The ferrous iron content of two vermiculitized biotites decreased by treatment with 0.1 N salts of copper at 70°C from 9.1–14% to 1.8–2.6%. Presumably, interlayer copper ions acted as a catalyst (here, an electron carrier) for the oxidation of iron by dissolved oxygen. The oxidized iron was ejected from the structure and formed crystalline iron minerals, such as hematite and goethite. Weight loss determinations, chemical, and X-ray powder diffraction data suggest that Cu(II) ions were polymerized to hydroxy-hydrous compounds in the interlayer space. Poor exchangeability of the resultant complex is attributed to the formation of strong electrostatic attractions between OH groups of the interlayer complexes and silicate oxygens.

The reaction of 2-methyl pent-2-ene with primary alcohols (C1-C18) at 95°C over an Al-montmorillonite gave yields of 20–90% of ethers of the type R-O-C(CH3)2C3H7. Lower yields were produced if secondary alcohols were employed, and tertiary alcohols gave only a trace of this ether. When a variety of alkenes was reacted with butan-1-ol at 95°C over a similar catalyst, no reaction occurred unless the alkene was capable of forming a tertiary carbonium ion immediately upon protonation. In this case the product was the tertiary ether t-R-O-nC4H9. However, at a reaction temperature of 150°C a variety of products were formed including (1) ether by the attack of butanol on the carbonium ions produced either directly from protonation of the alkenes or by hydride shift from such an ion, (2) alkenes by the attack of n-C4H9+ ions (derived from protonation and dehydration of butanol) on the alkene, (3) di-(but-1-yl) ether by dehydration of the butanol, and (4) small amounts of alcohol by hydration of the alkene. The differences in reactivity below and above 100°C are related directly to the amount of water present in the interlayer space of the clay and the degree of acidity found there. Although the clay behaves as an acid catalyst, the reactions are far cleaner (more selective) than comparable reactions catalyzed by sulfuric acid.

Jordanian natural kaolin and bentonite show good catalytic activity towards debutylating 2-tert-butylphenol, and varying debutylation vs. isomerization selectivity after acid activation. The resulting catalytic activity of these samples is dependent on the acid employed for activation; the samples treated with acetic acid showed relatively low conversions, whereas those treated with hydrochloric or phosphoric acid were found to be very active. Treatments with strong acids such as HCl have various effects on the activity of the samples depending on the concentration of the acid. For example, treatment with 1 M HCl gives the highest activity, whereas a treatment using 12 M HCl produced the lowest activity. The debutylation selectivity of the acid-activated samples is affected by the acid type and/or concentration. This selectivity ranges from 20 to 60%, whereas that of water-treated samples is between 46–82%.

Sulfonated carbon is a ‘green,’ solid-acid catalyst. For applications purposes, its surface area needs to be improved and its preparation needs to be made environmentally friendly. The objective of the present study was to provide a green and economical method of preparing a sulfonated carbon catalyst by using palygorskite (Plg) fiber as a support for sulfonated carbon. Sulfonated carbon/palygorskite solid-acid catalyst (SC-Plg) was synthesized via one-step carbonization-sulfonation by mixing palygorskite with sucrose as the carbon source and p-toluenesulfonic acid as the sulfonating agent. The catalyst was characterized by SEM, EDX, TEM, FTIR, and nitrogen adsorption-desorption isotherms. The results indicated that sucrose-derived carbon was loaded uniformly on the surface of Plg fibers and formed the SC-Plg catalyst. The inexpensive Plg fibers could replace sucrose-derived carbon and increase the surface area of the resulting catalyst. The SC-Plg shows significant catalytic performance and excellent stability when used in the esterification of oleic acid with methanol. The conversion of oleic acid reached 68.09%, even after five cycles. This work paves the way for the development of highly active, carbon-based, solid-acid composite catalysts using a natural Plg nanofiber template.

Glycerol is a byproduct of biodiesel synthesis by transesterification of triglycerides with short-chain alcohols in the presence of solid base catalysts. Because hydrotalcite is a potentially useful basic catalyst for the transesterification reaction, the interaction of glycerol with hydrotalcite is the focus of this work. Glycerol was intercalated into Mg-Al hydrotalcite with a Mg/Al molar ratio of 4 under elevated temperatures of 4432/503 K in the absence and presence of NaOH. The resulting materials were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, thermogravimetric analysis, and N2 adsorption. The amount of glycerol incorporated into hydrotalcite increased with increasing temperature of intercalation. However, the brucite-like sheets of hydrotalcite partially decomposed during the intercalation process at the highest temperature. The presence of NaOH stabilized the hydrotalcite layers against decomposition under high temperature (503 K). The intercalated materials exposed large surface areas ranging from 142 to 663 m2 g−1, depending on the preparation conditions. The glycerol-intercalated hydrotalcites were less catalytically active than hydrotalcite with OH− counterions for the transesterification of tributyrin with methanol. The lower reactivity of glycerol-intercalated hydrotalcite was probably the result of a strong interaction between the intercalated glycerolate (HOCH2-CHOH-CH2O−) and the partially decomposed brucite-like sheets.

De-tert-butylation of 2-tert-butylphenol was carried out over thermally-treated and acid-treated Jordanian bentonite clay samples. This reaction was found to follow first-order kinetics for all clay samples with different pretreatment procedures. The apparent rate constant, k, was also determined, and found to depend on the pretreatment. Thermal pretreatment at temperatures up to 250°C has an enhancing effect on surface acid sites. The total surface acidity (Ho <4.8) and the concentration of strong acid sites peaked at 250°C. Also, as a result, the maximum catalyst activity was obtained with samples treated at this temperature. Acid pretreatment with 0.10 M HCl, 1.0 M H2SO4 or 1.0 M H3PO4, followed by thermal treatment at 250°C produced the best enhancement effect on the surface acidity and catalytic activity.

Montmorillonite (Mnt)-based solid acids have a wide range of applications in catalysis and adsorption of pollutants. For such solid acids, the acidic characteristic often plays a significant role in these applications. The objective of the current study was to examine the effects of H3PO4-activation and supporting WO3 on the textural structure and surface acidic properties of Mnt. The Mnt-based solid acid materials were prepared by H3PO4 treatment and an impregnation method with a solution of ammonium metatungstate (AMT) and were examined as catalysts in the dehydration of glycerol to acrolein. The catalysts were characterized by nitrogen adsorption-desorption, powder X-ray diffraction (XRD), Fourier-transform infrared (FTIR) spectroscopy, scanning electronic microscopy (SEM), X-ray photoelectron spectroscopy (XPS), diffuse reflectance ultraviolet-visible (DR UV-Vis) spectroscopy, temperature programmed desorption of NH3 (NH3-TPD), diffuse reflectance Fourier-transform infrared (DR FTIR) spectroscopy of adsorbed pyridine, and thermogravimetric (TG) analyses. The phosphoric acid treatment of Mnt created Brönsted and Lewis acid sites and led to increases in specific surface areas, porosity, and acidity. WO3 species influenced total acidity, acid strength, the numbers of Brönsted and Lewis acid sites, and catalytic performances. A high turnover frequency (TOF) value (31.2 h−1) based on a maximal 60.7% yield of acrolein was reached. The correlation of acrolein yield with acidic properties indicated that the cooperative role of Brönsted and Lewis acid sites was beneficial to the formation of acrolein and a little coke deposition (<3.3 wt.%). This work provides a new idea for the design of solid acid catalysts with cooperative Brönsted and Lewis acidity for the dehydration of glycerol.

In this work, carbon nanotubes (CNTs)-templated binuclear metallophthalocyanines (MTAPcCF3)2C (M = Mn, Fe, Co, Ni, Cu, Zn) assemblies (MTAPcCF3)2C–COOH–CNTs are designed and obtained. Whereafter, the structure and morphology of target products are analyzed by many means such as infrared, X-ray diffraction, X-ray photoelectron spectroscopy, and scanning electron microscopy. The electrocatalytic performances of lithium-thionyl chloride battery catalyzed by (MTAPcCF3)2C–COOH–CNTs were carried out. The result shows that all catalysts can improve the battery performance including the discharge time and the initial voltage. The catalytic performance of (MTAPcCF3)2C–COOH–CNTs is ordered following the central metal: Mn > Fe > Ni > Co > Cu > Zn. The cell capacity catalyzed by optimal catalyst (MnTAPcCF3)2C–COOH–CNTs can expand to 28.08 mAˑh, with increase by 142.07%, and the (MnTAPcCF3)2C–COOH–CNTs can extend the discharge time to 551.6 s. Besides, the reaction mechanism is presented on the basis of cyclic voltammetry measurements.

Highly porous alumina-based oxides, γ-Al2O3, SiO2–Al2O3, and TiO2–Al2O3 were synthesized by a modified sol–gel method. Polivinylpyrrolidone was used as the pore expanding agent, whereas cetyltrimethylammonium bromide was used as the template in the presence of alkoxide inorganic precursors. Both as-synthesized and calcined solids were used as catalysts for esterification of glycerol with acetic acid (EG). The XRD and SEM-EDS measurements demonstrated that the Si-containing solids are amorphous while those containing Ti are semicrystalline with the latter composed of TiO2 rutile, TiO2 anatase, and γ-Al2O3 phases. All solids possessed ordered porous structures comprising of micro- and mesoporosity, with interconnectivity between these pores of different length scales. The high acidity of γ-Al2O3 and TiO2–Al2O3 materials resulted in good catalytic performances in the EG. Porosity of the solids plays a secondary role in determining the catalytic activity. Under the same conditions, the as-synthesized solids exhibited slightly lower catalytic performances compared to that of the calcined ones.

Catalytic activity of conducting polymers in biofuel cells has been studied in comparison with the performance of Pt-black (Pt-B). The cells were direct and passive type with structure of biofuel/anode catalyst/Nafion®/cathode catalyst/air. Conducting polymers of polyaniline, polypyrrole and poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT*PSS) were examined for the anode and cathode catalysts. L-ascorbic acid was used as the biofuel, and the Nafion® was served as a proton transfer membrane. In the standard Pt-B anode/Pt-B cathode cell, the typical Voc (open circuit voltage) = 0.52 V, ISC (short circuit current) = 8 mA/cm2 and the Pmax (maximum power density) of approximately 0.8 mW/cm2 were obtained. In a cell with catalysts of PEDOT*PSS anode/Pt-B cathode, Voc = 0.55 V and the maximum power density of 1.2 mW/cm2 were obtained, which were larger than that of the standard Pt-B/Pt-B cell. Polyaniline and Polypyrrole were also found to be a potential candidate for catalysts in biofuel cells.

Polystyrene spheres were found to be an effective assisted material in the growth of indium-tin-oxide (ITO) nanowire networks, bearing low temperature, high purity, and good control of size. The temperature and time of growth were studied to achieve ITO nanowire networks with high transmission and low resistivity. When prepared by PS spheres of 670 nm dia. for 15 min at 300 °C, the transmittance is above 90% after the wave length of 400 nm, and the sheet resistance is ∼200 Ω/□. Polystyrene-assisted ITO nanowires showed the high degree of crystallinity with lattice fringes, and well coincided cubic phase of In2O3. The density of ITO nanowire networks were controlled by polystyrene spheres and the residual polystyrene was removed by thermal annealing. ITO nanowire networks open new opportunities for optoelectronic devices needing special morphology for the improvement of light extraction efficiency, and as a new type of conductive film, which have an even broad application arena.

An eco-friendly, green aqueous technique for the preparation of NiO–Ag bimetallic and its individual monometallic nanoparticles (NPs) is succinctly described by utilizing nontoxic and abundantly available tannic acid at room temperature. The so-synthesized nanoscale particles were characterized using various techniques including HRTEM, DLS, zeta potential, SAED, SEM, EDAX, XRD, IR, and UV–vis spectroscopy. These monometallic and bimetallic NPs have a narrow size distribution with spherical morphology. Moreover, the average diameters of all these three different NPs are almost identical and ranges from 7 nm to 10 nm as measured from HRTEM. DLS readings further confirm that the so synthesized particles are in nano range. A comparative catalytic efficacy of the ensuing nanoparticulate materials were assayed employing photodegradation and chemical reduction of methyl violet (MV) at room temperature. NiO–Ag NPs exhibits higher catalytic potential and it took only 15 min to completely reduce MV in presence of NaBH4. The rate constants for both the chemical reduction and photodegradation reactions follow the order: kNiO–Ag bimetallic NPs > kNiO NPs > kAg NPs > kuncat. Higher catalytic performance of the bimetallic system is reckoned on composition effect which basically results due to synergistic electronic effect.

We propose an original methodology to integrate local measurement for nontrivial object shape. The method employs the distance transform of the object and least-square fitting of numerically computed weighting functions extracted from it. The method is exemplified in the field of chemical engineering by calculating the global metal concentration in catalyst grains from uneven metal distribution profiles. Applying the methodology on synthetic profiles with the help of a very simple deposition model allows us to evaluate the accuracy of the method. For high symmetry objects such as an infinite cylinder, relative errors on global concentration are lower than 1% for well-resolved profiles. For a less symmetrical object, a tetralobe, the best estimator gives a relative error below 5% at the cost of increased measurement time. Applicability on a real case is demonstrated on an aged hydrodemetallation catalyst. Sampling of catalyst grains at the inlet and outlet of the reactor allowed conclusions concerning different reactivity for the trapped metals.

Nanoporous carbon membranes (NCMs) were fabricated by the blends of resorcinol–formaldehyde (RF) resin and Pluronic F-127 through the processes of assembly, membrane-casting, solidification, and pyrolysis. The effect of the catalyst type (i.e., NaOH and Na2CO3) on the structure and property of precursors and their derived NCMs was investigated. The as-obtained precursors and NCMs were characterized by thermogravimetry, differential scanning calorimetry, x-ray diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy, elemental analysis, nitrogen adsorption, and gas permeation techniques. The results have shown that defect-free NCMs can be easily procured by the NaOH and Na2CO3 catalysts. In contrast, the precursor made from the Na2CO3 catalyst exhibits higher char yield than that from NaOH after pyrolysis. NaOH-based NCMs are beneficial for the separation of H2/N2 and CO2/N2 gas pairs. Na2CO3-based NCMs are more favorable for the separation of O2/N2 with an ideal selectivity of 6.29 and an O2 permeability of 3.27 Barrer.