherical carbons. These spherical carbons can be prepared with particle sizes larger than 10 μm, especially from saccharose, and have subsequently been activated using different activation processes (H3PO4, NaOH, KOH or physical activation with CO2) to develop their textural properties. All these spherical carbons maintained their spherical morphology after the activation process, except when KOH/carbon ratios higher than 4/1 were used, which caused partial destruction of the spheres. The spherical activated carbons develop interesting textural properties with the four activating agents employed, reaching surface areas up to 3100 m2/g. Comparison of spherical activated carbons obtained with the different activating agents, taking into account the yields obtained after the activation process, shows that phosphoric acid activation produces spherical activated carbons with higher developed surface areas. Also, the spherical activated carbons present different oxygen groups’ content depending on the activating agent employed (higher surface oxygen groups content for chemical activation than for physical activation).

Abatement of hydrocarbons by acid ZSM-5 and BETA zeolites under cold-start conditions

Simulated cold-start tests have been carried out to evaluate the performance of H-ZSM-5 and H-BETA zeolites as hydrocarbon traps under simulated gasoline car exhaust gases, paying special attention to the effect of water on their behaviour. It is concluded that the hydrothermal treatment of the zeolites in the acidic form contributes to the better performance of these materials as hydrocarbon traps since the stabilization of the zeolites takes place. Moreover, the decrease of the surface acidity of the zeolites results in an increase of the Si/Al ratio, which contributes to the decrease of the water affinity for adsorption sites. Thus, the competition with hydrocarbon molecules in the exhaust for the adsorption sites is reduced which increases their trap efficiency. The stabilized H-ZSM-5 is the zeolite that showed the best performance with a propene offset temperature of 240 °C, which should be high enough for the three-way catalyst to carry out its role as catalytic converter.

Evidences of the Cerium Oxide-Catalysed DPF Regeneration in a Real Diesel Engine Exhaust

The active phase Ce0.5Pr0.5O2 has been loaded on commercial substrates (SiC DPF and cordierite honeycomb monolith) to perform DPF regeneration experiments in the exhaust of a diesel engine. Also, a powder sample has been prepared to carry out soot combustion experiments at laboratory. Experiments performed in the real diesel exhaust demonstrated the catalytic activity of the Ce–Pr mixed oxide for the combustion of soot, lowering the DPF regeneration temperature with regard to a counterpart catalyst-free DPF. The temperature for active regeneration of the Ce0.5Pr0.5O2-containing DPF when the soot content is low is in the range of 500–550 °C. When the Ce0.5Pr0.5O2-containing DPF is saturated with a high amount of soot, pressure drop and soot load at the filter reach equilibrium at around 360 °C under steady state engine operation due to passive regeneration. The uncoated DPF reached this equilibrium at around 440 °C. Comparing results at real exhaust with those at laboratory allow concluding that the Ce0.5Pr0.5O2-catalysed soot combustion in the real exhaust is not based on the NO2-assisted mechanism but is most likely occurring by the active oxygen-based mechanism.

Clay-supported graphene materials: application to hydrogen storage

The present work refers to clay–graphene nanomaterials prepared by a green way using caramel from sucrose and two types of natural clays (montmorillonite and sepiolite) as precursors, with the aim of evaluating their potential use in hydrogen storage. The impregnation of the clay substrates by caramel in aqueous media, followed by a thermal treatment in the absence of oxygen of these clay–caramel intermediates gives rise to graphene-like materials, which remain strongly bound to the silicate support. The nature of the resulting materials was characterized by different techniques such as XRD, Raman spectroscopy and TEM, as well as by adsorption isotherms of N2, CO2 and H2O. These carbon–clay nanocomposites can act as adsorbents for hydrogen storage, achieving, at 298 K and 20 MPa, over 0.1 wt% of hydrogen adsorption excess related to the total mass of the system, and a maximum value close to 0.4 wt% of hydrogen specifically related to the carbon mass. The very high isosteric heat for hydrogen sorption determined from adsorption isotherms at different temperatures (14.5 kJ mol−1) fits well with the theoretical values available for hydrogen storage on materials that show a strong stabilization of the H2 molecule upon adsorption.

Total oxidation of naphthalene at low temperatures using palladium nanoparticles supported on inorganic oxide-coated cordierite honeycomb monoliths

A study on the preparation of thin films of ZSM-5 and BETA zeolites, and a SAPO-5 silicoaluminophosphate, supported on cordierite honeycomb monoliths by in situ synthesis was carried out for their use as catalyst supports. Furthermore γ-Al2O3 was also coated onto a cordierite honeycomb monolith by a dip-coating method for use as a standard support. Structured monolithic catalysts were prepared by impregnation of the aforementioned coated monoliths with polymer-protected Pd nanoparticles. The monolithic catalysts have been tested for the total oxidation of naphthalene (100 ppm, GHSV 1220 h−1). From the combined use of the zeolite with polymer-protected nanoparticles, enhanced catalytic properties have been found for the total abatement of naphthalene. The Pd/MBETA and Pd/MZSM-5 catalytic monoliths have shown excellent activity with a high degree of stability, even after undergoing accelerated ageing experiments.

Modifying enzyme activity and selectivity by immobilization

Immobilization of enzymes may produce alterations in their observed activity, specificity or selectivity. Although in many cases an impoverishment of the enzyme properties is observed upon immobilization (caused by the distortion of the enzyme due to the interaction with the support) in some instances such properties may be enhanced by this immobilization. These alterations in enzyme properties are sometimes associated with changes in the enzyme structure. Occasionally, these variations will be positive. For example, they may be related to the stabilization of a hyperactivated form of the enzyme, like in the case of lipases immobilized on hydrophobic supports via interfacial activation. In some other instances, these improvements will be just a consequence of random modifications in the enzyme properties that in some reactions will be positive while in others may be negative. For this reason, the preparation of a library of biocatalysts as broad as possible may be a key turning point to find an immobilized biocatalyst with improved properties when compared to the free enzyme. Immobilized enzymes will be dispersed on the support surface and aggregation will no longer be possible, while the free enzyme may suffer aggregation, which greatly decreases enzyme activity. Moreover, enzyme rigidification may lead to preservation of the enzyme properties under drastic conditions in which the enzyme tends to become distorted thus decreasing its activity. Furthermore, immobilization of enzymes on a support, mainly on a porous support, may in many cases also have a positive impact on the observed enzyme behavior, not really related to structural changes. For example, the promotion of diffusional problems (e.g., pH gradients, substrate or product gradients), partition (towards or away from the enzyme environment, for substrate or products), or the blocking of some areas (e.g., reducing inhibitions) may greatly improve enzyme performance. Thus, in this tutorial review, we will try to list and explain some of the main reasons that may produce an improvement in enzyme activity, specificity or selectivity, either real or apparent, due to immobilization.