Synthesis of Nickel In Situ Modified SAPO-11 Molecular Sieves and Hydroisomerization Performance of Their NiWS Supported Catalysts

SAPO-11 molecular sieves were modified with different Ni contents by the in situ modification method. The Ni-modified SAPO-11 molecular sieves were used as the supports to prepare the corresponding NiW-supported catalysts for the hydroisomerization of n-hexadecane. The Ni-modified SAPO-11 and the corresponding NiW-supported catalysts were characterized by X-ray diffraction, scanning electron microscopy, N2 adsorption–desorption, NH3-temperature-programmed desorption, pyridine adsorbed infrared, high-resolution transmission electron microscopy, and X-ray photoelectron spectroscopy. The results showed that Ni in situ modification preserved the crystal structure of SAPO-11; increased the BET specific surface area, mesopore volume, and medium and strong Brønsted acid amount of SAPO-11; and increased the stacking number of the active phase of the catalysts. 3Ni-SAPO-11 possessed the largest BET specific surface area, mesopore volume, and medium and strong Brønsted acid amount. NiW/3Ni-SAPO-11 possessed the highest dispersion of the active phase and the highest sulfidation degree of the active metals. The results of the hydroisomerization of n-hexadecane showed that Ni in situ modification improved the catalytic activity and selectivity of the catalysts for the hydroisomerization of n-hexadecane to varying degrees. Especially, NiW/3Ni-SAPO-11 had the highest catalytic activity and isomer selectivity, and the maximum yield of isomeric hexadecane could reach 71.18%.

A Systematic Study on Bio-Based Hybrid Aerogels Made of Tannin and Silica

Tannin-silica hybrid materials are expected to feature excellent mechanic-chemical stability, large surface areas, high porosity and possess, after carbothermal reduction, high thermal stability as well as high thermal conductivity. Typically, a commercially available tetraethoxysilane is used, but in this study, a more sustainable route was developed by using a glycol-based silica precursor, tetrakis(2-hydroxyethyl)orthosilicate (EGMS), which is highly water-soluble. In order to produce highly porous, homogeneous hybrid tannin-silica aerogels in a one-pot approach, a suitable crosslinker has to be used. It was found that an aldehyde-functionalized silane (triethoxysilylbutyraldehyde) enables the covalent bonding of tannin and silica. Solely by altering the processing parameters, distinctly different tannin-silica hybrid material properties could be achieved. In particular, the amount of crosslinker is a significant factor with respect to altering the materials’ properties, e.g., the specific surface area. Notably, 5 wt% of crosslinker presents an optimal percentage to obtain a sustainable tannin-silica hybrid system with high specific surface areas of roughly 800–900 m2 g−1 as well as a high mesopore volume. The synthesized tannin-silica hybrid aerogels permit the usage as green precursor for silicon carbide materials.

A New Approach for Controlling Mesoporosity in Activated Carbon by the Consecutive Process of Air Oxidation, Thermal Destruction of Surface Functional Groups and Carbon Activation (the OTA Method)

A new and simple method, based entirely on a physical approach, was proposed to produce activated carbon from longan fruit seed with controlled mesoporosity. This method, referred to as the OTA, consisted of three consecutive steps of (1) air oxidation of initial microporous activated carbon of about 30% char burn-off to introduce oxygen surface functional groups, (2) the thermal destruction of the functional groups by heating the oxidized carbon in a nitrogen atmosphere at a high temperature to increase the surface reactivity due to increased surface defects by bond disruption, and (3) the final reactivation of the resulting carbon in carbon dioxide. The formation of mesopores was achieved through the enlargement of the original micropores after heat treatment via the CO2 gasification, and at the same time new micropores were also produced, resulting in a larger increase in the percentage of mesopore volume and the total specific surface area, in comparison with the production of activated carbon by the conventional two-step activation method using the same activation time and temperature. For the activation temperatures of 850 and 900 °C and the activation time of up to 240 min, it was found that the porous properties of activated carbon increased with the increase in activation time and temperature for both preparation methods. A maximum volume of mesopores of 0.474 cm3/g, which accounts for 44.1% of the total pore volume, and a maximum BET surface area of 1773 m2/g was achieved using three cycles of the OTA method at the activation temperature of 850 °C and 60 min activation time for each preparation cycle. The two-step activation method yielded activated carbon with a maximum mesopore volume of 0.270 cm3/g (33.0% of total pore volume) and surface area of 1499 m2/g when the activation temperature of 900 °C and a comparable activation time of 240 min were employed. Production of activated carbon by the OTA method is superior to the two-step activation method for better and more precise control of mesopore development.

Mesoporous Carbons from Polysaccharides and Their Use in Li-O2 Batteries

Previous studies have demonstrated that the mesoporosity of carbon material obtained by the Starbon® process from starch-formed by amylose and amylopectin can be tuned by controlling this ratio (the higher the amylose, the higher the mesoporosity). This study shows that starch type can also be an important parameter to control this mesoporosity. Carbons with controlled mesoporosity (Vmeso from 0.1–0.7 cm3/g) have been produced by the pre-mixing of different starches using an ionic liquid (IL) followed by a modified Starbon® process. The results show that the use of starch from corn and maize (commercially available Hylon VII with maize, respectively) is the better combination to increase the mesopore volume. Moreover, “low-cost” mesoporous carbons have been obtained by the direct carbonization of the pre-treated starch mixtures with the IL. In all cases, the IL can be recovered and reused, as demonstrated by its recycling up to three times. Furthermore, and as a comparison, chitosan has been also used as a precursor to obtain N-doped mesoporous carbons (5.5 wt% N) with moderate mesoporosity (Vmeso = 0.43 cm3/g). The different mesoporous carbons have been tested as cathode components in Li-O2 batteries and it is shown that a higher carbon mesoporosity, produced from starch precursor, or the N-doping, produced from chitosan precursor, increase the final battery cell performance (specific capacity and cycling).

Binary and Ternary 3D Nanobundles Metal Oxides Functionalized Carbon Xerogels as Electrocatalysts toward Oxygen Reduction Reaction

A series of carbon xerogels doped with cobalt, nickel, and iron have been prepared through the sol–gel method. The doped carbon xerogels were further functionalized with binary and ternary transition metal oxides containing Co, Ni, and Zn oxides by the hydrothermal method. A development in the mesopore volume is achieved for functionalized carbon xerogel doped with iron. However, in the functionalization of carbon xerogel with ternary metal oxides, a reduction in pore diameter and mesopore volume is found. In addition, all functionalized metal oxides/carbon are in the form of 3D nanobundles with different lengths and widths. The prepared samples have been tested as electrocatalysts for oxygen reduction reaction (ORR) in basic medium. All composites showed excellent oxygen reduction reaction activity; the low equivalent series resistance of the Zn–Ni–Co/Co–CX composite was especially remarkable, indicating high electronic conductivity. It has been established that the role of Zn in this type of metal oxides nanobundles-based ORR catalyst is not only positive, but its effect could be enhanced by the presence of Ni.

Self-standing zeolite foam monoliths with hierarchical micro–meso–macroporous structures

The zeolite monoliths were synthesized by a facile polymer scaffold template assisted hydrothermal method. The selected foam-shaped template of a polyurethane (PU) foam monolith, was used to prepare the self-standing zeolite foam (ZF) monolithic materials. The obtained ZF products can preserve the same size, shape and macroporous network structure of the original PU foam scaffold template, although the zeolite nano-crystallites had been fully substituted for the PU template to form the new skeleton struts and walls. The as-synthesized ZF products demonstrated abundant hierarchical porosity (involving triple micro-, meso- and macropores). Meanwhile, compared with the conventional zeolite powders, the self-standing ZF monolithic materials exhibited greater total pore volume and nearly three times higher mesopore volume, suggesting wider applications as catalysts, catalyst supports and adsorbents in industry.

The Dynamic Change of Pore Structure for the Low-Rank Coal with Various Pretreatment Temperatures: A Case Study from Southwestern Ordos Basin

The pore characteristics of the low-rank coal are different from medium- and high-rank coals. The low-temperature N2 adsorption (LP-N2A) measurements with a single low-rank coal were launched, and the dynamic change of pore structures under various pretreatment temperatures from 120°C to 300°C was studied. The isothermal curves of the DFS coal sample feature IV type, the hysteresis loops convert from H4 type to H2 type, and the hysteresis loops tend to be closed with the increased pretreatment temperatures. The mesopores are dominant in the DFS coal. The dynamic of pore volume (PV) and pore specific surface area (SSA) features the three-step-style change with the cut-off temperature points at 150°C and 240°C, and this has a relationship with the loss of the moisture and volatiles in the DFS coal sample. The pores with an aperture below 10 nm are the dominant mesopores in the DFS coal, and the mesopore volume features bimodal pattern distribution with a higher left peak of approximately 1.7 nm and a lower right peak of approximately 3-5 nm, and the right peak continuously right shift with the increase pretreatment temperatures. The total mesopore volume decreases with the upgrading temperatures, while the ratio of pores greater than 5 nm increases. Finally, the mesopore evolution model with the increased pretreatment temperatures was summarized.